Applied Catalysis A: General 229 (2002) 7–10

Personal report
Future opportunities in zeolite science and technology

Modern zeolite science and technology arrived at Uniform catalytic acid sites, however, we have not
the half-century mark [1]. The discovery of strong achieved. In addition, it now seems surprising that it
acidity and acid catalysis with zeolites is 45 years old; took us over 30 years to propose the first satisfactory
the first commercial application as industrial adsor- scientific interpretation for the strong acid catalytic
bent reaches between these two time periods, and the phenomena with zeolites. By then, the use of acidic Y
first large, industrial catalytic application is also over zeolites had become the largest catalyst application in
40 years old. And still, the literature reports on new the worldwide chemical and petroleum industries.
zeolite phenomena, and new applications. The ques- The main reason for not achieving uniformity of
tions arise: acid sites rests on the chemical reactivity of tetrahe-
dral framework-aluminum ions to water, especially
• What drives zeolite research and industrial develop-
those adjacent to acidic O–H groups, and the insta-
ments for so many decades in diverse and fruitful
bility of the primary, defect-crystal structure formed
directions?
upon aluminum hydrolysis in the presence of steam.
• Are there still some new, important zeolite phenom-
In view of this experience we may ask the question:
ena to be discovered in the future?
does this chemical liability cast a shadow toward the
Taking the question on what drives the amazing zeo- future evolution of framework-transition-metal zeo-
lite science and technology machine, I think we would lites with uniform catalytic sites? I shall come back
all come to the same conclusions. The uniform in- to this question later.
tracrystalline microporosity, providing access to very The long delay in arriving at a satisfactory interpre-
large and well-defined surface, the molecular sieve ef- tation of the strong acidity of crystalline zeolites prob-
fect, and the strong electrostatic field centered at ze- ably results from the fact that the surface state of crys-
olite cations, promised unique opportunities from the tals remains much more difficult to characterize than
start for important efficiency and economic improve- that of the crystal matrix, especially when the surface
ments in gas and liquid sorption and separation tech- phenomenon of interest is related to a low concentra-
nologies. Indeed, in a short few years the practical tion of distorted, defect sites such as the acid sites.
use of these phenomena resulted in the development Theoretical modeling has been greatly developed in
of a variety of new, diverse industrial sorption and recent years, together with smart software and bet-
separation processes throughout the chemical and fuel ter computers; however, the necessity to consider the
industries, worldwide. long-range crystal effects in zeolites rendered reliable
In catalysis, from the start, the promise of zeolite conclusions via theoretical modeling a difficult target,
catalysts has been the evolution of a new catalyst gen- especially in the early years.
eration, with uniform catalytic sites. This has been Uniform catalytic sites are indeed desirable in all
our aim when we discovered the strong acidity and practical catalytic applications, in order to eliminate
catalytic activity of multivalent-cation X and Y, and very active but non-selective catalytic sites. Clearly,
the NH4 -cation derived, protic forms of Y zeolite. best catalytic process performance can be expected

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8 Personal report / Applied Catalysis A: General 229 (2002) 7–10

where the chosen process parameters are optimized to feature. In addition, oxidation catalysts also need the
all catalyst sites, to uniform sites in the best case. With absence of certain catalytic sites such as acid sites, in
a variety of active sites in a catalyst, at any given pro- order to avoid undesirable secondary reactions. Here
cess conditions some active sites will be inactive while again, zeolites, in spite of their large intracrystalline
the most active sites less selective, relative to the aver- surface, offer excellent control of acid sites by cation
age. Importantly, the need for uniform catalytic sites exchange, either by treatment with salt solution or by
is critical in stereospecific catalysis. Here, especially doping with alkali salts in the anhydrous state [2].
in pharmaceutical applications, the requirements for Of course, the synthesis of any zeolite crystal with
stereospecificity is very high; therefore, uniformity for uniform catalytic active sites is not a simple mat-
active sites is of special importance. ter. First, most zeolite crystal structures have several
Aiming at uniform active sites with zeolite catalysts crystallographically distinct framework-cation sites,
in the future is justified, based on the well-defined in- all with tetrahedral but nevertheless coordinatively
tracrystalline pore system, and the uniformity of atoms distinct configurations. Furthermore, the newly intro-
at same crystallographic positions throughout the zeo- duced guest framework ions with electron configu-
lite crystal. Importantly, in contrast to zeolites, crystal- rations and sizes different from the host silicon ions
lographically well-ordered surfaces for either covalent will form distorted sites, with different bond lengths
(metals) or ionic (metal oxides) crystal surfaces are and angles relative to the host. This may or may not
not readily achievable, especially with small crystals. be a problem, as long as the guest transition metal ion
Namely, well-formed metal crystals prefer recrystal- provides the needed chemical properties for selective
lization in a two-dimensional monolayer at the surface, catalysis. However, even if selective catalytic chem-
while ionic crystal lattice relaxes gradually, resulting istry is achieved by good choice of zeolite structure,
in positional changes in several atomic layers, at the transition metal type and concentration, the chemical
surface. As a result of these relaxation processes, the stability of the catalytic site becomes a major issue
surface state of both metal and oxide crystals tend to here.
represent non-uniform, disordered sites, especially in The progress in the synthesis and characterization
small crystals. of metal-substituted zeolites, and the high catalytic
Recent research in zeolite synthesis shows the abil- activity/selectivity reported, give us hope to realize a
ity to form zeolites with numerous guest cations in great goal in heterogeneous catalysis in the coming
zeolite crystal frameworks. The characterization of years: to develop solid catalysts with uniform active
crystal structures, pores, and guest cation sites are im- sites for a broad range of catalytic applications. This
portant themes. In catalysis, in several cases, catalytic expectation is based on good progress in the synthesis
activity, and importantly the selectivity, is achieved of a variety of transition-metal-ion-substituted zeolite
by the application of transition metal ions substituted crystals, on their catalytic activity, and on the multi-
for silicon ions in zeolite crystals. The low, tetrahe- tude of choices available to further optimize these cata-
dral coordination, the large variety of available zeolite lysts, including the selection of the zeolite crystal type
crystal structures and the large choice of transition and synthesis technique, choice of substituted metal,
metals at uniform framework positions offer outstand- and the application of bimetallic substitutions. In the
ing opportunities to optimize catalytic behavior to the latter case, one of the metals provides direct chemical
needs of the chosen catalytic chemistry. This is spe- interaction (redox or coordinative) while the second,
cially important in oxidation chemistry; namely, we adjacent metal ion is used to “optimize” the catalytic
all know that providing catalytic activity for oxida- site, by affecting the bond structure/coordination of
tion or for redox catalysis is usually not great virtue, the primary metal site or changing the ionic charac-
high selectivity is. Here, because of the great thermo- ter at the catalytic site (more basic framework ox-
dynamic boost given to subsequent oxidation steps, ide). In other cases it may accommodate/restrict the
even traces of catalytic sites of high activity but low catalytic reaction intermediates by topographical ad-
selectivity, can easily counteract the high selectivity justments, even to the extent to achieve stereospecific
shown for the majority of active sites. For these rea- configurations. The multitude of options and controls
sons, uniformity of catalytic sites is a very desirable available in metal-substituted zeolite synthesis will be
 Personal report / Applied Catalysis A: General 229 (2002) 7–10 9

most helpful if they can lead to catalytic sites that exposed to reactant hydrocarbons at ∼500 ◦ C and to
are not only chemically optimized but also similar, air + steam at ∼600 ◦ C.
and ultimately uniform, in their participation of the The interpretation of the high stability of the exten-
physical and chemical steps involved in the catalytic sively steamed H+ –Y may rest on the idea that here,
reaction. the retention or loss of crystallinity depends on the
Of course, there are many challenges against achiev- thermodynamic balance between crystal lattice energy
ing uniform catalytic active sites in zeolites, vide infra. and the relaxation of the protic site by acquisition of
On the other hand, by comparison with other covalent electron density from adjacent Si/Al–O bonds in order
(metals) or ionic (oxides) materials used in catalysis, to form stable sp3 configuration in the O–H bond. It
only zeolites offer a reasonable opportunity to achieve is then important to appreciate the outstanding stabil-
this important goal in heterogeneous catalysis in the ity of the steam treated H+ –Y with only about 2–4%
coming years. of framework cation sites occupied by aluminum ion
A special category of catalysts with uniform [3]. It seems, that at this low O–H “defect-site” con-
catalytic sites is represented by zeolites contain- centration the crystal energy is sufficient to counter-
ing catalytic molecules/complexes occluded via act the destabilizing effect of the protic sites. We have
ship-in-bottle synthesis. Discoveries in this field may used this argument earlier to explain the strong acidity
have great potential, if the chemical and thermal sta- and the retention of the crystal structure of silicon-rich
bility, and the diffusivity of these zeolite catalysts H-zeolites [4,5].
prove to be satisfactory for industrial applications. The important, positive aspect of the H+ -zeolite ex-
With metal-substituted zeolites, the critical problem perience cited earlier is that conceptually, here, a por-
beyond the challenge to achieve catalytic site unifor- tion of the zeolite-crystal-lattice energy is available
mity and good catalytic selectivity and activity, is the to counteract instability, resulting from “acceptable”
limited stability of most guest ions substituted into ze- lattice defects such as those introduced by metal sub-
olite crystal frameworks. The reduced stability relative stitution onto the zeolite framework, up to a certain
to the zeolite host ions (Si, Al) may stem from crystal concentration, where thermodynamics (crystal reten-
stress due to cation size, electronic configuration or tion versus relaxation of OH groups) still favor crys-
it may derive from reactivity to reaction environment tal retention. Based on this analysis we would like to
(water hydrolysis), vide infra. In order to assess the na- propose the following considerations in the synthe-
ture of the problem, and also to find fruitful chemical sis of new, framework-substituted zeolites, intended as
strategy here, it is worthwhile to consider the lessons catalysts:
learned from our experience from four decades of acid
• Be especially conscious of two aspects of crystal
catalysis with H-zeolites. Here, the protic site (acidic
destabilization in new, metal-substituted zeolites:
OH group), based upon the small size and large elec-
topological or bonding defects and chemical reac-
tron affinity of the H+ ion, exerts large electron affinity
tivity (hydrolysis, etc.).
upon adjacent T–O groups and loses crystallinity of
• Evaluate bimetallic substitutions with the idea that
aluminum-rich zeolites (X) while the more silicon-rich
one of the guest ions should correct/stabilize the
H–Y zeolite (and other silicon-rich zeolites) retain
defect introduced by the catalytic guest ion.
crystallinity. However, in the presence of H+ cation
• Evaluate thermal/hydrothermal stability of metal-
the adjacent aluminum ions readily hydrolyze when
substituted zeolite preparations at low (1–3%)
exposed to steam, even at modest temperatures, cre-
T-atom concentration, with an anticipation that at
ating crystal-defect sites. In this process the stability
low concentrations the quest cation sites may gain
of the steam-stabilized H–Y is greatly aided by the
high stability.
recrystallization of the primary, defect framework, by
• Characterize the catalytic sites for uniformity.
eliminating the defect sites by “recrystallization” and
formation of intracrystalline mesoporosity. Finally, we may ask the question whether we have
Importantly, at low framework-Al concentration overlooked some unique zeolite characteristic for fur-
(2–4% framework Al) the H–Y is stable in the ther study and eventual practical application. In indus-
FCC process for several weeks while intermittently trial applications of zeolites, we are using the zeolite
10 Personal report / Applied Catalysis A: General 229 (2002) 7–10

crystal’s large, well-defined intracrystalline pores and References

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Inspiration toward such concepts comes from the
amazingly rapid evolution of micromanufacturing in Jule A. Rabo
the electronic industry, moving down to molecular size UOP LLC
in electronic definition of semiconductor surfaces. In 19 Windmill Road
addition, recent scientific discoveries have shown that Armonk, NY 10504-2612
electromagnetic radiation can be transmitted through USA
micropores, formed in metal films, which are smaller
than the wavelength of the radiation [6]. Received 11 May 2001; accepted 15 May 2001