1995, 95, 661-666
Turnover Rates in Heterogeneous Catalysis
Department of Chemical Engineering, Stanford Universify, Stanford, California 943055025 Received October 7, 1994 (Revised Manuscript Received Janualy 31, 1995)
I. Introduction A. Definition of Turnover Rate B. Reasons for the Review 11. Measurement of Turnover Rate (or Frequency) or Site Time Yield A. Solid Acids B. Metals 1. Structure-Insensitive Reactions 2. Structure-Sensitive Reactions 3. How to Measure Upper Values of TOF 111. Applications of TOF Values A. Comparisons of Rate Data B. Catalytic Cycles IV. Conclusion V. References
66 1 66 1 66 1 662 662 663 663 664 664 664 664 665 665 666
mass of catalyst. The systematic use of areal rates in comparing catalytic activity of metals used in the form of evaporated films, large single crystals and supported particles or clusters ushered in the era of quantitative measurements of catalytic activity. Yet, ultimately the rate should, if possible, be referred to the number of active sites, because such a rate expresses the rate at which the catalytic cycle turns over: it is a turnover rate or turnover frequency. The purpose of this review is to examine the definition, determination, limitations, and advantages of turnover rates in heterogeneous catalytic reactions. Brief remarks will also be made on kinetic coupling of elementary steps in catalytic cycles, i.e., the mechanism that helps these cycles to turn over in spite of thermodynamic obstacles along the way.
A. Definition of Turnover Rate
The definition goes back to the early days of enzyme catalysis when the rate of reaction was referred to the amount of enzyme and called turnover Fifty years ago, the rate of heterogeneous catalytic number.’O This appellation was unfortunate, as reactions was frequently expressed in so-called arturnover number is not a number but has the dimenbitrary units. Activity was commonly expressed by sion of one over time. Besides, turnover number in conversion plotted us time at a given temperature. enzymatic catalysis usually denotes the maximum In either case, the information made it impossible to value of the rate per catalytic site, at saturation of reproduce the work, even if enough details were the enzyme by the reacting substrate, as defined by provided on the preparation of the catalyst. This Michaelis-Menten kinetics.1° This unfortunate limitradition was so ingrained that arbitrary units were tation is totally unnecessary and provides another used by Otto Beeck in a famous paper1 reporting his cogent reason to avoid completely the use of turnover extensive work on evaporated metal films of transinumber in catalysis. tion metals used as catalysts for the hydrogenation of ethene. Yet, Beeck had measured the area of his To the extent of my knowledge, the turnover films and he could have reported areal rates, i.e., number first appeared in the literature of heterogerates per unit surface area of the films. These were neous catalysis to denote the rate of reaction referred communicated privately later by one of Beeck’s to the number of surface platinum atoms titrated collaborators and used in a comparative study of with dihydrogen on a supported platinum catalyst.ll various platinum catalysts.2 Subsequently, the rate referred to the number of The measurement of areal rates on supported catalytic sites became known as turnover rate, ut, or metal catalysts became possible after the first atturnover frequency (TOF). It is simply defined as the tempt in Boreskov’s laboratory to obtain the area of number of revolutions of the catalytic cycle per unit supported metal particles by chemisorption of dihytime, generally the second.12 It is a chemical reaction dr~gen.~ In this way, areal rates for silica gel rate, a differential quantity depending on temperasupported platinum catalysts were obtained for the ture, pressure, and concentrations. Like all catalytic oxidation of sulfur dioxide4 and of d i h y d r ~ g e n . ~ rates, it is hard to measure. Frequently, turnover Boreskov’s technique was then applied for the first rate is replaced by a related, but generally not time to q-alumina-supportedplatinum-reformingcataidentical quantity, the site time yieldl3 (STY),defined lysts containing a much smaller weight fraction of as the number of molecules of a specified product metal than was the case for Boreskov’s catalysts: made per catalytic site and per unit time. that study in the Esso (now Exxon) laboratories revealed that the metal clusters were about 1nm in B. Reasons for the Review size.6 Sinfelt et al. at Esso then used the technique The difficulty in measuring a TOF is not only in to report for the first time areal rates on reforming determining the rate but in counting active sites. In fact, these were called specific rates, Besides, sites may not be all identical. In spite of but this expression is now reserved to rates per unit
0009-2665/95/0795-0661$15.50/0 0 1995 American Chemical Society
as reflected eventually in the size of clusters. there are many advantages in attempting to report a TOF. American Institute of Chemical Engineers. the 1977 Kendall Award and the 1985 Murphree Award. whether it turns over more than once. H. the 1991 Chemical Pioneer Award 01 the American Institute of Chemists: and the International Precious Metals Institute 1994 Tanaka Distinguished Achievement Award. An example deals with zeolites and reactions catalyzed by their protonic Bransted acidic sites. No.S. A third advantage of measurements of TOF on catalytic samples that differ in the amount of active materials that they contain is that they provide a clear experimental test of the absence of artifacts in the rate measurements as a result of heat and mass transfer.i. the same metal but a single crystal. After a lhree-year stay at the University of Califomia at Berkeley as Prolessor of Chemical Engineering. Princeton University Press. first at the Forrestal Research Center as a research associate (1950-1953) and assistant to the director of Project SQUID (1953-1954) and then in the Department of Chemical Engineering as Assistant Prolessor (1954-1958) and Associate Prolessor (1958-1961).1.S. He is also a Fellow of the American Association for the Advancement of Science. 1995. Paris (1980).e.e. Clearly the first task is that they be identified.
these experimental and conceptual difficulties. such comparisons are much more incisive than those made with specific or areal rates. degree in Chemistry from Princeton University. there seem to be cases for which turnover rates have been determined successfully. 1994). As a second advantage. values of TOF are useful in assessing the potential of new catalytic materials in relation to catalysts in current use. together with the method of counting sites.
/I. des Lenres et des Beaux-Arts de Belgique and its Royal Belgian Academy Council for Applied Sciences. 1974. 3
Michel Boudarl was bom in Brussels. He graduated from the University 01 Louvain with a B.. the number of turnovers during which the catalyst has lasted is a direct measure of the potential lifetime of the catalyst. and an Honorary Fellow 01 the California Academy of Sciences. values of TOF measured under identical conditions on samples of a catalytic material exposing different crystallographic planes or containing clusters of different size. and the National University of Saita (Argentina. Stanford University).. The focus is on the determination of the amount of catalytic sites. nique de Lorraine. Utah). a value of TOF can be reproduced in different laboratories. Kinetics of ChemicaiProcesses (1968). Next come two questions: are the sites identical and do they interact? Generally. the Wuhan University of Technology (Wuhan Hebei). In 1950 he received his Ph. and Beijing Polytechnic University in the People's Republic of China. Vol. Solid Acids
The arduous problems faced in the correct measurement of the rate of heterogeneous catalytic reactions in the absence of heat and mass transfer. R. If the atomic ratio of AI to (Si + Al)remains small. Anderson) of Catalysis: Science and Technology. originally published as Cinetique des reactions en cafalyse heterog. The Catalysis Society selected him as the 1986 Ciapena Lecturer. This is useful information in theory and in practice. Tokyo (1975). are not considered in this review. 95. as was the Catalysis Symposium of the 68th ACS Colloid and Surface Science Symposium (June 1994. He has received a doctorate honoris causa lrom the University of Liege. the American Academy 01 Arts and Sciences. and is currently a Fairchild Distinguished Scholar at the California Institute 01 Technology (1994-1995).4ne (Masson.662 Chemical Reviews. Salt Lake City. Michel Boudarl is a founder of Catalytica. Wilhelm Award in Chemical Reaction Engineering of the American Institute of Chemical Engineers. the University of Notre Dame. it can immediately reveal whether the catalyst is truly a catalyst. He is a member of both the National Academy 01 Sciences and the National Academy of Engineering 01 the United States of America. activation. degree (Ingenieur Civil Chimiste) in 1947. Cambridge (1984). At the other extreme. As a participating scholar in the Chinese University Development Project of the World Bank. The Symposium "Advances in Catalytic Chemistry 1 1 r (May 1985. 0. Paris. Measurement of Turnover Rate (or Frequency) or Site Time Yield
A.. Rio de Janeiro (1973). It can be compared to a value of TOF obtained on a different catalyst. which he chaired from 1975 until 1978. He has published more than 250 journal articles and holds lour US patents. 1982). interactions between A I ions and
. he remained at Princeton University until 1961. if the method and conditions of measurement of the rate are fully described. In a theoretical or mechanistic sense. he has visited Fudan University (Shanghai). But in spite of the difficulties. Vol. even if a value of TOF is only approximate because of the approximations made in counting sites. below ca. especially because identification and counting must be ideally camed out in situ.D. and Sigma Xi. was organized in his honor. degree (Candidature Ingenieur) in 1944 and an M." Zeolites are silicoaluminates that are available by synthesis in the form of pure single crystals of micrometric size. i. the R. e. there exists no unambiguous answer to these questions. Inc. has been translated into Japanese. Spanish. His honors include Belgian American Educational Foundation Fellowship.. Curtis McGraw Research Award of the American Society for Engineering Education. 1984. and French and was reprinted (1991) in the Bunerworth-Heineman Series of Chemical Engineering Reprints. both of the American Chemical Society. poisoning. or is merely a reagent. and the lnstitut National Polytech. Their crystallinity can be excellent. He selves on a scientific advisory board for the Brookhaven National Laborary and is a member of the Technology Advisory Board for British Petroleum. and deactivation. or a different material. Alter graduation. indicate the importance or nonimportance of crystalline anisotropy. 1948. He is co-editor (with J. during the catalytic reaction.g. Djega-Mariadassou). Procter Fellowship. Last. He is also the author of Kinetics of Heterogeneous Catalyiic Reactions (with G. and a foreign member of the Academie Royale des Sciences. First of all. Catalysis by zeolites is a vast subject recently summarized in its science and technology by Haag. 1949. Fourth. Le. He was the Keck Professor of Engineering from 1980 to 1994 and is now Emeritus. 1962. or a different metal. He belongs to American Chemical Society. he became Professor of Chemical Engineering and Chemistry at Stanford University in the Department of Chemical Engineering. 1-9 (Springer-Verlag). Michel Boudart has been a Visiting Professor at the Universities of Louvain (1969). Boudart's textbook. the University of Ghent.
No. 3 663
also interactions between their associated protons remain negligible. work
. in addition. the areal rate or the TOF under fured conditions does not depend or depends only slightly on surface crystalline anisotropy as expressed on clusters of varying size or on single crystals exposing different faces. Why not report a turnover frequency referred to the number of one or several types of surface atoms? For supported metals. a linear correlation between activity and concentration of Bronsted sites was also found. if there is one.l2 But whatever may be the explanation of structure insensitivity when it is observed on a supported metal. the question is whether surface reconstruction.22 More recently. the lack of effect of particle size was first noted for the hydrogenation of cyclopropane on supported Pt. if thermodynamically favored. structure sensitivity might still be observable.14 In that range.12 How is it possible to avoid significant effects of surface crystalline anisotropy on areal rates of values of TOF? First of all. both in the measurement of rate and in the counting of sites. Moreover. the rate-determining step in the reaction is the dissociation of hydrogen on this overlayer. “Turnover frequencies (TOF’s) for a variety of acid catalyzed hydrocarbon reactions could be determined for the first time.” It must be noted that this achievement in catalytic science was driven by its many industrial applications. just as in the case of zeolites discussed above. “The possibility to synthesize zeolite catalysts with a well-defined pre-determined number of active sites of uniform activity is certainly without parallel in heterogeneous catalysis. An operational definition of structure sensitivity is that the areal rate of the reaction or its TOF depends on surface crystalline anisotropy revealed by working on different faces of a single crystal or on clusters of varying size between 1and 10 nm. Haag concludes.20 Indeed. but rather the number of surface atoms counted by a fully described titration by chemisorption following a method that has been calibrated by means of independent physical techniques. For seven other acidcatalyzed reactions. it is not possible to be sure that all of the possible support effects12have been eliminated.l’ The effect of particle size was first observed for the synthesis of ammonia on supported iron.18respectively. for instance. a single crystal or both. in the range of composition covered in this study. Vol.lg Otherwise. at constant temperature and pressure. 1995.
I. Historically. Maybe.^^ If. turnover frequency has been measured for the same reaction under identical conditions on several faces of a single crystal of the same metal. should consist of only one surface metallic atom or of two adjacent ones at the most. identical or almost equal values of TOF were obtained with metal clusters supported on one or several carriers and on single crystals of the same metal. albeit in a more limited range of SUM ratios. Indeed. Indeed.17 must therefore be regarded as a critical step forward in the evolution of catalysis by metals toward a quantitative science. 95. and Somorjai. lWith ~ sodiumfree ZSM-5 (MFI) zeolites. the strength of such a statement relies on the fact that the same. But even with a catalytic site
consisting of a single metal atom. or a very close. was found to be strictly proportional to the A I content. the catalytic site involved in the rate-determining step.” Haag also adds. all accessible surface atoms can be considered as equally active sites. as pioneered by Kahn. surface reconstruction has been shown to be one of the possible mechanisms accounting for chemical oscillations in heterogeneous catalysis. rate. Such a value of TOF may be considered as a true one. for a structure-insensitive reaction. there may be sites that are inaccessible to reactants. can be reached kinetically in a catalytic run. yet was made possible by the synthesis of pure single crystals of the catalytic material. even with the best reproducible work on supported metals.21 Reconstruction of catalytic surfaces in adsorption or catalysis so as to minimize surface free energy was indeed proposed and advocated by Boreskov as a general principle in heterogeneous catalysis.Turnover Rates in Heterogeneous Catalysis
Chemical Reviews.16 But the concept of structure insensitivity and sensitivity received unequivocal confirmation from studies of the two above reactions on single crystals of platinum17 and iron. the surface coverage during reaction should be close to saturation and surface reconstruction at the few remaining isolated sites might have erased surface anisotropy altogether. This question will be reexamined below in connection with structure sensitive reactions. But again. This situation has been examined and reviewed by Barthomeuf: it depends on the topology of the zeolitic f r a m e ~ 0 r k . a range of almost 4 orders of magnitude. all catalytic sites are identical and noninteracting. The availability of TOF values on single crystals at pressures equal to those used with supported metals. Structure-lnsensifive Reactions
For a number of well-investigated reactions catalyzed by metal. Thus. Such an explanation has been proposed to account for the structure insensitivity of palladium in the oxidation of carbon monoxide on single crystals and supported clusters at pressures between 10-I and lo2 mbar. Clearly.
B. on certain faces of a crystal. Metals
The situation depends on whether a given reaction is structure insensitive or structure sensitive. the areal rate does not seem to be the best way to report the rate data. it is not the surface area of the metal that is measured. These striking results have been discussed in detail elsewhere. structure sensitivity should be recognizable. Indeed. the surface of a Pd tip used in field ion microscopy reconstructs as a result of CO adsorption at 1mbar. insensitivity to the subjacent metal structure becomes understandable. in many cases.23In every case. the lack of interaction between protonic sites has been checked by measurements of the specific rate for n-hexane cracking on samples with SUM atomic ratios between 15 and almost 100000. Another possible explanation of structure insensitivity is based on the formation of a reactive hydrocarbon overlayer on a metal surface during a catalytic reaction involving hydrocarbon^. Petersen.
This reconstruction is brought about or stabilized by catalyst promoters and/or by ammonia used in the reduction of the catalyst. Thus.20 These comparisons have led to the discovery of a new support effect consisting of the surface diffusion of CO adsorbed on the support t o the interface with supported palladium and subsequent reaction with oxygen. For ~ ~ the oxidation of carbon monoxide on palladium. one obtains a
mean or apparent value of the TOF that is a lower limit. Further applications of SSITKA to the direct determination of TOF without counting sites may well be another significant advance in the quantitative kinetics of catalytic cycles. differ only by 10%. it was shown that by far the most active face of iron single crystals in ammonia synthesis at 20 bar was the (111) plane by more than 2 orders of magnitude for the areal rate. With only one unit. for the hydtogenation of cyclohexene. In their application of SSITKA to ammonia synthesis on supported Ru catalysts. 25 Surface reconstruction again leads to the possibility of reporting what is believed to be a true TOF. say. How to Measure Upper Values of TOF There exists a technique that measures directly an upper value of the TOF without the necessity of identifylng and counting active sites. This will be also the first documented example of a structure-sensitive reaction on a metal surface that is reconstructed so as to expose the most active sites. it is because of anomalous TOF values that the supply of molecules of CO by surface diffusion could be assessed and explained quantitatively. a value for the TOF on Fe(ll1) can be obtained and extrapolated to TOF data on ammonia synthesis at 1 bar on a multiply promoted industrial catalyst. other hand. as in the case of the iron industrial catalyst for ammonia synthesis. If 8 is assumed to be unity. Structure-Sensitive Reactions
The best example is ammonia synthesis on iron. Another application of TOF values deals with the frequent occurrence of poisoning. by the chemisorption of hydrogen. sites..664 Chemical Reviews. what we call (T0F)minand (TOF). since there may be a distribution of activity among sites. This technique is called steady state isotope technique for kinetic analysis (SSITKA). This also suggests saturation of the active surface with adsorbed nitrogen (8 = 1). If so.18 This was attributed to special sites with a coordination number equal to 7. Goodwin and Nwalor report the following:28 on an unpromoted Ru catalyst.26 Indeed. Comparisons between supported and Wilkinson homogeneous rhodium catalysts for the hydrogenation of cyclohexene show very close values of TOF under similar ~ o n d i t i o n s . this comparison suggests that the industrial catalyst exposes predominantly the optimum C7 sites that are by far the most active ones in the reaction. (TOF)min.. it must be pointed out
.28 Ideally. where 8 is the fraction of active sites covered with the most abundant reactive intermediate involved in the ratedetermining step. The area under the exponential relaxation curve is a relaxation time r.30 It is hard to imagine how this effect would have been identified without the use of TOF values.28
Ill.27it will be the first time that a true TOF has been reported for a structure-sensitive reaction on a complex commercial metallic catalyst. as suggested earlier in work on supported iron clust e r ~ With . although possible complications may arise. The two TOF values agree within a factor of 2. the reported value of (TOF). 3. and of clusters supported both on a-Al203 single crystals and on high specific surface area y-A1203. No.26 Because of the uncertainties in the extrapolation and in the counting of iron sites on the industrial catalyst. It is also another example of the decisive results that can be obtained by studying a catalytic reaction on large single crystals at high pressures as started in the Somorjai laboratory.and (TOF). 1995. a typical structureinsensitive reaction. Indeed. namely the second. differ by a factor of 10 but on an Ru catalyst promoted with potassium oxide. some supported PUy A 1 2 0 3 catalysts were found to be poisoned with sulfur originating from sulfates on the support. if the number of sites is assumed t o be equal to the total number of surface atoms counted. If this tentative conclusion is firmed up by further observations on a working industrial catalyst. Applications of TOF Values
A. one On the obtains an upper limit t o the TOF: (TOF).12 values of TOF calculated by counting surface platinum atoms not covered with sulfur by means of hydrogen adsorption were found t o remain constant. TOF values at low and high pressures and low and high temperatures have been compared in the case of large single crystals. a reaction that continues to be of great industrial importance. ~ ~ these results.31 Again. the C. clearly a minimum value. The average measured TOF would be 5 x lop2s-l. the TOF is equal to 8/z. it may be con~ l u d e tentatively d~~ that the potassium promoter has brought about a reconstruction of the Ru surface to expose almost exclusively the most active sites. must also be close to the true TOF for ammonia synthesis on the promoted catalyst. 95. Comparisons of Rate Data
2. say from 14N14N H z to 15N15N+ H2 and the relaxation of the composition of the product expressed as [14NH3Y[14NH31 [15NH31 from unity to zero as a function of time.18 Thus. rate data in arbitrary units or plots of conversion us time are becoming the exception rather than the rule in the scientific literature of catalysis. in which the steady state of a catalytic reaction running in a continuous reactor with complete mixing is suddenly perturbed by a sudden switch of reactants. Vol. assume that 50% of the sites counted by a chemisorption method have a TOF of 1s-l while 50% have a TOF of s-l.. a value of turnover frequency offers a straightforward way to compare data obtained in different laboratories.. 3
with large single crystals becomes the standard by which the quality of the work on supported metals can be judged. (TOF). For the hydrogenation of cyclohexene. Within the latter approximation. The surface reconstruction of supported iron clusters with appearance of (111)facets after exposure to ammonia was reported earlier following studies with Mossbauer effect spectroscopy.
This problem is closely gives a more direct comparison. been identified as structure insensitive. It is the kinetic A major obstacle in the correct measurement of coupling between the elementary steps of the cycle. Catalytic Cycles size single-crystal zeolites exhibiting identical and noninteracting sites.34 In each cal and noninteracting. if proceeds in the forward direction at a rate that the same value of TOF is obtained for a given exceeds sufficiently the rate of the preceding step in reaction at fixed conditions on two catalytic samples the reverse direction. a particular step in the cycle that could be the ubiquitous parasitic effect of heat and mass equilibrated so as t o be severely limited by equilibtransfer. concept of TOF in heterogeneous c a t a l y ~ i s . What ~~. closed in structure insensitive reactions on metals. An important consideration application of TOF values in the assessment of in the understanding of what makes a catalytic cycle catalytic rate data.33 To be on the safe side. and H o r i ~ t i . The classical have been raised about the applicability of the example is ammonia synthesis on metallic iron. agreed under identical lytic cycle has taken hold largely as a result of the conditions with TOF values obtained on a platinum use of the measure of the catalytic rate as a turnover single crystal. These ideas have been developed on both samples. turnover is also a kinetic one. so well in practice has led to controversies that flare Finally. thanks to the well-known electronic rules describing their behavior. What kind of activity is We conclude that the concept of TOF is paramount it? And how does that activity compare with that in any form of catalysis. for instance in the related to the model of a Langmuirian surface case of molybdenum carbide as compared to rutheconsisting of adsorption and catalytic sites. This may explain why so many containing different amounts of metal on the porous catalytic cycles do proceed with a high TOF in spite support. the TOF be disfavored thermodynamically in the absence of should be measured at two different temperatures kinetic coupling. what is the value of reporting a without changing the rate per exposed iron atom. By TOF? contrast. previo~sly. Thus. Temkin. in the case of supported metals. through the hours representing the active intermediates and back to the starting point.12 frequency. especially with new matericeptable. cases are presented for which both TOF for the reaction. values of TOF can be obtained even in the closed sequences in catalysis or chain reactions was developed by Christiansen.. 95. Here again. all identinium for the hydrogenolysis of alkanes. serious questions the role of promoters in catalysis. it maintains higher specific area are not all the same. a catalytic reaction was presented Values of TOF can also be obtained in the case of as a closed sequence of elementary steps. the method used in counting sites knowledge that makes this model generally unacmust be fully described. ~ ~ describe data in a manner that is correct if not rigorous. This is a Thus. the mechanistic question is how. when surface reconstruction under high surface coverage obliterates non-Langmuirian sequence as a cycle turning clockwise from twelve behavior.
No. TOF values are true values. potassium oxide promoters do change the In this review. o’clock. ~ ~case of a structure-sensitive reaction on model and It was Chad Tolman’s idea to represent the closed real catalysts.Turnover Rates in Heterogeneous Catalysis
Chemical Reviews. per iron atom exposed.12 Why it works of the sites. the kinetic data are not disguised by heat of the fact that some of the component steps would or mass transfer. at least Langmuir kinetics and values of TOF appear to at high pressure and high values of c o n v e r s i ~ n . values of TOF come to one-way direction if the next step in the cycle the rescue. Although the of cyclohexene on many platinum catalysts supported Tolman cycle has been adopted so far only sporadion different supports and consisting of metal clusters cally in heterogeneous catalysis. Since catalysis is a kinetic phenomenon. exhibited by prior catalysts? While a comparison of this is also the case in spite of the special problem specific rates may be adequate. Kinetic analysis of Finally. values of TOF obtained for a given the rate at which catalytic cycles turnover is the reaction on a given supported metal are sometimes essential goal of catalytic research. i. By contrast. with consumed in the first step of the sequence and original surface crystalline anisotropy in both cases.e. the concept of TOF forces representation of catalytic cycles has become the rule investigators to make a hypothesis concerning the nature of the active centers and to measure their in homogeneous catalysis with organo-metallic coor-
. especially inside the pores of high specific rium if taken in isolation may actually proceed in a area materials. of course. insofar as it gives in striking d i ~ a g r e e m e n t ~ ~a reaction that has for detailed information on how the cycle turns over. 3 665
that the extensive TOF data for the hydrogenation dination compounds. Langmuirian kinetics is used almost unials for which there is little information on the nature versally in heterogeneous catalysis.~~ In a similar way. Conclusion a certain catalytic reaction. Vol.~~-~~ Another application of TOF deals with new catalytic materials. This In the last analysis. as studied the sense that the entity called the catalyst was with large single crystals or supported clusters. TOF values are most helpful in assessing up peri~dically. regenerated in the last step. In the case of catalysis with micrometerB. In heterogeneous catalysis. but only reminder of the exacting work demanded in catalytic after the cycle has been found to turnover at a rate rate measurements and another example of the measured by its TOF. 1995. intrinsic kinetic data in heterogeneous catalysis is Thus. It is frequently said that a new material is attractive because of its high activity in IV. In spite of all accumulated case. the use of TOF values presented by solid surfaces. Until recently. the notion of cataof size between 1and 10 nm.~~ Values of TOF reveal that promotion by alumina is is a site? How do we define and count them? If they only textural.
C. P. H.. References
amount in a way that can be reproduced from laboratory to laboratory. G.136. 1991. Topsee. 424. Catal.13-7.. J. Thus. it leads to values that can be reproduced in different laboratories. 1956. Boreskov. 1990. and it provides quantitative insights into the working of catalytic cycles. Eds.. 68.. Many prudent investigators omit to report a TOF even when they could estimate one because the rate may have been disguised by mass and heat transfer. C. Studies in Surface Science and Catalysis.36 Rh 5-100 Pd 11-76 2. In the absence of a TOF a site time yield. Gaussmann. K. H.204.53-2. Weisz. Zhur. Leclercq. and Pt differ by less than 1 order of magnitude in the gas phase and even less in the liquid phase.1. Taylor. Lee. L. and the rate was zero order with respect t o cyclohexene. 1982.74. M. J. M. Bennett. the space time yield for large catalytic processes is. Kieken. Bond. Catal. Boreskov.. J . R. Catal. Catal. J.2786.. R. C. Khim. Cheng. Boudart. Catal. Catal. Goodwin. a differential quantity. Boudart. E. Top. G.61.7. 1983. 294. L. W. Khim. G. 1982. K 1956. C. G. Lett. as a result of diffusional limitations into and out of the catalyst grains. S. 1977. Boudart. Djega-Mariadassou. CHEMTECH 1992. Bennett. Catal.136.43
V...44 5.. the order of magnitude values suggested above have been said to be at the center of a window on reality. 1975. M. 1994. Boudart. E. Gas Phase or Liquid Phasea supported % metal TOF. 0. Proc. 6th Intern. A n example of the type of comparison that becomes possible with TOF values is shown in Table 1where the catalytic activity of four different metals for the hydrogenation of cyclohexene is compared both in the gas phase and in the liquid phase. M. Che. Catal. K.. E. A. 1952..32-0. Phys. 305. Fiz.Boudart. Phys. J. 1994. Chem.. Oyama. Lett. P. 1984. Elsevier: Amsterdam. J . NJ. Catal. 127. Boudart. Top. G. R. 1984. Subj. Boreskov. 93. S. 92. M. is always hard to measure.95. 1981.(July). A.55. H.-Sci. Khammouma. s . Eds.25. J. for a given metal.Weitkamp. D. J .22. A. Harkins. L.. A. J .. Hurwitz. 1994.. Boudart. If they are not all equally active.. the concept of TOF is a useful one in heterogeneous catalysis. A. J . p 1.. J. Turnover frequency is by definition identical t o a turnover rate.25. J. 84B.94 0. M. Sajkowski. Bond.21. M. 1975. J. Catalytic Chemistry. 1981. Chem. Congress Catal. Catal. D. H. Second. 405. M. Djega-Mariadassou. C. Boudart. A. all pertinent references given in: Boudart. 1991.17 1. F. Faraday Discuss. 256. B.~ metal exposedb gas phase liquid phase 0. W. J. 1.. 10th Intl. Boudart.438. Boudart. Rel. G.Vol. Catal.87. A.e. W.35-1. 1pmol
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roughly into a STY equal to 1 s-l. For those who hesitate to estimate the number of sites. It is generally agreed upon that the nitrogen BET method of measuring the surface area of solids is based on Langmuirian assumptions that are totally unacceptable. C. 285. Phys.Vol. A turnover rate is even harder to obtain because of the necessity to determine or estimate the number of sites... Boudart. Sajkowski.72 Pt 14-100 2.. D. D. Boudart. S.
. J. Faraday Discuss.. I n Practice.633.In Zeolites and Related Microporous Materials: State of the Art 1994. Hz at Atmospheric Pressure. J. 1993. M. J.J. Similarly. 1993. if rates were much smaller. ButterworthHeinemann: Boston. Shulman. G..30. G. 1991.. J. S. In heterogeneous catalysis. V. 1964. Catal. 70. Chem. E. Academic Press: New York. First. S. 1995. Two facts emerge...36. Aldag.. Khammouma.. Kinetics of Heterogeneous Catalytic Reactions. Lett. 1814. 1994.Proc. J . i.666 Chemical Reviews. 2787. Rh. M.24. Loffler. 0.97. STY.. if rates were much larger.. M. Schoonmaker. Dumesic.92. Princeton University Press: Princeton. and catalyst deactivation..1. J. M.. K. Catal. 1994. 1992. 125. G.90. N. N. 1960.1559. U. Somorjai. G. Spencer. Fiz. D. 1966. 1992.. 1989. Sinfelt.23. Fiz. Pd. B. J . Elsevier Science B. D.16. et al.. C.. G.. 2962.M. Barthomeuf. J . Zhur. M. Sinfelt.37. 5763. J . Webb. Catal. 69.27. Kieken. 19902.. Catal.30.. Boreskov. Taylor. Kinetics of Chemical Processes. D.. Thomson. Heterogeneous Catalysis. at 298 K. Yates. V. 1965. 1976. Catal. the number of molecules of a specified product made per unit volume of reactor per unit time.30. Yates.. G. Reu.. Boudart.. M. Gonzo. F. Chem. Chem. J.17.. 2560. J.66
In the latter case. Chem. M. Dumesic.. W. 1986. Vol. Phys. M. M.88. M. Eng. Phys. Karnaukhov.. N. J. Dougharty..: Amsterdam. S. Catal. Zhur. 64. 0. .64.38 -3. 1945.Slin’ko.656. M. 57. SOC. Catal. V. G.1.1 . 92..I&EC Fundam.17. J. Rev. it is even harder because of problems of heat and mass transfer. Boudart. Chem. . In the units popularized by Paul Weisz. Congr.1. p 1375. H. No.16-1. M. in s-l... J. 1974. Second. the reactor would have to be too expensive for a given productivity.57. 305. G. the TOF in the gas phase is higher than that in the liquid phase by less than 1order of magnitude. I&EC Fundam. Che. also in order of magnitude.. J . cyclohexane was the solvent. 157.Boudart. The Chemical Society: London. M. Adu. Madon. 1993.34. B.Vol. 1991. and D. A.-C. Boudart.71. there is a last alternative: the space time yield. M. Kahn. Sinfelt. it is the number of molecules of a specified product made per catalytic site per unit time. Chesalova.26. J. T. 95. the TOF values for Ni. Haag. Cat. Chesalova. 3
Table 1. the catalyst and thus also the reactor volume would be poorly utilized because the heterogeneous reaction would be confined t o the mouth of the pores of the catalyst. Petersen. 1986. which translates order of magnitude. 1985. Mod. Delbouille. Phys.. H. J. Locatelli. A. Nwalor. S. Phys. et al.42 These values are dictated by two limiting considerations when porous catalysts are used.66 Ni 36-100 1. Boudart. Boudart.I&EC Fundam. Comm. Turnover Frequency (8-l) for Hydrogenation of Cyclohexene.129. D. J. as spelled out in the published papers extracted from Stanford investigations by R. Boudart..6. Phys. Somorjai.55-0. Yet the BET method is the universally accepted method of measuring the specific surface area of a catalyst: it can be reproduced from one laboratory to the next.29. G. M. 1960. G.J .