5 Chapter 1
RELATION BETWEEN ACIDIC AND CATALYTIC PROPERTIES OF ZEOLITES J Dwyer and P J O'Malley
Chemistry Department, UMIST, Manchester M60 lQD, UK
ACIDITY DEFINITION AND MEASUREMENT The acidity of solids is usually interpreted in terms of proton donor
Bronsted acidity (ref.1) or as electron acceptor capacity - Lewis
acidity ( 2 ) .
Basic sites in solids can also be utilised in catalysis.
Bronsted Acidity and Acidity Functions (H 0' HR) In homogeneous systems (aqueous and non-aqueous) a quantitative measure of
protic acidity may be provided by an acidity parameter ( 3 ) . For a weak base 'B' the parameter H
is defined as follows.
B + H+
KBH+ = aB%+/aBH+
where ai is activity, fi activity coefficient and[
1' /[ 1
K + BH BH
log (aH+ f /f + ) B BH
In dilute solution (f /f + B BH
1) and H
+ and, since BH for a weak base the equilibrium in (1) is on the product side, pK + is a BH negative number (Ho< 1). Extensive protonation of B gives H < pK BH+* Some typical values of Ho for homogeneous solutions are given in Table 1.1 For equal concentrations o f free and protonated base H
6 Table 1.1
HAMMETT FUNCTIONS(a) -(Ho)
From ref 3
Typically (4,5) acids with -H with -H these
5 are classified as weak acids.
= 8.2-12.8 as strong acids and for superacids -Ho>
for classification of
arbitrary. Superacids were initially, and arbitrarily, taken as acids with H than that for 100% sulphuric acid (4).
Superacids are usually produced by
adding a stronger acid to an initially strong acid or more commonly by adding a strong
autoprotonation equilibrium ( 5 ) . 2HA
+ L ==?
H2Af + LA-
In such cases there is a substantial increase in acidity (decrease in H ) over that of pure HA.
1.1.2Hammett indicators and the H
For two bases B1 and B reacting with acid solutions having the same 2 strength (from eqn ( 2 ) )
and is constant at fixed temperature. Hammett (3) assumed that, when B1 and B2 are sufficiently similar in structure, the ratio of the activity coefficients in a given solution is constant so that the ratio of K values can be obtained from experimentally measured concentration ratios.
If the strongest base in the
series (B1) can be protonated in pure water, where f. Z 1, then KBH+ can be calculated from equn (2).
The base B1 and a weaker base B2 can then be
protonated in a stronger acid (eg dilute H SO ) where f. 1 but the ratio of 2 4 activity coefficients in equn ( 5 ) is unity. From measured values of and [BiHf], KB H+ can be calculated from KBiH+. 1
The weaker base B2 can be used to
H+ for a weaker base, B3, using a stronger acid solution.
way a range of Hammett indicators have been developed which facilitate the measurement of Ho in homogeneous systems using equation (3) which requires that [ B H ' ]
should be measurable.
The initial Hammett indicators were
substituted primary aromatic amines
R. N H ~+ H+
but others have been developed. The vi idity of Ho functions determine in this way depends upon the assumption that
different bases is constant in a given acid solution.
This assumption implies
that a plot of log [BH+]/[B]
-1.0) for the series of
vs Ho is linear (slope
Other acidity functions have since been developed based on other
indicators, for example alkyl carbinols (6) which dissociate as, ROH + H+
R+ + H20
and generate ( 7 ) the function H R
An extensive discussion of acidity scales is available (8).
a 1.1.3Lewis Acids Whereas Bronsted acid-base interactions involve a common proton-transfer process there is no corresponding common process to provide a unique basis for comparison of the strengths of Lewis acids. coordinating
Consequently the strength, or
experimentally, its strength depends on the particular Lewis base. preferential
classification (9) of donors and acceptors as type 'a' or 'b' and subsequently to the more general classification (10) into
development of the principle of hard and soft acids and bases (HSAB principle). The HSAB principle states that hard acids 'prefer' to bind to hard bases and soft acids 'prefer' soft bases.
In very general terms soft acid-soft base
interactions involve a significant covalent contribution whereas hard acid-hard base interactions involve less covalent and more electrostatic interactions. Consequently, in aqueous solution, A13+ (hard acid) will bind to F- (hard base) in preference to triphenyl phosphine (soft base) whereas Ag+ (soft acid) will preferentially bind to the phosphine. Theoretical approaches to HASB interactions have been made (11) which, although they are not completely satisfactory, do result in representation of the interaction energy in terms of an electrostatic and a covalent term.
values for the electrostatic term are associated with pronounced hard-hard interaction and large values for the covalent term are expected for strong soft-soft interactions.
A semi-quantitative approach to such interactions
utilizes the enthalpies (AH) of formation of
estimate parameters which may be used to estimate contributions to A H of mainly electrostatic (Ei) and mainly covalent (Ci) terms (12).
Attempts to quantify
complexation of Lewis acids and bases via the use of donor numbers (DN) and acceptor numbers (AN) have also been made (13). As with Bronsted acids, superacids of the Lewis type are known.
taken arbitrarily as those Lewis acids stronger than AlCl (5). The difficulty, 3 outlined above, in defining the strength of a Lewis acid means that a unique scale cannot be generated. SbF5, AsF
However, it is evident that some Lewis acids (eg
have a greater ability to ionize alkyl halides than, for instance
A1C13, and consequently are much more effective catalytically. Additionally, in spite of the above difficulties, a wide range of experimental investigations have resulted in an order of relative Lewis acidity for the MFn type acids (5).
1.1.4Solid Acids The proton donating ability of a solid, reflecting its ability to protonate a base 'B', can, by analogy with solutions, be expressed in the equilibrium, H+ + B
HB+ such that,
= -log (aH+fB/fBH+ ) = p
fB etc refer to concentrations and activity coefficients on the catalyst surface. However, lack of knowledge concerning activity coefficients where [B], for
thermodynamically. Moreover, for solid acids, there is generally a distribution of acid site strengths. Consequently, surface acidity requires specification of the relative numbers of acid sites with given strength. Because surfaces can be heterogeneous so that differing types of acid (or basic) site can coexist it is common, in spite of the difficulty in defining strengths of Lewis sites, to extend the approach above to include Lewis acid sites using the equilibrium AB
KAB = (aA[B]/[AB]
[ I is the concentration of a
where aA is the activity of the Lewis acid site, B
neutral base ' B ' which interacts with the Lewis site and AB is the concentration of the addition product.
Scales based on both Hammett type
typically involving amine or ketonic species, and aryl alcohol indicators (HR) are utilised.
The Hammett type indicators tend to interact with both Bronsted
and Lewis sites on the solid, whereas the arylcarbinol indicators tend to react only with Bronsted sites ROH + H+
R+ + H20
10 For solid acids the availability of sites to molecular probes, especially
large indicator molecules must always be considered.
Table 2 gives a typical
classification of solid acids (14).
CLASSIFICATION OF MAJOR SOLID ACIDS ( 1 4 )
Zeolites and related materials Metal oxides and sulphides (eg A1203, V203,
Mixed oxides (eg Si02/A1203, Si02/Ti0 ) 2 Natural clays and pillared interlayer clays Supported acids (eg H3P04 on Si02) Metal salts (eg A12S04, MgS04) Heteropoly acids Cation exchange resins (eg Amberlyst Series, Nafion) Treated graphites
It is also evident that the acid function of many solids can be enhanced, for example halogenation increases the acidity of many oxides.
In some cases
enhancement can be sufficient to generate superacidity. Solid superacids may also be generated by deposition or intercalation of appropriate species (15).
1.1.5Zeolites An important class of solid acid catalyst is based on zeolites.
introduction to zeolite structures is now given and the acid catalytic activity of these materials is then discussed in some detail. Zeolites are crystalline aluminosilicates. The unit cell contents may be represented simply as M (A102)x(Si02)y w.H20 x/n
11 where the material within the brackets refers to the composition of the framework and the material outside refers to the charge compensating cations
(M) with valence 'n' and the intercrystalline water.
Both A1 and Si are
tetrahedrally linked to oxygens and each tetrahedral unit shares each of its oxygens with another tetrahedral atom ('TI atom) so that each IT' atom is linked via oxygens to four others in a three dimensional framework structure. A
more comprehensive representation has recently been proposed (17).
usual to represent zeolite frameworks by line diagrams.
The intersection of
lines represents a 'T' atom and the line represents an oxygen bridge.
of the tetrahedral angles the oxygens may be above or below the plane of any ring of 'T' atoms.
Rings containing four, five, six, eight, ten and twelve
tetrahedra are known in zeolites.
Zeolites are microporous and have, when
dehydrated, considerable void volume which is accessed by "windows" or .rings of tetrahedra.
The size of window restricting entrance to the micropore
volume of some commercially interesting zeolites is given in Table 1.3 along with pore dimensionality and cavity size. zeolites are shown in Fig 1.1.
The structures of some of these
Zeolites A and X (or Y ) have large cavities,
entered by eight and twelve ring windows respectively, the linking of which generates a 3D pore system.
The smaller cavities associated with the sodalite
units (six-ring windows) are, generally, not of catalytic significance. In mordenite the elliptical twelve-ring windows provide access to the single pores on which there are small side "pockets" entered via elliptical eight rings.
Void volumes in the pentasils are made up from two sets of
interconnecting ten-ring pore systems.
Mordenite and the pentasils do not
possess a cavity system but at the pore intersection of the pentasils there is significantly increased space. A proportion of the intersections is slightly larger in ZSM-11 than in ZSM-5. The introduction of each aluminium into the framework introduces a negative charge which must be compensated by extra framework cations. manipulation of cation types and of the framework ratio Si/A1 (O
0.5) (18) allows for considerable variation in the acidic properties of
zeolites. The windows into zeolite crystals are of molecular dimensions (Table 1.3) and window size can be used in selective sorption (molecular sieving). Snrbates entering the crystals are subjected to considerable electric field gradients, associated with the charges on cations and framework, and may be extensively polarised. Heats of sorption, which can be large, depend upon the
MORDENITE hannb 6 l x 5 6 A )
13 structure of the sorbate, particularly polarisability and dipole/quadrupole moments, and upon the composition of the catalyst.
Since zeolites are
microporous they show type 1 isotherms thereby concentrating sorbates within the crystals relative to concentration in wider pore (amorphous) catalysts. Given that most of the reactive sites are present within the crystals, shape-selective catalysis can arise when there is preferential sorption of one reactant from a mixture (reactant selectivity), preferential diffusion and egress of one product in a product mixture (product selectivity) or selective discrimination, on the basis of size, against a particular intermediate to preclude a reaction path (transition-state selectivity). Excellent reviews on shape-selective catalysis are available (19)
WINDOWS AND PORE STRUCTURES OF ZEOLITES
Peripheral in absence of 0-atom
Free Dimensions/A Dimensionality Types of
of pore system Cavity
and size/A 4.1
Sodalite(6.6) 26 hedron(ll.4)
3.6 x 5.2
23 hedron (6.3 x 13)
5.4 x 5.6
5.4 x 5.6
5.1 x 5.5 Mordenite MOR
6.7 x 7.0
Linde X,Y FAU
sodalite(6.6) 26 hedron(ll.8)
MEASUREMENT OF ACIDITY IN SOLIDS The measurement of acidity is more difficult for solid acids than for
solutions. This is due, principally, to the heterogeneous nature of the acid sites in most solid acids and to the availability of non-acidic interactive sites for basic probe molecules. An additional problem arises, particularly in micropnrous materials, when
access of basic
restricted. Difficulties also exist in the definition of appropriate acidity functions (section 1.1). The methods commonly used to test the acidity of solids include the following.
Aqueous titration Non-aqueous titration and use of indicators Sorption/desorption energetics or rate processes
- Spectroscopic methods -
Catalytic rate measurements
1.2.1 Aqueous Methods
Typically, a suspension of the solid in aqueous solution is titrated with a base, for example NaOH, to a neutral end point.
Such methods are not generally
recommended (20) but can provide useful information particularly if combined with other techniques (21). 1.2.2
Non Aqueous Methods Hammett, and other indicators (eg aryl carbinols), are widely used in non
aqueous solution, usually benzene or iso-octane, to determine surface acidity. When the colour of a sorbed indicator (B) corresponds to that of its acid form then Ho for the solid is equal to or is lower than pKBH+ for the indicator (equations (3)and ( 6 ) ) . Consequently, a series of indicators having a range of pK values can be used to bracket the strength of surface acidity.
indicators and procedures are given in references (15) and ( 2 2 ) .
acidity can sometimes be related to the strength of a sulphuric acid solution which corresponds to the mid-point of each indicator transition (the pKBH+ value).
Typical values for surface acidity are given in Table 2.1 (15a).
15 Table 2.1
SURFACE A C I D I T Y OF SOME S O L I D S (15a)
5.6 - 8.2
H PO /silica qel 3 4
1.5 - 3.0
Relative numbers of
acid sites with
strength between given values,
determined by indicators, can be established by titration procedures using an amine in a non aqueous medium. titration.
Typically n-butylamine in benzene is used for
Successive amounts of amine are added to the pretreated catalyst;
the system is allowed to equilibrate and the indicator is then added.
amount of amine to discharge the acid colour of the indicator is representative of the number of surface acid sites with strength greater than pKBH+ for the indicator.
A distribution of acid site strengths for a particular solid can
then be established.
Such distributions are frequently expressed as fractions
of sites with acidity between given concentrations of sulphuric acid. In practice, problems arise in the use of indicators involving;
correct interpretation of colour changes; (ii) the establishment of equilibrium between base and solid; (iii) the interaction of base with non-acidic sites; (iv) the
interaction of non-aqueous solvents with
accessibility of acid sites to base and to indicator.
Where possible, colour
changes should be observed spectroscopically (23) and the size of indicator molecules is particularly important in microporous solids such as zeolites (24). Moreover the concentration of indicator should be sufficiently low so that the equilibrium between surface sites and amine molecules is undisturbed by the indicator. The problems directly related to the indicator can be eliminated by using calorimetric, titration with non aqueous solutions of organic bases (25). However, problems associated with accessibility of sites, establishment of equilibria and interaction of base with non-acid sites (eg cations) remain.
further problem concerning all indicator and titration procedures is that they usually involve measurement under conditions far removed from those typical of catalytic processing.
1.2.3 Sorption/Desorption Methods
The adsorption of appropriate basic molecules can be used to probe surface acidity.
Interaction enthalpies can be measured directly by calorimetry (26) or
In both cases enthalpies may be represented as a function of
surface coverage and hence provide an acid site distribution.
largest enthalpy changes occur at low surface coverage where the base adsorbed on the more active sites.
Problems associated with site accessibility
and establishment of equilibrium can arise and, as with indicator methods, it must be remembered that strong interaction between a base sorbate and a solid does not in all cases imply strong catalytic activity.
For example, the
isosteric enthalpy of sorption of ammonia is higher on A1203 than on Si02/A1203 but the former is unreactive in isomerisation of o-xylene whereas silica-alumina catalysts
incrementally over a range of surface coverage can be used to develop acidity spectra, discussed later in this section. Enthalpies of sorption under conditions closer
catalysis can be made chromatographically (29). Typically, the solid acid is made up into a chromatographic column and the corrected retention volume of suitable probe molecules is determined as a function of temperature and of pulse size.
By determining the sorption enthalpy of a weak base (eg benzene) at
different surface coverages of a strong and well-held base (eg pyridine) a spectrum of acidity may be generated. Currently, a technique based on the temperature programmed desorption (TPD) of basic molecules is widely used.
Typically a small fixed bed of the solid
acid is pretreated in dry carrier gas.
The acid sites are then saturated with a
volatile base, for example ammonia, at
temperature is thenraised at a selected rate.
As the temperature increases
ammonia is desorbed into the carrier gas stream which is continually monitored. In principle it is possible to estimate the amount of base desorbed up to any particular temperature.
The number o f peaks in the temperature profile can be
an indication of the number of types of acid site, providing resolution is adequate, and the higher the peak temperature the more strongly acid is the type
000501 K r l As l l 2 St M -1 5 5
TEMPERATURV'C TPD curves for B,Fe,Ga and Al forms of ZSM-5.
300 400 TEMPERATURU'C Relationship between TPD temperature max. and GO".
Fig.2.1. Isomorphous substitution of A V S i in HZSM-5. (Ref. 31).
3800 3400 @cm-1 Of Wdine dosed Imol'unit cel'l Fig.23.1.R hydroxyl stretching regkn for a).HY, b).NaHY-600, Fig. 22. Isomerisation of cy&Epane. Poisoning c). NaHY -45.6, and d)CeY. Rf.34b). -bygyridine.(UMIST),
Moreover, by making appropriate assumptions (30) it is possible to
determine activation energies associated with desorption processes. Some recent TPD results (31) for ammonia sorbed on pentasil (ZSM-5) type structures containing B, Fe, Ga, or A1 in the framework are shown in Fig 2.l(a) and acidity as reflected in peak maximum is compared with the stretching frequency of the acidic hydroxyl in Fig 2.l(b). Using TPD methods it is possible to compare catalysts reasonably quickly but it should be noted that results from TPD studies can vary somewhat with heating and carrier gas flow rates.
Moreover, difficulties can arise in
completely eliminating the effect of physisorbed species and it is important to know exactly what is being desorbed.
Measurement of pressure changes in static
TPD experiments or of physical changes in the carrier gas stream are unreliable and can result in spurious descriptions of desorption by
spectrometry eliminates most
Monitoring of these problems
different species including any decomposition products can be recognised.
with other sorption/desorption processes TPD does not define the types of acid site.
A modification of the sorption technique involves the use of sorbed bases in catalytic titration (32).
Incremental additions of a base are made to a
catalyst and the activity is measured following each additionuntil activity is effectively eliminated.
In this way the number of catalytically active sites,
under selected conditions, may be estimated.
shows typical results
.2.4 Spectroscopic Methods
The previous methods based on titration using indicators or calorimetry or on sorption give information about the interaction of bases with solid acids but provide no information on the chemical nature of the acid sites.
studies can provide this information. 22.214.171.124 Infrared Spectroscopy
The infrared technique is one of the most widely used to determine the surface acidity of solids.
The strength of Bronsted acidity, within a series of
similar solid acids, varies inversely with the stretching frequency of the acidic surface hydroxyl groups.
In simple terms this may be related to the
decrease in bond force constant with decrease in stretching frequency.
Bronsted and Lewis sites, in solids may be probed using sorbed bases. An excellent and comprehensive review of the use of infrared spectroscopy
19 in the study of acid sites in zeolites is available (33).
In what follows only
the principal features of the technique, together with
developments not covered in ref (33), are outlined. (a) Infrared Studies of Hydroxyl Groups on Solid Acids F o r amorphous silica only one OH stretching band, at approx 3740 cm-l, is
observed and it is assigned to the ESi-OH group terminating polymer chains. In addition to this terminal ;Si-OH
group, other bands are observed in zeolites
(and in silica-alumina), the number and frequency of vibration depending upon zeolite structure, pretreatment and composition. The types of hydroxyl found in zeolites are discussed subsequently (section 1.4) in detail.
It is sufficient,
here, to say that infrared studies result in the classification of zeolite framework hydroxyls as either bridging.
The bridging hydroxyls are in the vicinity of a framework aluminium
The location of framework hydroxyl groups within zeolite structures can also be investigated, using infrared spectroscopy. Evidence for location, in the small pore region of zeolite HY, of hydroxyls giving rise to the low-frequency band and evidence for location of the high-frequency hydroxyls in the supercage can be obtained in this way ( 3 3 ) .
Typical infrared spectra of the hydroxyl region
of HY and M/H-Y zeolites dehydrated at 4OOOC are shown in Fig 2.3. Overlapping peaks in the infrared spectra of the hydroxyl region make it difficult to distinguish between sites which differ slightly in resonance frequency.
Deconvolution techniques used to separate out both "low frequency"
(34a.3and, more recently, "high frequency" (35) components of bands in HY
zeolite, have been helpful in this regard.
Enhanced resolution increases the
capability of the infrared technique. Diffuse reflectance infrared spectroscopy (36) has recently been shown to provide additional information, compared with previous transmission work, om surface hydroxyls
in silica, silica-alumina
reflectance technique is particularly appropriate when the concentration of hydroxyls is low, as in the high-silica zeolites.
Moreover, extension into the
near-infrared permits the examination of overtones and combined bending and
stretching vibrations as well as fundamental transitions (36). (b) Infrared Studies of Sorbed Species The infrared spectrum of an adsorbed molecule, for example a base, is frequently modified by the nature and degree of its interaction with a surface site.
For example, the infrared spectrum of sorbed pyridine depends upon
whether the pyridine molecule is hydrogen bonded or is protonated by surface hydrogens or whether it is coordinated via nitrogen to a Lewis acid site (33). The infrared characteristics of pyridine in different adsorbed states are given in Table 2.2 and
typical IR spectra of pyridine sorbed on zeolites are given
in ref (33). The interaction of a weak base such as benzene with surface hydroxyls can result in broadening of the infrared hydroxyl band and a shift to lower
The measured "bathochromic" shift in frequency (AV ) OH is observed (38) to vary directly with the Bronsted acidity of zeolite hydroxyls absorption frequencies.
(see Fig 4.8, Section 1 . 4 ) .
The stretching frequency of molecular hydrogen
adsorbed at 77 K on solid acids also shows a dependence on the particular type of adsorption site (36).
The assignment of H2 stretching frequencies (Table
2.3) is of particular interest since it suggests that different types of Lewis
site may be distinguished.
However, in view of recent NMR studies (39) the
Lewis acid species may need reconsideration. In general the infrared technique can be used for quantitative studies of sorbed species, as well as for .identification, especially relative values.
However, a detailed knowledge of extinction coefficients is
not available and values cannot be assumed to be constant for a similar species sorbed on similar solid acids.
21 Table 2 . 2 ( 3 7 ) INFRARED SPECTRUM OF PYRIDINE
Sorbed s p e c i e s Pyridine
ADSORBED ON ALUMINOSILICA
( 3087 )
( a ) R e s u l t s Wavenumber/crnfh)
1.P i n d i c a t e -
p r o t o n a t e d p y r i d i n e and MP r e f e r s t o m o l e c u l a r l y adsorbed hydrogen bonding t o s u r f a c e h y d r o x y l s .
p y r i d i n e with
Table 2.3 CHARACTERISATION OF SOLID ACID SITES IN ZEOLITES USING H2 SORPTION AT 77 K
Infrared Frequency (
Extra framework aluminium hydroxy species
Bronsted Acidity due to bridging 0-H
Lewis Acidity (a) Trigonal Si
( b ) Trigonal A1
126.96.36.199 Nuclear Magnetic Resonance Spectroscopy
Recent developments including superconducting magnets, magic angle spinning (MAS) and improved computerisation have resulted in the application of nuclear magnetic resonance (NMR) spectroscopy to the study of solid acids (41). (a) The Quantity and acid strength of surface hydroxyls The total hydroxyl group concentration of a solid acid simply involves measuring the area under the proton magnetic resonance signal and relating this to a standard of known H'
content (eg adamantane).
Table 2.4 gives results for
NaY and HY where the expected decrease in concentration of hydroxyl groups with increasing pretreatment temperature is observed.
Table 2.4 (41) TOTAL NUMBER OF HYDROXYL GROUPS PER CAVITY FOR ZEOLITES NaY AND HY FOLLOWING HEAT TREATMENT BETWEEN 300'C
300) AND 700°C (90 HY
Number of hydroxyls
However, in order to distinguish between sites having differing acidity, which show different chemical shift values, it is necessary to use narrowing
contributions to the H '
resonance signal, is particularly effective in this
respect and leads to the desired resolution.
The enhanced resolution allows
recognition of sites of differing acidity in zeolites which are separated by only a few ppm (Fig 2.4). Based on the premise that, as the acid strength of a hydroxyl increases, the chemical shift 6
of the H '
proton magnetic resonance increases, the bands
(a) (b),(c) and (d) in Fig 2.4 have been assigned to terminal hydroxyls (associated with amorphous material and defect sites in zeolites) (a), to bridging hydroxyls (b) and (c) and to hydrogens in NH4+ ions (d). Consequently, NMR
spectroscopy but allows for a more accurate quantification of the numbers of hydrogens giving rise to a particular signal.
7 45 2 hPPm Fig.2-4. Effect of MASNMR on the hydrogen band envelope. (Ref.41b).
-5 ?Ym 5 3660z
%2! 4.0 .u c
25 (b) Adsorption characteristics of basic probe molecules As
with infrared spectroscopy, suitable sorbate molecules may be used to
probe surface acidity.
The terminal hydroxyls giving rise to band (a) in Fig
2.4, which are present in silica and silica-alumina, as well as in zeolites, are
shifted by 6-8 ppm on adsorption nf pyridine.
This shift arises from hydrogen
bonding between the surface ZSi-OH group and the sorbed pyridine molecule. Interaction of pyridine with the bridging hydroxyls (giving bands (b) and (c) in Fig 2.4) results in severe line broadening of the resonance, corresponding to formation of the pyridinium ion. Chemical shifts in the I5N resonance are also used (39) to probe Lewis adsorption sites and some recent results are given in Table 2.5.
Table 2.5 MASNMR CHEMICAL SHIFTS VERSUS LIQUID F'YRIDINE
IN THE 15N MASNMR SPECTRA OF
PYRIDINE SORBED ON ZEOLITES (39)
Observed Chemical Shift/ppm
-26 2 1
-50 to -80
188.8.131.52 Other Spectroscopic methods Electron spin resonance (esr) has been used, particularly to examine Lewis acidity (40). An early explanation for superacidity in zeolites was also based
on esr results (41) but confirmation for the species proposed is lacking.
recently (42) external and internal pore sites have been probed using esr signals associated with specific radicals formed by interaction of sorbates and surface sites.
spectroscopy provides a means to probe charge
transfer complexes formed between appropriate sorbate molecules and surface
The OIs binding energy of metal oxides, determined by XPS, is a l s o
proposed as a measure of the basic strength of oxides, and XPS studies of sorbed nyridine(NIS) can be used to recognise Bronsted and Lewis acid sites (42).
1.2.5 Sites for Acid Catalysis in Zeolites
Catalytic sites in zeolites may
involve separate phases as discussed
subsequently. In the absence of other phases zeolites can act as both basic and acidic catalysts and free radical processes also occur in zeolites.
acidic catalysis is the most widely studied aspect of zeolite catalysts. The hydroxyls within the channels provide the Bronsted sites which are usually generated from the ammonium exchanged zeolites by calcination. Na(Z) + NH +(as)4
NH4(Z) + Na+(aq)
Hydrogen forms of zeolites (HZ) may also be made by direct exchange of Na+ for H+ using mineral acids, providing the structure is stable in acid, but some
dealumination is to be expected especially at surfaces (47). Brnnsted sites are also generated by hydrolytic processes involving water coordinated to polyvalent counter ions
and by appropriate reduction (18). In true hydrogen forms of zeolites these hydroxyls may be regarded as protonic bridges bound to negatively charged framework oxygens associated with AIOq-
tetrahedra. A t higher temperatures (T>200
mobile moving between sites and at T>550
O C )
Bronsted hydrogens can be
they may be lost by dehydroxylation
which is accompanied by an increase in Lewis acidity.
(AtW 0 0 0 0 \si/ \i/ \si/ h h h h
A first stage in dehydroxylation was assumed to result in a vacancy with tricoordinated framework A1 and Si+ species (48a). However, direct evidence for these tricoordinated framework atoms is not available and, in view of the fact that dehydroxylation appears to occur with dislodgement of aluminium from the framework, the current view is that dislodged aluminium species provide the source of Lewis acidity, a point made initially on the basis of x-ray fluorescence results (48b) and subsequently supported by infrared results (48c).
However, the situation is more complicated than is implied by
above. Additionally, there is some evidence for the existence of a small number of very strong acid sites (superacids). Early investigations using epr (44) lead to the suggestion that superacid sites arise from inductive effects on Bronsted sites generated by neighbouring Lewis sites.
Superacid O\ Site
,O\ Si h
A1 I Si h i h
However, doubt about the existence of
has lead to
suggestions that superacidity arises (49) from synergism between dislodged aluminium species and framework hydroxyls.
. . (A103p
The above classification is somewhat simplistic particularly with regard to the acid sites associated with extraframework aluminium species and with defects. Further discussion is reserved to later sections.
1.2.6 Zeolite Acidity - Relationship to Composition and Structure 184.108.40.206 General Considerations
The acid strength of zeolites can be measured using the techniques outlined earlier.
Infrared studies, using self-supporting discs reveal at least two
types of surface hydroxyl in the hydrogen f o r m s of zeolites. A band around 3740 -1 cm , which is also observed in silica and silicates, is assigned to terminal hydroxyls located at the outer surfaces of crystals or at defects where the framework is interrupted or when non-lattice hydrated silicieous material is present.
Defect sites where missing tetrahedra are replaced by hydroxyl nests
are particularly evident in silica-rich pentasils ( 5 0 ) and in some dealuminated zeolites ( 5 1 ) .
Bands in the region 3710-3740 cm-l have been assigned to defect
hydroxyls vibrating freely and a broad band centred around 3,400 cm-' is assigned to hydrogen bonded internal silanols ( 5 2 ) .
Hydroxyl stretches in
the region 3600 to 3650 cm-l, depending on zeolite composition are assigned to the bridged structures
show lower vibration frequencies when they are located in smaller pores ( 6 or 8 rings) presumably due to electrostatic perturbation ( 5 3 ) .
For example in
zeolite Y the bridged hydroxyl located in the small cages gives
and that in the large cages, which XRD ( 5 4 ) and neutron diffraction ( 5 5 ) locate
mainly on O1 oxygens, vibrates with
Bronsted acidity in
zeolites is largely associated with accessible bridging hydroxyls although some The lower
defect hydroxyls show weak acidity as revealed by ion exchange ( 5 6 ) .
vibrational frequencies of bridged hydroxyls reflects their weaker 0-H bonds and stronger acidity.
Typical infrared spectra of the hydroxyl region of zeolite Y
are shown in Fig 2.3.
The decrease in
increase in silicon content of the increased acidity as Si/Al increases.
the bridged hydroxyl with
(Fig 2 . 5 )
Results correlate well with chemical
shifts for lH MASNMR which also reflect acidity (Fig 2 . 5 ) .
strictly involves interaction with a base this point is more evident in the bathochromic shifts arising from interaction of bridged hydroxyls with the weak base benzene
(Fig 4.8, Section
intermediate electronegativity increases, reflect increased interaction between
29 zeolitic hydroxyls and benzene resulting from weakening of 0-H bonds and stronger zeolite acidity. Patterns in Figs 2.4 and 4.8 are consistent; acidity of bridged hydroxyls tends to increase with increase in Si/Al.
have been made to explain this observation and these are more fully discussed in Sectionl.4. At this point it iS convenient to recall that the effective acidity of Bronsted sites in faujasitic zeolites can be interpreted simplistically in terms of the proximity of aluminium atoms within the framework. Accepting this point a simple localised model (57) for H-forms of zeolites is,
(TjO)3Si / \ A1(OSi)3 where T. = T1, T2, T may be, according to Lowensteins rule, either A1 or Si. 3 J This model predicts four types of bridged hydroxyl involving 1, 2, or 3 second neighbour aluminiums, the number of each type depending upon Si/Al.
(35a), hydroxyl stretch assignments have been made to at least four types of supercage hydroxyls in zeolite H-Y by numerical deconvolution of the high frequency bridged hydroxyl band (Fig 2.6a) and similar results are obtained by deconvolution (35b) using resolution enchancement (Fig 2.6b).
A consequence of this simple localised model is that, for an ordered three dimensional framework structure, there is only one kind of hydroxyl unit at Si/A1 2 7 .
Consequently the properties of zeolitic Bronsted sites should become
independent of composition at higher values of Si/Al.
It is of course important
to consider the distribution of A1 as well as the ratio Si/A1 but the notion that the acidic properties of H-forms of zeolites reach a limiting value as Si/A1 increases, although controversial theoretically as discussed subsequently, is supported by much experimental evidence (58).
results support this view (41a).
Recent infrared and H'
Although the effect is exaggerated in Fig 2.5,
and similar plots where Si/A1 is used as the variable, it seems that a limiting and is reached when S i / A l Z 10. value for H Structural differences between zeolites having the same framework
composition may also affect acidity. Preferential siting of A1 atoms may differ between structures so that A1-A1 distances are not the same at a given Si/AI. Additionally the hydroxyl stretch for bridged hydroxyls depends upon the bond angle /SiOAl which can vary within and between structures. Consequently the is not likely to be limiting ratio Si/A1 for zeolite properties, including
y 0.80 z a
3520 WAVENUMBER /cm-l
Fig.26. Infrared spectra of hydroxyl region of H-Y zeolite. (a1Numerical deconvolut ion. (Ref.35a). (b1Deconvolution by signal enhancement. (Ref. UMISTI.
Fig.2.7. TPDA from NHI, mordenite degassed at 2OoC; heating rate 4°C/min.(ref.UMIST).
the same for all framework structures. Both Bronsted and Lewis sites in zeolites have been probed by infrared studies (33) of sorbed bases. 1450 cm-'
Pyridine is widely used, and bands at 1540 and
which are assigned to pyridinium ions and coordinatively bound
pyridine respectively (Table 2.2) are used to monitor Bronsted and Lewis sites. It is reported (59) that, over a range of composition (Si/Al), only Bronsted sites are present in carefully prepared H-ZSM-5.
However, preparation of
silica-rich faujasites by chemical or hydrothermal methods can result in the presence of non-framework ions or dislodged aluminium species which could act as centres of Lewis acidity.
Sorbed bases are also used in conjunction with I5N
NMR to examine Bronsted and Lewis sites in zeolites.
The number of pyridinium
ions per cavity can be determined using I5N NMR of sorbed pyridine (41b) and measurements using acetonitrile show that the electron acceptor strength of hydrothermally treated Y zeolite increases with temperature of activation and water pressure (ie severity of the hydrothermal process)(4lb). In general the dependence of acidity on framework composition of zeolites as revealed by spectroscopic investigations (eg IR and H ' sorption/desorption studies using basic sorbates.
NMR) is supported by
The temperature programmed
desorption of ammonia TPDA is widely used in work on zeolites.
preferred because of its stability during TPD and because of its size.
bases can be used in TPD but difficulties associated with decomposition during heating and with accessibility can arise (60). Even with ammonia it is important to use a detector which detects ammonia rather than changes in pressure, thermal conductivity or weight loss etc.
Fig 2.7 shows a TPDA profile for hydrated
Mass 16 gives NH3 in the presence of H 0. Reports based on 4 2 indirect methods sometimes wrongly assign the high temperature dehydroxylation
peak to very strong acid sites (61). When the zeolite (NH4- or H-
form) is first outgassed at
temperatures and then cooled to sorb NH3 prior to the TPDA temperature
run, a NH3
This low temperature peak is minimised by sorbing
ammonia at elevated temperatures, usually around 1 0 0 O C . forms of faujasites the sorption of ammonia at T >lOO°C
However, in cation
can lead to trapping of
NH3 in small cages which is then desorbed at higher temperatures along with ammonia from acid sites. The broad, frequently asymmetric peaks, associated with chemisorbed ammonia are not readily deconvoluted
as to provide clear evidence for different types
of Bronsted site in zeolites (62).
However, one report (63) presents results
32 for zeolite Y which give good agreement between the acid site distribution
determined from TPDA and that predicted by calculation based on a random siting of Al, subject to Lowenstein's rule (Fig 2.8). The pattern observed is broadly consistent with that obtained by deconvolution of the infrared spectra ( 3 5 ) discussed earlier.
The distribution of A1 in faujasitic frameworks is discussed
in Section 1.4. Considerable effort has been put into TPDA studies of ( N H /H)-ZSM-5. 4
Differences in reported TPDA profiles presumably
experimental technique and in sample composition or quality. A high temperature peak
400 OC) is assigned to ammonia chemisorbed on acid
Bronsted sites in ZSM-5, and lower temperature peaks to ammonia sorbed on weakly acid internal silanols (64) or on cations or, at T < 15OoC, to specifically" sorbed ammonia (65).
Measurements on NH -2SM-5 4
rather than on
HZSM-5 on which ammonia has subsequently been adsorbed show clear evidence for
only one TPDA peak at approx.400
TPDA peaks associated with NH3 chemisorbed on acidic sites span a wide temperature range indicating an acidity spectrum, in agreement with measures of acidity using microcalorimetry ( 6 7 ) , conventional sorption ( 2 7 ) and titration procedures (68). Additionally, activation energies calculated from TPDA results on ZSM-5
agree well with
TPDA has been used to demonstrate the effect of framework Si/Al on
the acidity spectrum ( 6 9 ) .
It should be emphasised, however, that TPD studies
although useful in characterisation of zeolite acidity do not differentiate Bronsted and Lewis acidity.
A combination of TPDA and infrared, for example,
can resolve this point. Energy changes associated with the interaction of bases with zeolite surfaces may be estimated from calorimetric measurements of differential heats of adsorption (q) as a function of surface coverage (70). On the acid form of mordenite (H-M)
and on H-M
dealuminated with H C 1 very strong Lewis sites ( q =
170 kJ mol-I), on which ammonia is sorbed dissociatively, and weaker Lewis sites (q = 100 kJ mol-l) where ammonia is undissociated are observed.
sites are assigned to q values of 120 2 5, 130 2 5, 140 2 5 and 150 2 5 kJ mol-l.
The strongest Bronsted sites (q
5 kJ m o 1 - l )
are found on acid
leached mordenite (Si/A1 = 10 and 27.5) or on synthetic mordenite (Si/Al
Since only the acid leached samples have the strongest Lewis sites and the synthetic materials had no strong Lewis sites it appears that the strongest Bronsted sites observed donotrequirethe presence of strong Lewis sites,
The above discussion covers some spectroscopic and TPDA results in relation to framework Si/Al.
It should be clear that the dependence of acidity on
framework Si/A1 is not always straightforward even within a given structural type.
For example, in the mordenite and ZSM-5 frameworks there is evidence of
preferential siting of A1 which might be expected to influence acidity so that acidity per site could change as Si/A1 is reduced even though Si/Al
Moreover, dislodgement of aluminium should be avoided during any pretreatment prior to acidity measurement since the loss of framework aluminium can result in a reduced number of acid sites and changes in acidity (49). It is abundantly clear, therefore, that the acidity spectrum in zeolites is related to framework composition.
The distribution of aluminium within the
framework and the presence of other species, ions, dislodged aluminiums etc.can also influence acidity.
Consequently it is necessary to discuss some of these
more common modifications.
220.127.116.11 Modification of Zeolite Catalysts
Typical modifications to zeolite catalysts include ion-exchange; thermal/ hydrothermal treatment; dealumination by extraction of aluminium with acids or complexing agents; modification by secondary synthesis in which framework 'T' atoms are replaced by other 'T' atoms (isomorphnus substitution); incorporation of additional phases, usually metals, metal oxides or salts.
In what follows
consideration will be given only to modifications which affect acidity. include
synthesis; incorporation of oxides or halides.
(a) Modification by Ion Exchange In well-crystalline zeolites containing no other phases the effect of counter ions on Bronsted acidity is well established.
Ion exchange of Na+ for
polyvalent ions results in generation of Bronsted sites by a hydrolytic process, for example
M+(OH) + H+
The H+ neutralising a framework A104- tecrahedra constitutes the Bronsted site. Acidity is enhanoed by cation polarisation, proportional to e/r for the cation ( 3 3 ) , and by increases in the framework ratio Si/A1.
e . u
Fig.2.8.Schematic TPDA profile of NHLY zeolite (!iOAl/UC) and estimated numbers of types of Al atom (Nil.(ref.63).
(060 .dnlatliu N spckr
416 L blZS N# L acid-OH
Fig-210-Diffuse ref'ectance I study of thermally modified HZSM-5. (Ref. 36).
Fig.Z.PLa).n-kxane cra&ii Over tiUfl-5 steamed at W fa 2.5hwrs.lRef.771. o----oFOmin on stream. n-----oZC-Omin. on stream. 0 parent zeolite. *-----raM d dislodged Al to framewrk kl. parent zedik.
1 2 3 L A H W T ff 16HASS PEAU AT 4COY larb unihl
Fig29(b).Rate of n-kxaw cracking (at 28SoC1 Over steamed H-ZSM-5 (steam treatment at 600°C for 25hoursl. (Ref.771.
35 For the alkali metal ions acidity increases in the order Cs-Li
higher for Y than X zeolites (Si/Al(Y)
However, alkali metal
zeolites are much less acidic than H-forms or polyvalent cationic forms and in fact the high aluminium content X zeolites counterbalanced by heavier Ia cations can function as basic catalysts (71). The acidic forms of zeolites are usually produced by ion exchange of sodium forms, for example exchange with NH4+ is used for H- forms.
there is a distribution of acid sites and there is evidence, mainly catalytic, that the stronger acid sites retain Na+ ions more strongly than weaker sites. For example, in zeolite Y evidence for strong acidity was not obtained (72) until 30% of the Na+ ions were exchanged for H+ ions.
Hence residual Na+ ions
in H+ forms of zeolites can have a disproportionate effect on catalysis of demanding reactions. Recent work (70) assigns three types of Bronsted site in synthetic H-M (Si/Al
Increasing ion exchange from 40 to 90% is reported
to result in increases in both the stronger and the weaker sites and a reduction in the number of intermediate sites. This implies that there may be some redistribution of Na+ ions as exchange progresses.
A further point concerning cations in zeolites is that they are inherently electron acceptor sites and can function as sorption centres and as Lewis acid sites (18).
(b) Modification by Dealumination Dealumination
several processes including hydrothermal
treatment and secondary synthesis, which are discussed subsequently.
consider the extraction of aluminium under conditions where clear evidence for extensive replacement of A1 by
Si is not forthcoming.
treatments are used but extraction of A1 by mineral acids o r complexation with EDTA is most widely reported.
Framework A1 can be extracted by an aqueous
solution of EDTA (73).
If this extraction is made slowly it appears that some replacement of aluminium by silicon takes place since up to 80% of the aluminium can be removed
crystallographic evidence that occupancy factors remain close to unity after 53% dealumination and 29Si NMR supports some replacement of A1 by Si (51). However, other XRD results suggest that occupancy factors are less than unity so that substitution of Si for A1 on treatment with EDTA is not extensive.
Recent MASNMR, FTIR and sorption results (51) suggest that, as dealumination
generated and extensive replacement of A1 by Si is not observed and there are no reports of complete dealumination, with retention of crystallinity, using this method (EDTA).
Nevertheless, some "healing" is achieved possibly from
incorporation of soluble silica species or perhaps by migration of defects although this must be slow at the temperatures involved.
Furthermore, it is
clear that EDTA preferentially attacks the outer crystalline surface, even in large pore
(Y) zeolites, resulting in compositional inhomogeneity
NMR shows that non framework octahedral aluminium, which can
influence catalytic properties is removed by EDTA (51). Accepting some uncertainity in the extent of healing and the composition of frameworks dealurninated by EDTA it is interesting to consider acidity studies of dealuminated X and Y zeolites. A measure Bronsted acid sites is very
of the efficiency of
nicely established, using titration/indicator
methods, and shown (68) to depend linearly on the number of aluminium atoms per unit cell (NAl)
a. = 1.40 - 1.45
The effective acidity is zero when NAl
= 96 (Si/A1 = 1) and is unity when N A l= 28 (Si/Al = 6). This is taken to imply that the effective acidity of Bronsted
sites in faujasitic zeolites is constant for Si/Al>6.
Explanations for this
pattern, based on the distribution of aluminiums in zeolite frameworks, have been proposed and are discussed in Section 1.4.
(c) Thermal/Hydrothermal Treatment Heating zeolites in the H- or NH
forms at temperatures around 45OoC and
higher can result in loss of structural water by dehydroxylation of surface This may be seen for NH -M as a mass 18 peak around 5OO0C 4 (Fig 2.7). Dehydroxylation of the H/NH - zeolite in a shallow bed (SB) with 4 effective removal of water results eventually in structure collapse. On the
basis of infrared studies it was proposed that dehydroxylation of H-Y resulted in generation of
aluminium which was associated with observed Lewis acidity as discussed above. However, this scheme
requires that an initial ratio of bridged hydroxyls to
four coordinated framework A 1 of unity should decrease as dehydroxylation proceeds since two hydroxyls are lost for the destruction of one tetrahedral A 1
(see 1.2.5 above).
this scheme was
' forthcoming from X-ray fluorescent analysis (48b) nor from H
and 27Al MASNMR
results (73). During SB treatment the number of bridged hydroxyls remained in approximate
Consequently, it appears that, during SB dehydroxylation, A1 is continually removed from the framework which eventually results in structural collapse. Heating the H/NH -zeolite in a deep bed (DB) without effective removal of 4
water or heating in a gas stream containing sufficient water also results in release of aluminium from the framework, a fact first recognised in the generation of ultrastable zeolite Y
hydrothermal attack and, at suitably high temperatures, silica is sufficiently soluble and mobile in the presence of steam, to substitute in the vacant 'TI site (74d) resulting in structure healing.
S i -0-9-0-9
The healing process can be aided by migration of vacancies in a 'T' jump mechanism
Substitution of silicon
framework reduces the number of bridged Bronsted sites and in the case of zeolites initially rich in aluminium (eg Y ) , increases their effective acidity (cf EDTA dealumination). The above is, however, oversimplistic particularly in representing the dislodged aluminium as A1(OH)3. steaming Na/H or Na/NH4
Investigations using 27Al MASNMR show that
Y zeolites results in dislodgement of some aluminium
octahedrally coordinated to oxygen (chemical shift approx 0 ppm from A1
More extensive steaming results in a broad 27Al signal around 50 ppm assigned to low-symmetry oxyaluminium species probably polymeric at least some of which can be readily complexed by acetyl acetone (75a). reported that broad peak around 50 ppm from A1
More recently (76) it is
(as) is due to tetrahedral A 1
with a peak shift of 30 ppm due to quadrupole effects.
2 7 ~ 1 NMR results
suggest that aluminium species five coordinated to oxygen can also be produced during steaming (76~).
radial distribution analyses are
interpreted in terms of half unit cells of a boehmite phase which are said to be generated in faujasitic supercages during extensive steaming ( 74e ) .
Additionally there is clear evidence that at around 6OO0C the aluminium is dislodged by attack throughout the crystals in a homogeneous manner but that at elevated temperatures, in the presence of steam, migration of aluminium to outer crystalline surfaces takes place (47). available
Taking into account all the nature
non-framework aluminium (within and between crystals) depends upon the initial composition (particularly Si/Al, Na/NH ) and structure of the zeolite and the 4
severity of the hydrothermal process (T, t, pH20) (77). aluminium species can modify dCidity.
In particular there is evidence from
both catalytic and ammonia desorption studies that increased acidity and enhanced catalytic activity can be generated by the presence of appropriate oxyaluminium species interacting with framework Bronsted sites (49)(77)(78) (Fig 2.9).
However, the nature of sites having enhanced activity and acidity
is not yet clear (Section 1 . 4 and Chapter 71.
Infrared studies of hydrothermally treated zeolites show additional bands around 3600 and 3700 cm-'
which are weakly or non-acidic and are assigned to
A1-0-H units associated with dislodged A1 species.
A line in the H '
spectrum at 2.6 ppm (from TMS) is assigned to these A1-OH units (79). Infrared investigations using sorbed hydrogen have provided a new look at active sites in zeolites and other acid catalysts (36). Comparison of bands in the hydroxyl region (3000
with bands due to sorbed hydrogen in the near
infrared and observing the effects of heat treatment suggests that bands due to interaction (Table 2.3).
Typical results are shown in Fig 2.10.
After heat treatment of
HZSM-5,in addition to those assigned to interaction with bridged hydroxyls (4105 cm-')
and silanols (4125 cm-l), three bands due to sorbed hydrogen are
observed at 4060, 4010 and 4030 cm-'.
The band at 4060 cm-'
is seen only after
heating the zeolite at 1270 K when a band in the hydroxyl region is clearly seen at 3680 cm-' aluminium.
and assigned to AlOH species associated with dislodged
The band at 4060 cm-'
Bands at 4010 cm-'
and 4030 cm-'
Lewis acids ?A1
is, therefore, assigned to H2 sorbed on AlOH.
having comparable intensities are assigned to associated with tricoordinate A1 and Si atoms in
Deep bed calcination of Y zeolite followed by heating and
evacuation to achieve complete dehydroxylation gives bands at 4035, 4060 and 4125 cm-l.
The band at 4060 cm-l is now major and since extensive nnn
framework aluminium is present this result is taken as confirmation that the 4060 cm-'
band arises from the interaction of hydrogen and AlOH species and
bands at 4035 cm-l and 4010 cm-l arise from interactions of hydrogen with
39 tricoordinated silicon and aluminium. The presence of a band at 4035 cm-' hydrogen sorbed on
silica gel, previously
assignment of this band to
and the band at 4010 cm-'
interacting with S A l . In view of the previous discussion concerning H ' these assignments can probably be challenged. aluminium
thermal/hydrothermal treatments frequently amorphous silica. available
and 27Al MASNMR results
The nature of the dislodged
Consequently it is not yet certain what kinds of site are
interaction with hydrogen.
Currently NMR evidence is quoted for the existence
of aluminium in at least 3 types of coordination to oxygen (four, five and six) so that more than one type of Lewis site associated with dislodged material
must be a possibility and interpretation may not require the existence of framework tricoordinated A1 and Si.
A further point in relation to pentasils
is the fact that internal silanol groups might provide sites for H2 (weak Bronsted interaction). However, it has to be recognised that MASNMR is largely a bulk technique so that the absence of evidence for trigonal aluminium and silicon at oxygen defect sites cannot be taken to preclude such sites in small concentration.
In fact the hydrogen sorption work does suggest that only a few
percent of the total A1 in H-Y is in tricoordinate framework sites.
suggestion that such sites are major in dehydroxylated H-ZSM-5 and H-mordenite (36) is most interesting but remains to be established by other techniques.
Dehydroxylation of both of these zeolites results, as for other zeolites, in
loss of framework aluminium and it is not immediately clear why framework sites should be stabilised in these zeolites.
Moreover there is no
doubt that under steaming conditions aluminium is dislodged from the framework of both
outersurfaces as in the case of H-Y ( 4 7 ) ( 8 0 ) . At this time the detailed nature of Lewis sites and their function in hydrothermally treated zeolites is incompletely understood. (d) Secondary Synthesis Secondary synthesis involves the replacement of framework 'TI atoms by 'TI atoms from a separate source.
A multiplicity of T atom substitutions is
reported (81) but here we consider, briefly, the substitution of Si for A1 to generate silica-rich zeolites and the incorporation of A 1 to activate zeolites rich in silica.
Most reports concern the modification of faujasitic zeolites
40 using SiFg2-(aq) (82) or SiC14(g) ( 8 3 ) . (a) NH4 A102(Si0 ) 2 x (b) M l I n A102(Si02)x
) SiF6 = 4 2
l/nMCln + A1C13 +
Both of these processes have received much attention recently.
mostly based on MASNMR, IR and sorption studies demonstrates that isomorphous replacement of A1 by Si in faujasitic frameworks can take place with generation of few defect sites. A1F6 3-)
Contamination of the zeolite by aluminium fluorides (eg
species may occur in process
(a) and such species can
effective washing (51). Similarly, occluded aluminium species can result from reaction with SiC14 as evidenced by 27Al
MASNMR (84) but the quality of the
product depends, as in (a), on process conditions (85).
In principle these
secondary syntheses techniques do provide the possibility
zeolites with framework compositions outside the normal range of primary synthesis and with more control over non-framework species, hydroxyl nests and secondary pores than is the case with typical hydrothermal treatments. The reverse of these processes, substituting A1
frameworks in order to increase the number of acid sites is also widely reported (16 ) .
In some instances the process largely involves condensation of
hydrated aluminium species into nested hydroxyl vacancies. (e) Modification by Incorporation of oxides, metal salts or by halogen treatment A series of papers and patents demonstrate that the catalytic activity and selectivity of zeolites can be modified by incorporation of oxides, usually by impregnation from solution (84). In particular oxides of B, P and Mg have been used to change acidity and diffusivity, and for example in the case of phosphorus oxide modification of Bronsted acidity is presumed to involve interaction of bridged framework hydroxyls and hydrated oxide species. This is reflected in a decrease in the number of strong Bronsted sites and an increase in the number of weak
Depending upon mode of
incorporation the phosphorus can be concentrated onto outer dispersed more evenly (47c).
A wide range of techniques has been
monitor changes in acidity due to incorporation of oxides.
The incorporation of metal halides into solid acids is reported to generate superacid sites (89) and the acidity of zeolites is enhanced by incorporation of aluminium fluorides (90)(51) or by treatment with fluorine (91).
Superacidity is established by
indicator methods, by
TPDA and by
catalytic testing for modified H- mordenite (92). Vapour phase deposition of volatile compounds of silica such as SiH4 (93) a Si(OR)4
(94) or of volatile halides ( 8 6 ) is also used to modify sorptive
and/or acidic properties of zeolites.
ACID CATALYSIS IN HYDROCARBON TRANSFORMATIONS
1.3.1 Carbocation reaction intermediates in solution
In the case of acid oxides generally, and particularly in the case of zeolites the bulk of the experimental evidence, most noticeably that based on reaction
The initial steps leading to carbocation formation are not in
all cases the same nor is there always a consensus view about this.
initial steps are discussed subsequently. 2
The main hydrocarbon transformations proceeding via carbeniurn ions (sp hybrid bonding and empty p orbital at the charged carbon centre) include the following (SCHEME 1).
RIH + R 2 +;=R1+
a ) Classical 1,2 shifts of Alkyl or H involving non-branching rearrangement
C + I
c-c-c-c I 1 H H
c-c-c-c + I
b ) Branching rearrangement.
The cyclopropane intermediate is frequently
particularly to avoid reaction via primary carbenium ions.
* c-c-c-c I
C C H+ \ fY
C C 1eavage
- c-c+cf 1:
Addition to olefins (repetition leads to polymerization)
I 1 C-C-C-C-R
and similar addition to arenes
43 These reactions are the basis for the typical hydrocarbon transformations; isomerization, cracking, polymerization and alkylation which take place over solid acids.
For example, conjunct
Several steps may occur in sequence.
polymerization involves, polymerization, isomerization, cyclization and hydrogen transfer. The properties of carbenium ions have been established largely by studies in homogeneous acidic media.
Stabilities of carbenium ions decrease in the
order: tertiary ie
> secondary > primary
with approximate energy 1 changes (AElkcal mol- )
These differences in stability are reflected in reaction rates and hence in product distributions. An example (95b) is given is SCHEME 2.
+ C' C H C I l l
c c I I
C H C I I I C-C-C-C-C
- 10 at
c c c
I l l
= 5 x
at - 8 8 ° C
+ n~ "
In reaction (a) the initial and final ions are tertiary whereas in (b) the interconversion of 2 , 4 , 4 and 2 , 3 , 4 trimethylpentyl ions proceeds via a secondary carbenium ion.
The difference in stability between the secondary and tertiary
ions results in a high activation energy and much lower rate.
For reactions in acidic solutions, extensive work has established broad correlations between acid strength and the type of reaction which may be effectively catalysed. Typical examples are included in Table 3.1 (95a). Variation in temperature and in reactant type can result in a effective function of weaker acids.
The effect of temperature is particularly
appropriate to reactions over solid acids.
Weaker solid acids can be effective
catalysts, in part, because reactions can be made at higher temperatures. From Table 3.1 it is clear that product distributions from acid-catalysed hydrocarbon transformations depend upon acid strength.
For example in the
isomerization of butenes (SCHEME 3) the double bond shift, involving only proton transfers is catalysed by weak acids whereas methide shift requires stronger
In the case of butene isomerization the methide shift requires a change
in the nature of the carbenium ion resulting in an activation energy increased by the corresponding changes in carbenium ion stability.
t The demanding rearrangement to isobutene appears to proceed via a cyclopropane intermediate ion (cf scheme 1, 3bl.
Use of a stronger acid to promote methide
shifts can, of course, promote other reactions, for example polymerization of butenes so that product distribution will be a function of acid strength and also of reaction conditions.
Selectivity in acid catalysis is therefore
dependent, among other factors, on acid strength.
illustrates this for alkylation of m-xylene (95a).
45 Superacids provide a direct route to carbenium ions via carbonium ions which are presumed (96) to be intermediates or transition states possessing two-electron three-centre bonds (SCHEME 5)
Protolytic Attack on C-H
Protolytic Attack on C-C
Reactions proceeding via (a(2))
result in hydrogen generation, the reverse
reaction being reduction of a carbenium ion with molecular hydrogen.
proceeding via route (b) produce a carbenium ion and a smaller alkane.
reverse reaction is similar to that in SCHEME 1 (reaction 2) but with formation of a new C-C bond.
In the presence of superacids, alkanes including CH4 and C2H6 are reactive (20)
However, factors other
influence selectivity in
hydrocarbon transformations catalysed by acidic solutions. F o r example, product isomers from the alkylation of alkyl benzenes in solution depend upon:
strength and amount of acid catalyst; (ii) the temperature and duration of the reaction; (iii) the type of alkyl group(s) on the benzene ring
reactivity of the substituting alkyl group;
(iv) steric established
substitution of alkyl benzenes in solution and, in the absence of soatial constraints these also hold in solid acids and zeolites (98). The factors, discussed above for solutions, also affect activity and selectivity in hydrocarbon transformations over solid acids.
and selectivity are dependent upon reaction conditions and can be influenced by acid
(type, strength, concentration
Additionally, especially in microporous solids, spatial restrictions can modify activity/selectivity patterns, producing shape-selective catalysis.
cases thermodynamic considerations must be recognised when evaluating catalyst selectivities.
For example production of isobutene (SCHEME 3) is not favoured
under equilibrium conditions at higher temperatures.
Olefin reactions ( e g double bond shifts)
skeletal alkanes; conjunct
Catalyses the above reactions and acidity is
47 1 . 3 . 2 Factors Affecting the Activity of Zeolites in Acid Catalysis
Zeolite catalysts have been very
extensively investigated, and what
follows is an attempt to provide some insight into the subject by use of selected studies rather than to provide a comprehensive review.
excellent reviews are available (18)(19)(99)(100). Catalysis is generally considered in terms of total feed conversion and of product distribution.
In hydrocarbon transformations over zeolites these
parameters depend upon the chemical composition of the feed, the structure and framework composition of the zeolite, the nature of any non-framework species and the catalytic process conditions.
Since zeolite catalysts frequently tend
to deactivate readily, in association with coke build up, process conditions must include time-on-stream, in addition to reaction temperature, pressure, contact time, mixing regime and catalyst activation. studies activation procedures should be considered.
In any comparative
Fig 3.1 shows the effect
of temperature of activation on the type of acid site (Bronsted vs Lewis) and of catalytic activity.
These results suggest that xylene isomerization takes
place largely on zeolitic Bronsted sites so that rates are reduced after activation procedures which cause dehydroxylation.
0 4 1
12 Bronsted acidity
. -20 Iwiq
600 700 800 CALCINATION TEMP ,OC Fig. 3.1. Acidity and catalytic activity for 0-xylene isomerisation of magnesium decationised Y as a function of calcination temperature. (ref. 110).
Hydrocarbon transformations over acid forms of zeolites, that is those containing bridged hydrogens, result in product distributions which, in many cases are consistent with mechanisms involving carbocation intermediates. Reactions which proceed via protonated intermediates have been widely used as test reactions to assess factors affecting catalytic activity.
readily isomerized by Bronsted acids, via proton addition, with first order kinetics. Over solid acids the intermediate is presumed to lie on the surface with one methyl group pointing away from the surface.
Since the probabillties
associated with loss of hydrogens HA and HB are expected to be equal then,
isomerization of 1-butene should give a 1:l ratio of cis- to trans-2-butene. This is observed for solid acids and also for acidic solutions.
detailed kinetic study of butenes isomerization over metal sulphates (Mg and
A l ) demonstrates that the stronger acid (A1 2 ( S O4 ) 3 ) stabilises the carbocation more than the weaker acid and also favours conversion, from the common carbocation intermediate, to 2-butenes relative trans-butene
increases with the acidity of the catalyst.
This means that
This is observed (100) over
zeolites (Fig 3 . 2 ) where acidity is seen to increase with framework S i / A 1 as Bronsted sites become more acidic (and \3 OH decreases), and is also observed in acid solutions. Fig 3.2(a) presents a schematic representation (18) of kinetic features showing the increase in stabilisation of the carbenium ion ( A ( A H ) ) (where 4 H may be thought of as the enthalpy of formation of the carbenium ion) on increasing acid strength.
A simple thermodynamic cycle is proposed
(107)(18) to represent the
enthalpy of formation ( A H ) of a carbocation in a zeolite as
RELATIVE RATE AT 1509
SURFACE ACTIVATION ENERGY/k Jmol-'
PRODUCT RATIO Cis-/ l-
50 where DOH is the heterolytic dissociation energy of the bridged OH bond, P is 2 the proton affini-ty of the (organic) reactant, e /477Eor is the coulombic energy of the carbocation/zeolite ion-pair and
represents the coulombic interaction of the carbocation/zeolite ion pair with other ions within the zeolite cavities at a distance R. and possessing an effective charge
The above equation is incomplete in that other factors
can influence the stability of ions as guests in zeolites and site geometries are not the same in all structures s o that reorganization energies may differ. Nevertheless, for a given reactant in a given zeolite structure with similar cations the equation probably includes the major effects.
Moreover, it is
clear from Fig 3.2(a) that relative changes in the stability of carbenium ions ( A ( A H ) ) can be associated with changes in activation energies via a typical
linear free energy relationship (102) such that
isomerization of cyclopropane is taken as a test reaction and framework composition is varied by steam/acid leaching. so
Cyclopropane is a small molecule
that intercrystalline diffusion is rapid and the isomerization is a first
Utilising results with mass balances better than 90% it is
observed that the activation energy for the surface reaction decreases rapidly as Si/Al increases to around 6 and thereafter remains constant at least until very low aluminium content when there is evidence for an increase (58b)(103) perhaps reflecting a changed mechanism.
Pyridine sorption and
poisoning experiments enable turnover numbers to be obtained and these appear to be constant at Si/A1 greater than about 6. A constant turnover number with decreasing number of sites as Si/A1 increases beyond 6 2 1 leads to a linear decrease in rate with decrease in aluminium content for siliceous faujasites, and the rapid decrease in activation energy with increased Si/A1 below Si/Al = 6 results in a rapid increase in rate with decrease in aluminium content for aluminium rich faujasites.
The consequence is a volcano curve for rate as a
function of the aluminium content of faujasites (Fig 3 . 3 ) . This
isomerization which is also Bronsted catalysed (77) and the volcano curves for
._ 3 -1.->
Cracking of c5,c6 over Y zeolites treated with lNH&)* SiF6
n-Hexane lT=350°C? r
RELATlVE INTMSlTY 0 F ” A I - M R
Fig34Dependence of catalytic a c t i v e on intensity of 2ksigml for Al in tetrahedral cdinah’onlref.661.
5 6 fluoride content/w t%
INITIAL Al CONTENT/Wt %
TOTAL ALUMINIUM IONS /UNIT CELL
Fig.35. Comparison of activity enhancement on steaming (a1 and No of (paired] aluminiums distributed. initially in doubly occupied 4-rings (b) in H-ZSM-5 zeoMes.(R.M. Lago et al.Tokyo 1986). (ref.781.
reactivity ,with linear dependence of rnte on aluminium content for framework cornpositions iMit.h Si/Al>
6 is also observed in n-hexane cracking (58d).
where increased rates are not observed
Si/Al increases from 2.5 to 5 or 6
(58e) the linear decrease with aluminium content in more siliceous faujasites is observed. An optimum ratio Si/Al is also observed in other zeolites.
the rate of isomerization of n-pentane over acid extracted mordenites is said (104) to be optimal around Si/A1 = 8.5.
In the above work, and in similar studies, enrichment of silicon is achieved by chemical or hydrothermal treatment which can lead to changes other However
than those associated with framework composition (sections 1.2 a n d 1 . 4 ) .
ZSM-5 can be synthesised over a wide range of compositions having framework
Si/Al from around 15 to
Results for hexane conversion show that, in
carefully prepared and activated H-ZSM-5, rates of cracking are directly proportional to framework aluminium content at least up to Si/A1
linear correlation is observed ( 6 6 ) between reaction rate and the intensity of the 27Al MASNMR signal associated with tetrahedral aluminium (Fig 3.4). All
these results suggest that the catalytic acitivity of sites
associated with aluminium atoms in zenlitic frameworks reaches a limiting value as Si/Al increases.
At lower levels of framework aluminium the catalytic
activity is directly proportional to the framework aluminium content
turnover numbers remain constant with further decrease in aluminium content. This is generally true providing that sites are not activated by dislodged aluminium species and providing no other phases, contributing active sites, are present. However, the situation at very low levels of aluminium may not be clear in all cases.
For H-ZSM-5 synthesised with very low levels of aluminium
the linear correlation between catalytic activity and aluminium content appears to hold down to ppm levels of Al.
However, in faujasitic zeolites where
aluminium content must be reduced by dealuminatinn procedures there is some evidence that the correlation may not hold as A1-a 0.
In the isomerization of
cyclopropane activation energies tended to increase at very low levels of aluminium
requires confirmation using
reactions, suggests that either structural features or, perhaps more plausibly, preparation procedures which might result in different types or extent of defect sites may be responsible for differences in reactivity observed at very
For example steadacid leaching can
low levels of aluminium in faujasites. result
non-framework aluminium which would eliminate Bronsted sites.
53 basis for the general dependence of activity on aluminium content is discussed in section 4. The stability of carbenium ions within zeolites, as in solution or gas phase
reactions is of prime importance in acid catalysis, as discussed above.
Recently, carbenium ion stabilites have been correlated with dehydration of alcohols over H-ZSM-5
the ease of
as revealed by TPD studies (105). Results
are used to establish a scale of relative stabilities for oxonium and carbenium ions for C1 to C4 alcohols and the olefinic products of dehydration.
chain length of the alcohol increases the stability of the carbenium ion increases and temperature programmed desorption tends to favour dehydration rather than desorption of the alcohol. The discussion of acid catalysis and composition has so far centred on the H-forms
incorporation of countervalent metal ions, or of other oxide or metal phases or treatment with steam, etc, can affect acidic properties (section 18.104.22.168) and catalytic properties (section 1 . 3 . 3 . 1 ) . Ion-exchange of Na+ for NH
creates, on activation, more Bronsted sites
However, in zeolite Y strong acidity and associated
and increases activity.
catalytic activity is not detected until around 30% of the sodium ions are exchanged ( 7 2 ) . effectively
Stronger acid sites are presumed to retain sodium ions more
hydrocarbon cracking, quite small residues of sodium can affect results (106). Ion exchange of sodium for multivalent ions can also result in generation of Bronsted sites by hydrolytic processes eg
The extent of this, or similar, hydrolytic reactions and the location of the cation and liberated proton are major factors in acid catalysis rather than the simple degree of ion exchange. 2+
For example removal of the hydration sheath
ions with associated location of Ca2+ in site 1 (hexagonal prims)
of zeolite Y, without generation of CaOH' sites (107).
or H+ species does not produce active
The effect of ion siting is also evident in instances where
catalytic activity is found to increase rapidly after a limiting level of exchange of Na'
For example the rate of isomerization of butenes
increases after about 25%-30% exchange of Na+ for Co2+ (108),and the rate of isomerization of cyclopropane after about 30% exchange of Na+ for Co2+ in NaX zeolite (109).
From a combination of catalytic and sorption studies it appears that the fraction of supercage protons which is catalytically active in faujasitic zeolites depends upon the reaction (18). However, for more demanding reactions such as skeletal isomerization and hydrocarbon cracking it appears that only a relatively small number of the acid sites available in H-Y are involved (110). The lack of a more direct correspondence between the concentration of Bronsted sites and the rate of isomerization of xylene has been explained on this basis (Fig 3.1). The emphasis on hydrolytic generation of Bronsted sites, discussed above, does not preclude a more direct role for cations. enhanced activity with multivalent
In fact, explanations for
ions initially emphasized the lack of
shielding of Mn+ ions, due to the distances between charge compensating A10 4
units in zeolites, which could clearly result in electron acceptor (cation) sites.
Such sites have the capacity for electron pair bonding (Lewis acidity)
or may, in the case of transition metal ions, act as redox centres.
can, of course act as sorption centres (111) in overall catalytic processes and the charge distribution within zeolites causes electric field gradients which can strongly polarise sorbed molecules (27) thereby facilitating proton or electron transfer processes. The effect of hydrothermal treament of zeolites depends upon the process conditions and on the composition of the initial zeolite.
aluminium is dislodged from the framework and may be replaced by silicon. Consequently, the framework is enriched in silicon and this can lead to the generation of stronger acid ("isolated" Al) sites (section 1 . 4 ) when the initial zeolite is aluminium rich, and in all cases results in a reduced number of framework sites.
Additionally, it appears that, in some instances dislodged
aluminium may be involved in the formation of sites of enhanced catalytic activity.
This may be seem from Fig 3.5 which shows results (77) for the mild
steaming of H-ZSM-5.
The maximum in the rate of cracking of n-hexane is
explained by assuming that steaming decreases the number of framework sites but dislodged aluminium proximate to a framework site can enhance its acidity (section 1 . 4 ) .
Hence, there is an initial rise in activity followed by
decrease as more extensive steaming depletes framework sites and as dislodged aluminium agglomerates and migrates to outer surface sites.
This pattern for
H-ZSM-5 has been examined in some detail over a range of compositions and results interpreted qualitatively in relation to the siting of aluminium in paired or single sites in four rings ( 7 8 ) .
A role for non-framework aluminium
55 in the generation of stronger acid sites was earlier proposed for faujasitic zeolites ( 4 9 ) . Modification of acid catalysis by incorporation of oxides and salts is discussed briefly, in relation to alkane conversions in section 1.3.3. The role of
hydrogenation/dehydrogenation are considered in Chapters 6 and 7.
1.3.3Hydrocarbon Transformations over acidic zeolite catalysts Evidence for the role of carbenium ions in hydrocarbon conversion (and related reactions) over acidic zeolites is available from a consideration of product distributions and
there is some more direct evidence for sorbed
carbenium ions. Butenyl carbenium ions are generated from butene sorbed on Si0,/A1,03
and uv studies also show (112) that cyclopentenyl and cyclohexenyl
carbocations are formed from CH OH and olefins on H-ZSM-5.
cyclic carbocations are converted to protonated aromatic and then polyalkyl and polyaromatic cations.
In H-M and in Na/H-M similar cyclic carbenium ions are
produced from allene, cyclopropane, propene, isopropyl alcohol and acetone (113). The rate of formation and oligomerization of carbenium ions is strongly affected by zeolite Bronsted acidity.
Sorption/reaction studies of 2-propanol
and propene are also readily interpreted by assuming that, under appropriate conditions, both sorbates can give a common propenyl carbenium ion. results of a TPD study of a series of alcohols sorbed in H-ZSM-5
in terms of the stabilities of carbenium ion intermediates which are formed during reaction ( 1 0 5 ) . Among the hydrocarbon transformations, cracking reactions continue to be of
temperatures up to around 5OOOC the products from conversion of C
5) over acidic zeolites are generally consistent with reaction via carbenium ion
explained, taking into account thermodynamic and shape-selective effects, on the basis of the reaction types listed in section 1 . 3 . 1
(Schemes 1 to 5 ) .
However, there is a continued interest in the generation o f the initial carbenium ions.
Traces of olefins in an alkane feed can be readily protonated
to carbenium ions
and the addition of traces of olefins can increase reaction rates.
Lewis acids (L) may also produce carbenium ions by hydride abstraction
Additionally, in so far as zeolites can behave as solid superacids there is the capacity
measurements of H
and similar acidity parameters do not place unmodified
zeolites in the superacid category there is growing evidence that they may behave as such at elevated temperatures.
For example, in a reaction sequence
involving only an initial (p-scission) cracking of a carbeniurn (R')
either from an olefin or via a Lewis site (a,b above) the products consist of
an olefin and a smaller carbenium ion (R,')
which can abstract a hydride from
the alkane to continue the process.
This sequence suggests that the initial ratio of alkane/olefin is unity. Alternatively, if the initial carbenium ion is generatcd by direct protonation the sequence may be written as follows, where attention is focussed on a
particular bond C-R' ( R '
H or R =
alkyl) in the alkane
R= [F; R=H
[smaller) carbenium ion+olefin
The (smaller) carbenium ion, which does not crack readily, is available to continue the sequence by typical bimolecular hydride abstraction (reaction (d)) to produce a carbenium ion from the reactant alkane and a smaller alkane. Consequently,
At temperatures in the range 673-743 K, results suggest
that n-heptane is cracked over LaHY zeolite to give a primary product ratio 1 and since no hydrogen is detected a protolytic attack on a C-C
bond is proposed as the first step (114).
MIND0 calculations suggest t'ne
formation of a hydrogen bridged intermediate.
It is then energetically
favourable for this intermediate to crack directly (activation energy 12-18 kcal mol-l) rather than convert to other structures (114).
distribution their involvement in conversion over H-ZSM-5 is less likely since pyridine sorption shows no evidence for Lewis-sites ( 5 9 ) on well-crystalline H-ZSM-5 (although it must be admitted these may be generated during activation procedures).
The reaction of C6 alkanes over H-ZSM-5 at T in the range 623-823
K adds support to a direct protonation mechanism.
As temperature increases,
product distributions suggest that there is an increasing contribution from the monomolecular reaction (e) over the bimolecular reaction (d).
In this work
p r o t o n a t i o n of C-H, used
t o produce H
a s a p r o d u c t , i s proposed and r e s u l t s a r e 2 d e c r e a s e i n c o n s t r a i n t index ( r a t i o of t h e
t e m p e r a t u r e (115). S i m i l a r l y , i n t h e i n i t i a l s t a g e s 05 r e a c t i o n , a t low c o n v e r s i o n , propane
is s a i d t o react o v e r H-ZSM-5
by p r o t o n a t i o n of t h e C-C
bond t o g i v e methane
and a carbenium i o n a l t h o u g h e n e r g e t i c a l l y t h i s must be u n f a v o u r a b l e ( 1 1 6 ) .
A t h i g h e r l e v e l s o f c o n v e r s i o n i r ; i s proposed t h a t propane i s a c t i v a t e d v i a
h y d r i d e a b s t r a c t i o n by s o r b e d carbenium i o n s ( ( d ) a b o v e ) . Energetic parameters associated with -1-ene
o v e r H-USY
isomei-ization o f
a r e found (117) t o be similar t o t h o s e same
super-acid s o l u t i o n s (Table 3 . 2 ) .
TABLE 3 . 2
I s o m e r i z a t i o n o f Methyl P e n t e n e s (117)
A c t i v a t i o n Energy/k c a l mol-I Rearrangement
Superacid s o l u t i o n s
S i m i l a r l y , t h e primary p r o d u c t s from c r a c k i n g o f i s o b u t a n e on H-M a r e p r o p a n e , n-butane pentane r a t i o - 0
and i s o p e n t a n e (118).
and t h e propane/pentane
(Si/A1 = 8.5)
A t v e r y low c o n v e r s i o n t h e n / i s o
r a t i o >1.
carbeniurl! i o n p r o c e s s a c c o u n t s f o r a l l t h e r e s u l t s o b t a i n e d u s i n g I 3 C
i s o b u t a n e (119). A l k y l a t i o n of i s o b u t e n e by t h e t e r t i a r y b u t y l c a r b e n i u m i o n t o p r o d u c e t h e
carbenium ion is rate determining and all labelled products can be accounted
for by subsequent rearrangements of the C8
ion and by
However, the bimolecular disproportionation process above usually occxrs only on superacids, again providing support for zeolite superacidity. In view of the previous discussion it is not surprising that product distributions are frequently interpreted in terms of types of acid site. Product distributions from alkane cracking have been used to estimate the relative effects of Bronsted and Lewis sites (120) and the oligomerization of ethylene over HY and H-ZSM-5
at 300 K is said to produce largely branched
structures in the presence of Lewis acidity and largely linear structures in the case of strong Bronsted acidity. sites
In this latter study (121) the Lewis generated
characterised by infrared including the spectra associated with hydrogen sorbed at
However, as mentioned previously, there remains some uncertaintv
about the nature of Lewis sites generated by thermal treatment of zeolites. Moreover, the authors suggest that, in the presence of strong Bronsted acidity, the surface species is closer to a sorbed ether than to a carbenium ion, accounting more readily for the lack of chain branching.
22.214.171.124 Alkane Conversions over Modified Zeolite Catalysts Typical modifications
and section 126.96.36.199) to zeolite acid
catalysts include modification of composition by hydrothermal treatment or by dealumination or secondary synthesis and modification by
separate phases such as oxides, halides or metals. The reaction/regeneration cycle associated with hydrocarbon cracking to produce gasoline involves treatment with steam at elevated temperatures. Consequently, hydrothermal treatment of zeolites is
elevated temperatures, in the presence of steam, aluminium may be dislodged from framework sites and replaced to a greater or lesser extent by silicon. The shorter Si-0 compared to the A1-0 bond results in a shrinkage of the unit cell and a secondary pore system is developed (122)(74d) which is associated with intracrystalline voids developed by localised collapse of crystals and with generation of amorphous material. The increase in framework Si/Al, following hydrothermal treatment, results in changes in acidity as already outlined.
Additionally, there is evidence for
the influence of nnn-framework aluminium species
Hydrothermal treat.ment results in an increase in t.he number of Lewis sites and a reduction in the number @f Bronsted sites and there is.some evidence for the generation, under appropriate conditions, of superacid sites (49)(77)(78). Mild steaming of H-ZSM-5 can result in enhanced activity in the cracking of n-hexane (77)(78) and this is associated with increased acidity as measured by
TPDA (77). Prolonged steaming causes more extensive dealumination and results in reduced activity.
These catalytic features are explained in terms of a
synergistic effect of dislodged A1 species on bridged hydroxyls associated with tetrahedral framework aluminium.
necessary that dislodged aluminium should be
in the appropriate form and
sufficiently proximate to a tetrahedral framework aluminium.
In the case of
H-ZSM-5 theoretical calculations (section 1.4) suggest that aluminiums show preferential siting in TI2 and T2 sites. the four-rings which may be
A separate approach implies siting in
singly occupied, in which partial
hydrolysis of one aluminium in a doubly occupied ring could result in a "dislodged A l "
still attached by one or more links to the framework but
representing termination of the -A1-0-Si chain such that it does not occupy a framework 'T' site.
In such a situation the dislodged A1 would be proximate to
the framework 'T' site aluminium present in the original four-ring.
for partial hydrolysis of aluminiums is available from recent infrared studies (123) but at this time the nature of any superacid sites generated in H-ZSM-5
by hydrothermal treatment is speculative.
Simple formulations of these sites
are used (49)
to imply interaction between Lewis sites (A10')
and Bronsted sites to enhance
Bronsted acidity by electron withdrawal from the bridging oxygen. detailed chemical structure of the dislodged A 1
acidity there is attraction in the identification of superacid sites as Bronsted sites having enhanced activity due to synergistic interaction with Lewis sites both because of analogies with superacid solutions (96) and because there is some supporting evidence for this (49)(77)(78). Because ZSM-5 has interconnecting channels but no definite cage system any aluminium dislodged will tend, initially, to be in the main channel system.
61 However, in H-Y zeolite dislodged aluminium may occupy small and/or large cage regions, depending upon treatment s o that the product of steaming is likely to be more dependent upon process conditions. showing enhancement of acidity and of
Nevertheless, similar results,
transformations are reported over hydrothermally treated Y zeolite (49). The role of hydrothermal treatment of zeolite Y in connection with alkane conversion reactions is of particular interest because of the commercial scale of
steam-stabilised "ultrastable Y" (USY) are widely used.
During operation these
catalysts are subjected to hydrothermal processes which cause changes in framework composition, secondary pore structures and amount of non-framework aluminium, as previously discussed, and associated reduction in cell parameter a
The cell parameter reflects, largely, the framework ratio Si/Al which
determines the density of framework A 1 sites and the distribution of types of A 1 framework site having different acid strength (Section 1 . 4 ) .
parameter (ao) is found to correlate well with changes in both catalytic activity and selectivity in the cracking of gas oil over hydrothermally 0
modified faujasitic zeolites (106) for a o s 24.32 A where most of the sites correspond to those of stronger acidity (ie a framework A 1 possibly one A 1 in its second coordination sphere).
with zero or
In this region activity
tends to decrease and selectivity (octane number) tends to increase with decrease in a
(increase in framework Si/Al).
Increased selectivity is
attributed to reduced hydrogen transfer, which gives a more olefinic naphtha and
isolated framework A 1
considered to make for proximity between sorbed carbenium ions and sorbed hydrocarbons resulting in more facile hydride abstraction.
On a more isolated
site the carbenium ion more readily cracks to produce an olefin and a sorbed carbenium ion. However, it is not clear in all cases, that the role of extraframework species, for example dislodged aluminium, nor that of the secondary pore structure generated by steaming can be eliminated from discussions of the activity and selectivity of commercial cracking catalysts.
Currently there is
considerable interest in comparisons of FCC catalysts based on USY and on zeolite Y enriched in silicon by reaction with SiF62-
(124), and it is
suggested that steaming of these initially different A1 content zeolites to the same value does not produce identical catalytic behaviour (124).
reduced by steaming the number of framework aluminiums is much reduced and the
amount of extraframework aluminium is increased.
Moreover, in the presence of
steam, aluminium migrates to the outer surface of the zeolite forming a separate phase (47).
Consequently, the catalytic activity of the zeolitic
aluminium is diminished and the role of any enhanced.
Extraframework aluminium readily leads to the generation of Lewis
sites, perhaps similar to those found in active alumina, which can be effective in hydrogen transfer reactions.
Therefore, and especially in the cracking of
large alkane molecules which are likely
crystalline surfaces, it is to be expected that active sites associated with extraframework aluminium will become more and more a feature of the reaction as a
Consequently, catalysts starting from very different framework
compositions (Si/Al) may be dealuminated to the same values of a not have the same amounts of non-framework aluminium.
but they will
Moreover, the relative
numbers of the different types of aluminium generated during dealumination by steaming are likely to depend upon the initial composition as is the nature of the hydrothermally generated secondary pore system (122). These features could well account for the differences reported for USY zeolites made from a starting material with Si/Al
2.5 and catalysts prepared from a modified Y zeolite
with a silicon-rich framework (124).
Differences in Lewis activity for these
catalysts may explain the differences in coke and olefins observed at very low a
values. Treatment of oxide catalysts with halides can enhance their activity in
acid catalysed reactions (125) and similar effects are observed in zeolites. Fluoride treatment of H-M increases activity in cumene cracking and increases acidity as measured by the use of indicators or by calorimetric measurements of heats of sorption of ammonia (92). Enhanced catalytic activity in hexane and pentane cracking (Fig 3 . 6 ) is observed in faujasites containing occluded A1F species (51).
Infrared investigations using pyridine (126) show increased
numbers of Lewis sites in the presence of A1F involved in enhanced activity.
species which are presumably
Similarly the treatment of HAlY with fluoride
can enhance catalytic activity in cumene cracking, a reaction which takes place readily at Bronsted sites.
The conditions reported for treatment of zeolites
with fluorides are varied so that products must differ and a single explanation for enhanced activity may not be adequate.
Nevertheless, the evidence, to
date, suggests that in many instances enhanced catalytic activity can arise from strong Lewis acidity and Bronsted acidity which may, at least in some treatments, be involved cooperatively.
However, in a more general sense the
relative role of Bronsted and Lewis sites will depend upon their numbers,
A role for Lewis sites is
accessibility and upon reaction type and conditions.
well illustrated by studies of modified oxide catalysts. containing
For example in A1 0 2 3 active centres for the
isomerization and decomposition of light alkanes at low temperatures (127) and appear to be involved in butane conversion over metal oxides containing SbF 5 (126). Zeolite catalysts are also frequently modified by oxides in some instances to reduce acidity (Mg,B,P oxides) or to add a second catalytic function ( V 0 2 5’ In the case of medium pore zeolites such as ZSM-5 these oxides
(Mg,B,P) can also modify shape-selective effects.
For example the selectivity
in para-xylene production from methanol and toluene depends on the relative rates of acid catalysed alkylation and isomerization and on the relative diffusivities of the xylenes.
Both of these factors are favourably modified by
incorporation of oxides ( 8 7 ) .
Moreover, since active sites at external crystal
surfaces are non-shape selective, there can be advantages in surface enrichment of oxides (47c).
188.8.131.52 The role of free radicals and radical ions
Over non-acidic Na-forms of zeolites, hydrocarbon transformations occur, at relatively high temperatures to give product distributions anticipated from reactions via radical intermediates ( 1 2 8 ) . in acid forms of zeolites.
Radical processes are also observed
Early reports suggest that radicals may be
generated at sites associated with transition-metal impurities (eg Fe(II1)) but recent reports emphasise the role of “defects” in the zeolite structure (129). It is clear that radical species are readily formed, even temperatures, on hydrogen forms of zeolites. olefins form radicals at -78OC, sorbed. implying
On hydrogen mordenite (H-M),
their nature depending upon the type of olefin
However, at 2OoC a series of olefins give rise to the same signal a
oligomerisation (130). The influence of ammonia demonstrates that, although Bronsted sites are not essential for radical/radical ion formation they can be involved in stabilisation of radical species. olefins, to
Heating H-M, containing sorbed such
(acetylene, ally1 chloride, butadiene, n-hexane, methanol) form a radical having a 1-,2-dialkylbenzene structure.
These higher temperature
transformations are strongly inhibited by ammonia implying the participation of Bronsted acid sites. The rate of generation of signal intensity, due to
o-xylene sorbed at 20°,
depends upon Bronsted sites as does the steady state
concentration of radicals. Radicals are also detected in the effluent stream from the conversion of methanol over H-ZSM-5 at T
K, and a radical
mechanism is proposed for formation of the first C-C bond in the methanol to hydrocarbons conversion. Product distributions are also used in support of radical intermediates during hydrocarbon conversion over acidic zeolites.
For example the major
isobutane conversion products to be expected from the tertiary carbenium-ion intermediate differ from those expected from a radical/radical ion intermediate (131).
Experimentally it is observed that products from conversion of isobutane at 700-920 K over amorphous solid acids differ from those over H-USY and it is suggested that, in both types of catalyst, the initial reaction involves an electron acceptor site ( E A ) . iC H
i-C4H10 + EA
/ 0 4 8 4
+ H2 + EA
+ CH4 + EA
Differences in product distribution are attributed to subsequent transformation of olefins into carbenium ions by the acidic H-USY zeolite which results in consumption of hydrogen, increased amounts of paraffins and C5+ and reduced CH4.
However, i-butane conversion is also interpreted in terms of direct
protonation by H-M
(118) to produce carbonium ion intermediates.
difficulties in resolving the extent of radical involvement by reference to product distributions over strongly acid catalysts.
involving carbenium ions mask the initial product distribution and at very low alkane conversions where primary products may be detected, protolytic attack and radical reactions can, in many instances, give a similar product slate. further and general problem associated with
concerns increased difficulty in analysis and increased distortion by any trace impurities.
Procedures involving extensive experimentation are reported to
give identification of primary products (132).
could clarify mechanisms in some cases. There remains the question of the nature of the electron acceptor sites. One proposal relates their generation to modification of Bronsted sites in H-ZSM-5 during calcination processes ( 1 2 9 ) .
4 - 0 -Al-
Electron acceptor (EA) (solid defect site)
Bronsted s i t e
The electron acceptor site can then react according to
I *+ I I I
The charge transfer process in (b), generating the species R t ,
is said to occur
readily for organic molecules with ionisation potential less than the adiabatic ionisation potential (12.61 eV) of the nonbonding lone pair orbital in oxygen. Subsequent transformation of the radical ion may result in carbenium ions. For example, (129)(131),
I -+ I
-Si-0 - A l -
carbenium ion +
aromatisation of alkyne radical ions is available (129).
It is a l s o suggested
(130) that strained T-0-T links may be the source of EA sites.
may be a feature of distorted four rings in H-M which are stabilised by Na+ ions in NaM.
Strained four rings may also arise from elimination of water from
hydroxyl nests (132).
In H-M it is suggested, based on esr studies in the
presence of ammonia (133), that the radical/radical ion is formed at an oxidising site (EA) and transformed at a Bronsted site. The previous discussion reviews some current thinking on hydrocarbon transformations. Table 3.3 provides a summary of possible routes to carbenium ions in acidic zeolite catalysts. In the absence of dehydrogenation centres alkanes convert to carbenium ions via carbonium ions or radicals or directly in
the presence of strong Lewis acid sites.
The relative roles of direct
protonation, hydride abstraction or radical/radical ion fo:nation
on the type (Bronsted vs Lewis) number and strength of the acid sites and on the availability of electron acceptor sites.
In turn these depend upon the
structure and composition of the zeolite and on particular pretreatments.
influence of these sites will a l s o depend upon the chemical nature of the hydrocarbon and on process conditions.
Once the surface is "covered" with
carbenium ions products could be expected to follow by typical carbenium ion processes (section 1.3.l)subject to thermodynamic and soatial restraints.
TABLE 3 . 3 Summary: Hydrocarbon Transformations over Acidic Zeolite Routes to Carbenium Ions
+He strong site
-H2 or-alkane CARBENIUM ION
Theoretical Aspects of Zeolite Acidity Several theoretical approaches have been made to explain the properties of
zeolites. In this section emphasis is placed on molecular orbital calculations using cluster models and on calculations associated with distribution of T atoms with'in zeolite frameworks. Other approaches are considered briefly.
1.4.1 Quantum Mechanical Calculations on Clusters 184.108.40.206 Ab Initio Methods Techniques of quantum chemistry can provide powerful tools for elucidating microscopic details of structure and bonding (134). It has recently been shown that molecular orbital calculations can provide useful information concerning the intrinsic properties of acid sites in solids.
A variety of molecular
orbital calculations are available varying in complexity from essentially empirical to completely correlated wave function analysis.
chemical investigations of solid acid sites utilized semi empirical methods such as CNDO, I N D O and more recently MIND0 (135), and these are discussed subsequently. Recent developments in computer technology plus the availability of efficient small gaussian basis sets have rendered feasible ab-initio calculations which can in many cases give structural data with an accuracy close to that of experimental observation.
Some detailed accounts of the
earlier semi-empirical literature with reference to available (135) and is discussed subsequently. focussed
This sectinn will mainly be
semi-empirical methods are discussed in the following section. For feasible molecular orbital calculations it is necessary to choose a suitable model, (Fig 4.1) which should be sufficient for description of the intrinsic properties of the hydroxyl group representative of the Bronsted acid site in zeolites.
After selection of the model it is necessary to choose an
appropriate basis set to perform the quantum chemical calculation.
is limited by the computer cost and whereas use of an extended basis set together with
calculation of choice, such an extensive calculation is not feasible at present with the units of Fig 4.1.
Although many Calculations have been performed
using the STO 3G basis set (134), in recent years the 3-21 G basis set has been developed where the outer valence shell is split to allow for a more diffuse gaussian function in the valence shell.
In most molecules this effect leads to
an improved description of bonding characteristics. Hydroxyl groups in zeolites can be broadly classified into terminal and bridged forms (136). These are referred to previously in Sections 220.127.116.11a in discussion of experimental evidence which shows that the terminal forms exhibit a much lower acidity.
Using models (a) and (b) of Fig 4.1 to represent
terminal and bridged hydroxyl groups respectively, ab-initio calculations using the 3-21 G basis set have been performed in the hope of gaining some insight into their acidic behaviour.
Full geometry optimisation is performed for these
units (under the constraint of Cs symmetry) and the resulting geometries are
A Mulliken population analysis and an OH stretching
outlined in Table 4.1.
frequency calculation have also been performed and the results obtained are outlined in ,Table 4.2. It is apparent that the OH distance, the OH stretching frequency, the qH and 1q q I values are all predicted to be larger for the O H This is in agreement with the experimentally observed
bridged hydroxyl group.
greater acidity of the bridged hydroxyl group. calculated frequencies (64 2 20 cm-') difference of approx 80 cm-'. as charge distribution
The difference between the
is also close to the experimental
Whilst the calculation of static properties such and
OH bond strength do give an insight into the
potential acidity, the true Bronsted acidity can only be assessed by measuring the ability of the OH group to protonate a suitable base (137).
A more direct
measure of Bronsted acidity therefore is the weakening of the OH bond brought about by interaction with a suitable base.
We have referred to experimental
characterisation of acidity in this wayin section 1.2.4 possibility of
interactions of CO and NH
and now investigate the
with models (a) and (b) of Fig 4.1 are investigated
by monitoring their effects on the charge distribution and strength of the OH bond.
The results obtained are presented in Table 4.3.
These data indicate
that the perturbation of the bridged form is greater than that observed for the terminal form. NH
For example, whereas a
value of 440 cm-'
is observed for the terminal OH form, a much greater
is observed for the bridged aluminium form.
on interaction with value of 1150 cm-1
In this respect it is useful to
note that the difference in shift between the bridged and terminal form is much greater than the difference observed in the free OH frequency (approx 60 cm-l). This
perturbations, a conclusion which is in agreement with many experimental observations. Experiment shows that the acidity of zeolite solid acids is dependent on the framework composition (Si/Al).
As discussed in previous sections, acidity
Fig.4.1. Model units used for Ma calculat'm.
ELECTRONEGATIVITY Fig.4.2.ta)Expt. A3 value on C6H6 adsorption. (b)Theoretkal A3 for H20 interaction as a function of electronegfity (ref.138).
Mcy d d N t W * , pH - I ~ dihr
38 w M YHOERYH IMERMDIATL ELECTROHGATIYITI
Fig.43. Ab-initio Mo calculation i3-21G ; SCF). Symmetrical units X,SiiOH)Al X, iX=H,F).
Fig.44. Model units used to monita acidity variation as a function of nearest Eighbour Al (ref.121).
Moleculw Geometry Calculated for Units ( a ) and ( b ) of Figure 1 using 3-219 Basis Set (from ref 36)
rSiH rSiH /OSiH /OSiH /RSiH r(Si0) r(0H) /SiOH
147.6 149.0 106.9 112.4 108.9 167.4 95.9 127.8
147.9 147.1 104.5 108.5 111.2 173.4 96.7 119.6 130.7 192.7 162.2 161.1 96.8 102.7 117.3
r(A1H) /OA~H -/OAlH /HAlH
Bond distances in pm
TABLE 4.2 OH Bond Properties for Terminal and Bridged Hydroxyl Groups (refs 136,139,2451
OH Bond Characteristics
IqHqO I OH fOH
increases with Si/A1 ratio.
One interpretation of this effect is that
replacement of aluminium by the more electronegative Si atom leads to increased electron withdrawal from the OH bond which results in increased acidity. Ion-exchange effects on acidity have also been explained in terms of the Using the OH stretching frequency as a
electrnnegativity principle (38).
measure of acidity a linear correlation between the OH stretching frequency and the intermediate Sanderson Electronegativity is observed (38). Deviations from this linear relationship are attributed to electrostatic or crystal field effects on OH groups in small cages.
The effect of increased electronegativity
on the OH properties has been investigated theoretically using the models of Fig 4.lb by progressively replacing the hydrogen atoms by fluorines (138). The effect of
Representative results obtained are presented in Table 4.4.
increased electronegativity on the change in hydroxyl frequency ( A D O H ) for interactinn with
experimental trend observed on adsorption of benzene is also given.
results indicate that increased electronegativity does lead to increased acidic properties and the theoretical trend of Fig 4.2
does mirror that observed
experimentally. Recent work shows that "zeolites" containing elements other than A1 or Si in framework positions can be synthesised.
The range of elements incorporated
into the framework continues to grow and experimentally it is shown that quite large variations in acidity can be achieved by such substitutions. interest, therefore, to investigate the aprinri prediction by
It is of
calculations, of the acidic properties to be expected in these materials.
our laboratory we have recently instigated such a study (139) using the unit of Fig 4.lb where A1 is replaced by B and Ga.
Experimentally it is shown that the acidity varies in
collected in Table 4.2. the order A1
> Ga.> B
The data relevant to acidity are
The theoretically calculated OH stretching
frequency, and charge distribution for the OH bond, are in agreement with the experimental
substituted form has also been investigated and the results are presented in Table 4.3.
It can also be seen that the perturbation of the properties of the
OH group for the boron unit is much less than that for the bridged aluminium unit, and is similar to that calculated for the terminal OH model.
is in agreement with experimental acidity measurements of boralite which indicate a Bronsted acidity value close to that of silica (31).
c l m
m m m m
m m m
m In 0
N m P
P r ' m
Free OH Group Properties in Model Compounds of Figure 4.lb and its Fluorinated Derivatives (from ref 138)
3.44 3.79 4.17
3920 3911 3901
0.4449 0.4757 0.5048
(1,l) Corresponds to one fluorine atom replacing a H atom on each side of the bridging OH group
Effect of /SiOA1 angle on OH group properties
126 140 150 160 170
0.966 0.970 0.974 0.978 0.981
3931 3870 3828 3773 3717
0.472 0.465 0.456 0.445 0.432
Recently the effect of geometric structure on the properties of the bridging OH group has been investigated (140). The variation in properties of the OH group with increasing SiOAl angle are presented in Table 4.5.
general it appears that increasing SiOAl angle leads to a decrease in OH bond strength.
The ionicity of the bond is also decreased.
(ZSM series, mordenite, THETA-1 etc) generally have more acidic Bronsted sites than low-silica structures. Si/A1 ratio. angles.
This has been attributed mainly to the higher
However, they are also characterised by much larger TOT bridging
/TOT in faujasite
above results suggest that it may be important to take into account structural properties as well as compositional, a point made previously, when attempting to explain acidic behaviour of zeolite catalysts. hydrogen charge on both
The dependence of the bond
graphically in Fig 4.3.
As with the ab-initio applications discussed previously, most approaches in this field make use of cluster models which are taken to represent a specific unit and active site of the relevant polymorph or crystalline structure.
The cluster model is usually terminated by hydrogen atoms to mimic
the lattice environment although other approaches such as pseudoatoms with variable orbital ionisation potential (141) or electrnnegativity (142) have also been used. In
calculations are Calculations.
similar quantities obtained
This is principally due to the extensive parameterization and
approximations used in semi-empirical type methods.
utilise the parameterisatinn given in the original formulation (143) however it has been recently shown (144) that reparameterisation for third row atoms can lead to more accurate geometric results.
Absolute values of charges
calculated by CNDO methods have been shown to be too low accurate
(145), however, relative
in comparison with trends
distribution and energy can in general be accurately reproduced.
applications to solid acid sites one is primarily interested in the relative charge distribution or bond strength and in such cases the results of CNDO or similar semi-empirical methods can be of use. Extensive application of CND0/2 in the characterisatinn of solid acid
sites (zeolites in particular) has been carried out by Beran and co-workers (13,146). In these studies the standard version of the CND0/2 method (143) and an
basis for the Si and A1 atoms was used.
Inclusion of d orbital
basis sets dbes lead to a considerable reduction in the charges calculated, however, no noticeable change is observed in the relative charge distribution (145). A
distinct advantage of
calculations is the ability to perform calculations on large units. using the CNDO/2 method studied
due to the much less prohibitive computer costs of the former.
the electronic structure of HX and HY
zeolites using 4-ring cluster models such as Si A 1 0 H(OH)8-, Si A 1 0 H (OH)8, 2 2 4 2 2 4 2 Si A10 H(OH)8 and Si A 1 0 H(OHl8Na. Formation of hydroxyl groups at 01 and 03 3 4 2 2 4 was favoured. The calculations also indicated that the hydroxyl groups of HX zeolite are less acidic than the corresponding HY hydroxyls.
In general it
was found that the presence of two A 1 atoms in the four-ring decreased the acidity of the hydroxyl group. This was taken as quantum chemical support for the previously
effect of nearest neighbour A 1
characteristics of the hydroxyl groups.
This is discussed later in this
section. The location of an Na’ ion in the SI position was shown to exclude formation of OH groups of the 03 type.
The acidic characteristics of HZSM-5
were also studied using the CND0/2 method (146). modelled by clusters of the T505(OH),o
The ZSM-5 structure was
and T 0 (OH)12 type (T 6 6
Si or A l ) .
The affinity of the skeletal oxygen atoms for the protons was found to be lower than in faujasites and decreased with increasing TOT angle.
TOT angles of ZSM-5 compared with faujasite can, therefore, be expected to give rise to an increased acidity.
However, analysis of the charge on the
hydroxyl hydrogen reveals that this parameter decreases with increasing angle. These trends have been confirmed by ab-initio calculations (see above) and suggest that the location of protons near the large TOT-angle sites is improbable and that the protons migrate to more normal positions with deeper potential wells.
described previously for ab-initio studies a better
description of the Bronsted acidity of surface OH groups can be obtained by investigation of their perturbation upon adsorption of basic molecules.
et a1 (146) have investigated the interaction of ethylene with the hydroxyl group of faujasites and HZSM-5 zeolites.
It was shown that interaction
leading to the formation of a stable n-complex
I \ is energetically most favoured and results in a weakening of the OH and C=C
The interaction with hydroxyl groups of HZSM-5 was shown to be
energetically more favourable than the interaction wi-th faujasitic hydroxyls and was attributed to the higher acid strength of HZSM-5. faujasitic type zeolites with A1
, A1(OH)2+ and A1(OH)2+ cations located
the SII and SI cationic positions were studied by the CND0/2 method (146~). All these species were shown to exhibit strong electron acceptor capabilities with the Lewis acidity varying in the order A13+)
OH groups bound to the A1 ions were shown to be less acidic (Bronsted) than the skeletal hydroxyls. Dehydroxylated forms of faujasitic zeolites were also investigated by the CND0/2 method
It was demonstrated that the
tricoordinated A1 produced by dehydroxylation is a very weak Lewis acid in contrast to tricoordinated 5Si+ whose electron acceptor ability is much greater and comparable with that of the A1(OH)2f species coordinated in the cation posi-tions in the zeolite.
Kazanski et a1 (147) have used the CNDO
characteristics of silica and zeolites.
The cluster models were bonded by
univalent hydrogen-like atoms (A) with variable valence orbital ionization potentials (VOIP) that allowed one to modify the acidic properties of the OH group.
Calculated shapes of -the potential energy curves for the (OA) SiOH 3
fragment coincided well with experimental curves calculated from near-infrared data.
These calculations provided support for experimental observations,
using overtones, which suggested that neither the shape of the potential curves for surface OH groups nor indicators of acidity.
frequency of vibration
More reasonable characteristics were proposed to be
the protonic charge and the heterolytic dissociation energy of the OH group. The effect of increasing Si/A1 ratio on acidity o f zeolites has been investigated by
combinations as shown in Fig 4.4
The charges on the protons
calculated for each unit are presented in Table 4.6.
Increasing the Si
content was found to lead to an increased charge on the bridging proton which leads to an increased bond polarisation and results in enhanced acidic behaviour on the interaction with a
increased protonic charge with increasing Si/Al ratio would appear to be
similar to the proposal of Jacobs (38) concerning the effect of increasing electronegativity it is,important to note that the model of Kazanski ( 3 6 c ) is concerned with local effects on a particular bridged unit.
In the correlation
proposed by Jacobs (38), in addition to the local aluminium content, the influence of all the aluminium atoms in the crystal is taken into account. This would result in a continuous spectrum of acidity with the hydroxyl stretching frequency being dependent on the bulk electronegativity which should give rise to only one type of OH group. The local model proposed by Kazansky however predicts that four different types of OH group should be present, corresponding to the four units of Fig 4.3, the relative quantity of each one being dependent on the Si/A1 ratio of the particular investigated.
1 all four types of OH groups should be
present, whereas for high-silica zeolites ie S i / A Y 7 only one form should be observed and its acidity should remain constant for values above 7.
available experimental data does provide support for a localised model which explains (a) the simultaneous occurrence of several hydroxyl groups with different acidity (Section 1 . 3 . 2 1 and (b) the constancy in acidity at higher values of Si/Al (Section 1.3.21.
However, longer range effects presumably
generate an acidity spectrum within each particular type of hydroxyl site resulting in the more complex acidity spectra seen by TPDA. Moreover, this model is over simplistic in that it takes no account of structure nor of any factors influencing the distribution of aluminiums within the zeolite framework.
is evidence for
preferred siting in some zeolites and distribution may be more or less ordered.
Consequently the local composition may not reflect the global
framework composition so that the value of Si/A1 = 7 should not be accepted as uniquely defining all the acid sites in any zeolite with that framework composition, and this is discussed subsequently. A modified CND0/2 study was carried out by Chen et a1 (142) and Geerlings et a1 (137a) into the acidity of silica
To account for the
effects of framework termination, the cluster models were terminated by hypothetical hydrogen-like atoms, L, with variable electronegativity.
allowed for cluster models in which the negative oxygen charge was the same as the positive charge on Si thereby simulating fragments with a large number of tetrahedra.
Variation of the electronegativity of the L atoms demonstrated
theoretically the greater sensitivity to structural composition of bridged type hydroxyl
molecular orbital calculations have been reported by Kazansky (148) on the
electronic structure of the protonated intermediate formed by the transfer of a proton from an acidic centre of an aluminnsilicate surface and from a molecule of sulphuric acid to an ethylene molecule in the absence of solvation effects.
In both cases the most stable state was found to be an ester with a Evidence for carbonium ion
moderate positive charge on the ethyl group. formation was not present.
This result was presented as evidence that inn
pair formation arises as a result of secondary solvation effects in the liquid state.
The authors conclude that the absence of such effects in the gas phase
aluminosilicate surfaces casts
ion-type catalytic mechanisms.
doubt on proposed
in favour of carbenium ions this is somewhat surprising. remembered
However, in view of the experimental evidence
stabilisation of ions in zeolites (section 1 . 3 . 2 1 .
It must be influence
MINDO/3, INDO and CND0/2
methods were used by Gorb et a1 (149) to calculate the stabilisation energies associated with the interaction of the bridged and open forms of protonated ethylene and benzene with a charged surface centre or with a polar solvent. The bridging forms were shown to be more strongly stabilised on a charged surface and the open ones in a polar solvent. In conclusion it can be said
the application of
molecular orbital methods to the investigation of solid acid sites has proven useful.
Computer cost is much
than for similar ab-initio
calculations of this type are adequate. TABLE 4.6 Calculated Protonic Charge (q,)
OH I OH I1 OH I11 OH IV SiOH
for Units of Fig 4.l(b)
No of surrounding A1 atoms
1 2 3
3 1.7 1
0.404 0.392 0.384 0.376
Acidity and the siting of Aluminiums in Zeolite Frameworks Early studies showed that acidity increased with increase in framework
Si/A1 in the order NaHX(NaHY
Consequently, the dilution of the
aluminium concentration in the framework was recognised as a factor leading to increased acidity per site.
This was emphasised by careful work on the
dealumination of faujasitic zeolites which established (68)(72) that: a typical Y zeolite ( -
56 Al/u.c.) strong acidity was detected after about 30%
exchange of Na for H ions, indicating that about 30% of the aluminiums were associated with weaker acid sites; (ii) the effective acidity
acid site increased with dealumination up to a ratio S i / A l c z 6 (iii) about 30% of the aluminium was more easily removed during dealumination, than the remainder and (iv) only strong acidity was observed with faujasite frameworks containing 35 or less aluminiums per unit cell. that
These results which suggested
interpreted (150) by the recognition that, subject to Lowenstein's rule, the closest
neighbours diagonally opposed in 4-rings.
Weaker acid sites were presumed to
be associated with aluminiums within the 4-ring system having more than one diagonal neighbouring aluminium. Proximity of aluminiums rendered them less strongly bound, electrostatically, within the framework and facilitated their removal during dealumination.
Similary hydrogens associated with aluminiums
proximate to other aluminiums were predicted to be weaker in acidity because of their increased interaction with surface sites. Discussion of aluminium distribution in faujasites is clarified by the recognition that the crystallographically identical 'T' sites are in three 4-rings, two 6-rings and one 12-ring (Fig 4.5). The first 'TI atom coordination sphere for any A1 atoms must consist of four Si atoms (Lowenstein rule).
The second IT' atom coordination sphere
contains nine T atoms (sites 1 to 9 in Fig 4.5) which may be either A1 or Si. Aluminiums in the 4-ring second neighbour sites (1,5,8) are at a shorter distance than aluminiums in the remaining second neighbnur sites (2,3,4,6,7,9) and presumably interact more strongly with the central aluminium. the 4-ring system
, therefore, results in four types of site for an
' Ia,b,c,d) and second (1 to 9) cwrdition spheres of a framewwk'T' a h . (Ref. 152).
MWINIW A M Y U
Fg.4dDistributim of types of Al atoms in fwjasites. (Ref. 52). unique structures of Cambridge group. d e e d unit ceIl(26).
TYPES OFAl ATOH
Fjk7.BAluminium fraction from ?Si NMR ?9Si NMR intensities of dealuminated Y zeolite. ( m t h curves calcdated for a random distribution of All
81 aluminium atom which may have 0 , 1, 2 or 3 diagonal neighbour aluminiums (Fig 4.5).
Weaker acid sites, which are observed at higher levels o f
aluminium, are associated with increased aluminium site density. An
acidity "spectrum" for faujasites was obtained (151) by calculating
the relative numbers of sites Ni (i
0, 1, 2, 3 ) , for a range of framework
compositions (Si/Al), assuming a random distribution of aluminiums (subject to Lowenstein's rule) over 'T' sites.
Population densities for the four types of
acid site were in agreement with thermal analysis for a Y zeolite with about 50 A 1 per unit cell (151) (Fig. 2.8). This approach was
include other models
distribution and further consideration was given to end effects to reduce
A separate approach utilized the siting of aluminiums in
possible bias (152).
independent 6-rings to investigate the first coordination sphere of silicons in faujasite frameworks (153). The relative numbers of types of aluminium site, based on several models are readily calculated from published data (153).
If the probability of
occupancy by aluminium is the same for the three diagonal 4-ring sites (1, 5, 8) then this is given by N
NAl 3 ! / ( 3
3-i i P) P
where N(i) (i = 0, 1, 2, 3) refers to the type of site, NAl is the total number of aluminiums per unit cell
P is the probability that a diagonally opposed site is occupied by Al.
In general fractional occupancies of the three diagonally opposed sites (1 and 5 or 8) may not be equal in which case the above expression must be extended
as appropriate. and gives results for the N at (i) (i) different framework compositions (Si/Al), for two extreme model distributions Fig4.6 shows the types of site N
of aluminiums in zeolites.
One model is based on a completely disordered and
the other on a completely ordered structure. Strong acidity has been associated, variously, with the No sites which, since they have no aluminiums as second 'T' neighbours in the 4-ring system, may be regarded as isolated sites o r with both the No and N1 sites.
faujasite frameworks cannot be synthesised at low aluminium levels so that comparison of computed and experimental results over a range of Si/A1 is limited.
The aluminium content of zeolite Y can be reduced by dealumination
or secondary synthesis procedures (Section 18.104.22.168 and Chapter 7 ) but the effect of dealumination on the relative numbers of sites depends on the initial distribution and the relative rates of aluminium removal from the various sites. A theoretical treatment of changes in Ni on dealumination based upon initially specified values and on specified values of (first order) rate constants for dealumination is available (151) but
treatment awaits experimental determination of rates of dealumination. However, estimates of different types of silicons are available from 29Si solid state NMR.
These data (Fig 4.7) which reflect different treatments, operators
etc, are well-scattered, particularly for the Si(lA1) signal which may reflect some contribution to intensity from >Si-OH centres. /
for random placement of aluminiums
especially at lower A1 levels.
Of more significance is the fact that the
Si(2A1) peak persists to relatively low levels of aluminium which means that some aluminiums have a second aluminium within the full (9 atom) second 'T' atom coordination shell, and consequently are not isolated, in the range of global composition where catalytic results suggest there is only one type of site.
This suggests contrary to present opinion, that at higher values of
Si/A1, aluminiums linked through 0-Si-0 to a second aluminium may be as active as isolated aluminiums.
However, it must be accepted that NMR is a bulk
technique and results of the kind shown in Fig 4.7 may reflect inhomogeneity in samples so that this point requires further investigation. Although topological termination is taken at the 4-ring 'T' sites on the second coordination sphere for the specification of No, N1, etc, it is clear that particular sites could be modified if a more extended topology is considered. For instance taking the full second coordination sphere of 9 IT' atoms into account it seems reasonable that although aluminiums in these sites are farther from the central aluminium than those in the 4-ring system they may have some influence.
In which case aluminiums of type 'i' could vary
somewhat due to perturbation by different arrangements of aluminiums in the extended second or even higher coordination spheres. In applying the results of calculations of N. to acid catalysis it is necessary to make assumptions regarding their involvement. Only the strongest sites (N ) may be considered, or, a weighted average could be used depending 0 upon the particular reaction. An attempt to provide an answer to this type of question leads to the development of a parameter 'P' based on the 4-ring system and a parameter Q based on the full second coordination sphere of 'TI atoms (58b)(152).
Parameter P is the average occupancy by aluminium of one of
83 the three diagonal second neighbour sites (1, 5, 8) for an aluminium in the 4-ring system.
The parameter Q extends this over the nine second neighbour
composition (Si/Al) and on the distribution of aluminiums over 'T' sites. the aluminium content of the framework tends to zero P(Q) experimental values for effective acidity in zeolites by (1
P ) or (1
can be approximated
Q ) as can some catalytic properties
parameters, therefore, reflect the self-shielding of aluminiums in
faujasite structure ranging from a value of zero at zero aluminium to unity at the maximum loading allowed by Lowenstein's rule (Si/Al = 1). Considerations of average acidity have utilised the average distance of separation of aluminiums and the topological density of aluminiums (58e) which is the product of the aluminium fraction and the topological density of 'TI sites taken over the second to the fifth coordination layers of tetrahedra around a 'T' site.
In this latter study (58e) relative rates of reactions
involving strong acid sites and relative effective acidities are presented as a function of framework composition for a series of zeolites (FAU, MOR, LTL and MOR).
The framework composition(Si/Al) below which aluminiums should have
no aluminiums in the second layer of T atoms is given for these zeolites based on a value for faujasite estimated by extrapolation of the experimental effective acidity of faujasitic zeolites ( E ) to a value of unity where Si/A1 = 5.8.
An earlier topological model dealt with acidity in zeolites and included a consideration of compensating cations (154).
Results were compared with
computations from a model based on a binomial distribution of Si and A1 over second neighbour
'TI atoms and correlated with acidity measurements and
catalytic results on faujasite and mordenite. However, there are some difficulties in relating strong acidity to 'isolated'or other types of site without reference to structure. In general, the IT' sites in zeolites are not all equivalent crystallographically,as they are in faujasite, and detailed structural features for example bond angles and lengths can affect acidity at a given site.
Moreover, there is some evidence
that aluminium shows preference for particular sites in some zeolites. Preferential siting of A1 in the 4-ring system of H-ZSM-5
is used to explain
(78)the observed enhanced activity consequent upon mild steaming ( 7 8 ) ( 7 7 ) .
Hydrothermal treatment is presumed to dislodge one aluminium from a 4-ring site containing two aluminiums. The proximity of the resulting framework and dislodged A1 atoms is presumed to give rise to an enhanced activity, in hexane
84 cracking, for the A1 remaining in the framework IT' site. Since, in the unmodified zeolites, catalytic activity constant
over a wide range of aluminium levels (58a)(66) up to compositions
where extensive pairing is predicted this means that, in H-ZSM-5,
with either zero (isolated) or one second neighbour aluminium contribute equally to catalytic activity.
Consequently we should not expect to find
correlations with the number of "isolated" sites.
It might be argued that
pairing in four-rings of H-ZSM-5 is exaggerated and that, in a general case, providing the number of preferred sites in a zeolite structure sufficiently exceeds the number of aluminiums then preferred siting may not distort results too much.
Additionally the mobility of hydrogens in silica-rich zeolites may
smooth differences resulting in an "averaged" effect. possibility
of pairing must
discussion of the acidity of pentasils.
MO calculations (155,156) do not and sorption
suggest extensive pairing of aluminiums in 4-rings of ZSM-5,
results suggest that not all the aluminiums are confined to 4-rings in mordenite.
Moreover, the * ' S i
NMR results (Fig 4.6) suggest that aluminiums
may not be "isolated" at Si/A1
in the faujasite structure, a conclusion
also suggested in the case of H-ZSM-5 and mordenite by 29Si NMR (157,158). It must be concluded that a constancy of turnover number etc. over a range aluminium levels, which implies that sites have equal activity, does not prove that aluminiums are, in all cases isolated and this should not be presumed.
1.4.3 Electronegativity Concepts and Zeolite Acidity The
electronegativity of neighbouring atoms is well documented.
the Sanderson intermediate electronegativity ( S ) is found to correlate well with many zeolitic properties, including acidic and catalytic properties (38). According
the principle of
different atoms, when combined in a molecule, achieve a common (intermediate) electronegativity
electronegativity is given by the geometric mean of the electronegativities of the constituent atoms.
For example, the hydrogen forms of dehydrated
zeolites, with framework aluminium fraction x/(l HxAlxSil-x02
+ x), may be written (58c) as
with intermediate electronegativity (SHz) given by
on any particular atom with atomic electronegativity ( S . ) is
calculated, taking as a reference NaF (assumed to be 75% ionic), from the intermediate value ( S HZ) as (ji= ( SHZ - Si)/2.08
Note, since example
linear function of SHz the charge on particular atoms, for
equivalent in correlations involving experimental data.
Moreover, since the
electronegativity of silicon exceeds that of aluminium electronegativity ( S ) and the charge on the hydrogens HZ silicon replaces aluminium in the framework.
Additionally, this formulation allows, at least in principle, for the effects of cations and of 'T' atoms other than A1 or Si in the framework,
that a single parameter can be obtained for effective correlation (Fig 4.8). However, since the intermediate electronegativity is determined by composition it can take no account of properties which are strongly structure dependent. Preferential siting of aluminiums or local compositional o r differences at active sites cannot be structurally
electronegativity do not, in many cases, appear to reflect experimental results at low levels of aluminium.
For example, in well prepared H-ZSM-5
zeolite the turnover number for n-hexane cracking is constant over aluminium loading down to very low levels of aluminium (66).
However, if turnover
number is a linear function of electronegativity it should continue to increase as A 1 4 0 as indeed should the charge on the hydrogens.
the rate of increase of intermediate electronegativity (SHz) with decrease in aluminium content reaches it maximum value (for 0 zeolites) when A1+0
0.5, typical of
as may be seen (58c) by differentiation of equation ( 7 )
with respect to x (mol fraction of aluminium).
Results for other zeolites
also' suggest that, at low levels of aluminium, properties tend to become linearly dependent upon aluminium content rather than electronegativity and, although discontinuities may arise in very highly dealuminated zeolites as A 1 4 0 (Section 3.2) there are no reports of maximal turnover as A 1 4 0 in any zeolite structure. However, intermediate electronegativity is clearly a feature in the physical/ chemical properties of zeolites and related materials and excellent correlations over a range-of
composition testify to the utility of the
concept. Recent theoretical formulations (160) confirm the electronegativity
a) Acid hydmxyl stretching frequencies.
blShift in OH frequc cy sorption of benzene.
I cl Catalytic
acfiity CH3 CH (OHlCH3 =CH, 423K -CH,CH Integral reactor.
Fig.4-8.Dependence of some zeolite Properties on intermediate electmgativity. - (38).
equalisation to a common intermediate value as proposed by Sanderson and describe conditions sufficient for the
principle. The concept of orbital electronegativity has also been utilised in zeolite
electronegativity is maintained but partial charges on crystallographically distinct atoms of the same element are distinguished due to differences in bond lengths and angles.
Electronegativity (160a,162) may be defined more
generally in terms of the chemical potential of the electrons
where E is the total energy of the system, N the number of electrons and the electronegativity. is
Na Np, 9
If the number of electrons on the atoms in a molecule
etc then the total energy of the molecule may be written as a
function of: charges Zcr Zfi...
(i) the number of electrons on each atom; (ii) the number of etc; and (iii) the internuclear distances
ground state energy of the molecule the equalization of electronegativity requires that
XIS etc so
Using this approach (163) a charge dependent "effective" electronegativity
an atom in a molecule is represented as
represents the isolated atom electronegativity, n>
- ,,N ) andbxkand A"& are corrections to the atomic charge, (4, = 2, q, isolated atom electronegativities and hardness due to the confinement of the atom in a molecule.
Confinement in a molecule or crystal results in an
external potential generated by surrounding charges (q
) at distances R
This potential is represented by the summation term ( fqk /Rap ) which, in a solid, may be evaluated by a Madelung-type summation. This approach is still in development but has already produced some
interesting results on
including those with zeolite frameworks.
Moreover, it demonstrates clearly
the importance of structure type in determining charge distribution and average electronegativity. Differences in the properties of silica polymorphs (Si02) are,
1.4.4 A Qualitative Approach to Zeolite Acidity
Zeolite acidity is also discussed in terms of the principle of "Hard and Soft Acids and Bases" (HSAB) due to Pearson (lOa)(lOb).
A theoretical basis
for this principle may be provided by calculating the energy of interaction between an electron acceptor (A) and an electron donor (B) on forming an adduct (AB).
If the interaction energy (AE) is not too large the wave
functions for the product ( of the reactants ('PA, theory.
may be approximated taking the wavefunctions starting points and utilizing perturbation
Both valence bond and MO
theory give similar results.
simplified case, considering interactions involving only the highest occupied molecular orbital on an atom of the donor or base (H(B)) and the lowest unoccupied molecular orbital on an atom of the acid (L(A)) the interaction energy can be approximated as
QB, QA are the charges on donor and acceptor atoms RAB is the interaction distance is the dielectric constant CH(B) is the MO coefficient of the AO(H(R)) on the donor atom CL(A) i s the MO coefficient of the AO(L(A)) on the acceptor atom EH(B) is the energy of the orbital H(B) and E is the energy of the L(A) (The orbitals H(B) and L(A) are frequently referred to
as the frontier orbitals.
For the aluminosilicate ion the oxygen 2p
orbital may be taken as H(B).)
AB is the interaction integral
The interaction energy is represented as the sum of two terms, the first representing purely electrostatic interactions and the second representing orbital contributions. Although this separation represents the nature of the wave functions initially chosen rather than physical
nevertheless, been found useful in qualitative discussions of acidity to regard the first term, containing classical electrostatic parameters, as an approximation of hard-hard interactions, and to regard the second term, which represents the perturbation energy and depends upon orbital overlap and energy separation, as a measure of soft-soft (covalent) interactions. Catalytic properties have recently been used
(98c) to evaluate the
relative hardness or softness of the anion in aluminosilicate frameworks
Both the acid strength of the site, which determines the base strength of the anion, and the softness of the anion are assumed to determine the final interaction with the incoming base (or carbocation). The reaction of toluene with electrophiles (X
) may be considered as
The pattern established in reactions with different electrophiles is that the harder electrophiles tend to give the ortho- and softer ones the para-isomer. If, for a given electrophile (eg CH30H2+) it is accepted that its hardness will be increased the harder the anion with which it is in contact then the ratio o / p xylene can be used to generate a scale of hardness for various zeolite frameworks.
Of course, the influence of other factors on o / p ,
example, shape selective effects must be eliminated. The following is proposed for increasing softness of zeolite framework anions. Na-M, Na-Y, Ca N -Y, H-M(Si/Al = 150), H-M(Si/Al = 40). H-Y(Si/Al = 175!, 0.15 0.7 Ca0.3Na0.4-Y, HOe3Naom7-Y, H0.7Na0.3-Y, H-Y(Si/Al = 8.5), H-ZSM-5(Si/Al = 36.5) 2+
This suggests that exchange of Na+ for either Ca anion.
or H+ produces a softer
gives softer anions and softness is structure
dependent (M < Y <
selective effects might
However, particularly in the case of H-ZSM-5 shape modify
relationship is found to hold for the Y-type zeolites as reported previously (98a) and also in a series of papers (98b) involving a detailed study of ion-exchanged Y zeolites. It is suggested (98c) that increased softness in the aluminosilicate species (I) favours orbital controlled reactions and, over harder surface anions, charge-controlled reactions are preferred.
methylation of toluene, orbital control tends to give para- and charge control tends to give orthoxylene. The use of HSAB and linear free energy relationships has been
effective in correlating a wide range of chemical reactions and, as zeolites become more widely used in organic chemical reactions, it might be that this approach will be effective in correlating different types of reaction. Immediately it would be helpful to use MO theory on simple clusters to generate a "theoretical" scale of softness for comparison with experimental results.
Acknowledgements We thank BP Research Sunbury-on-Thames for an EMRA for research into zeolite chemistry and catalysis.
JD would like to thank research students and
associates, past and present, and the chemicals industry particularly BP Research Centre, Laporte Inorganics, and CrosfieldAJnilever and Shell BV, for support.
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