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Abstract
This review deals with the mechanism that is arbitrarily called below the Mars and Van Krevelen ŽMvK. mechanism. The
characteristic feature of this mechanism is that some products of the reaction leave the solid catalysts’ surface with one or
more constituents of the catalysts’ lattice. First in this review, the position of this mechanism amongst other ways of
catalytic activation will be defined. Then, the experimental evidence for this mechanism will be presented. Some less
common reactions running with this mechanism will be discussed in more detail, among them the deoxygenation of
nitrocompounds and carboxylic acids.
The participation of the lattice components ŽO, S, Cl, H. in the formation of products leads to a relation of the catalytic
activity with the thermodynamic parameters characterizing the catalysts lattice. A proper use of such quantified relation will
be also discussed. q 2000 Published by Elsevier Science B.V.
Keywords: Mars and Van Krevelen mechanism; Catalytic activation; Deoxygenation of nitrocompounds; Deoxygenation of carboxylic
acids; Oxygen exchange reaction
At the same time as Berzelius formulated his catalytic public even then did not really acknowledge
ideas, Michael Faraday explained the catalytic effect the importance of the new idea that oxygen is not
of platinum as Athe result of an attractive force simply added to the reductant but is first activated by
exerted by the solid on the gasesB w2x. In other transformation into a lattice oxygen. The steps of the
words, the catalytic effect is according to Faraday lattice oxygen depletion and the subsequent replen-
induced by the adsorption of reaction components. ishment can even be separated into two consecutive
This idea appeared to be very stimulating; neverthe- steps Žswing reactor., with sometimes an appreciable
less, up till now, discussion is going on regarding the technological advantage Že.g. to circumvent the ex-
problem as to how the adsorption affinities are re- plosion limits.. The real breakthrough in the appreci-
lated to the catalytic effect. A great deal of truth is ation of the idea only took place after the publication
probably expressed by the so-called Sabatier or Bal- of the paper by Mars and Van Krevelen, in 1954 w12x
landin principle w3x: the optimal adsorption bond is and after a series of papers with a successful applica-
neither too weak nor too strong. tion of the idea in the kinetics Žsee e.g. w12–14x..
A mathematical form of Faraday’s idea appeared It can be expected that sulfides, chlorides or
later. The Aactive massB in the expression for the hydrides also can sustain a similar mechanism like
rate is related to the surface coverages that are that observed with oxides. Here, we called it the
calculated from the corresponding Langmuir Mars and Van Krevelen ŽMvK. mechanism, but one
isotherms Žsee w3–5x — in w4x is given the develop- can find for it other names also in the literature:
ment of the theory summarized.. This approach is redox or regenerative mechanism. However, all oxi-
usually called the Langmuir–Hinshelwood kinetics. dations are redox reactions, even when the prevailing
Homogeneous enzymatic reactions were described in mechanism can not be called an MvK mechanism.
a formally similar way much earlier by Henri w6x and To complete the list of various ways of catalytic
Michaelis and Menten w7x. activation we shall mention that with some reactions
With the adsorption mechanism, catalytic reac- radicals are created on the surface which are then
tions occur as interactions among adsorbed released into the gaseous phase where they react
molecules, adsorbed radicals or fragments of the further Žsee e.g. w15–18x.. The well-known examples
reactant molecules. However, it has also been sug- of these reactions are the ammonia oxidation w19x at
gested Žsee e.g. w3x. that a reaction by collision of high temperatures and the oxidative coupling of
molecules from the gas with the adsorbed species is methane w20,21x. Of course, there are also low tem-
possible too. So far, this so-called Rideal mechanism perature oxidations involving radicals w22x, but these
has been only confirmed indirectly, from the reaction reactions involve adsorbed radicals and are thus of
kinetics. the Langmuir–Hinshelwood ŽL–H. type.
In the shadow of the development of the Lang-
muir–Hinshelwood kinetics, another idea on the cat-
alytic activation was, but only very slowly, getting 2. Early experimental evidence for the Mars and
its shape — the idea that the catalysts’ lattice com- Van Krevelen mechanism
ponents appear in the reaction products. Pease and
Taylor w8x studied the oxidation of hydrogen on Roginsky summarized in 1953 w23x his earlier
copper and they conclude their paper with these work w24x on the exchange of isotopically labeled
words: Athe results are believed to be satisfactorily atoms between gas molecules and solid catalysts and
explained by assuming that the combination takes wrote: Asubstantial result of those papers Žpublished
place mainly as a result of the alternative oxidation in the thirties. was that a propensity has been clearly
and reduction of the catalyst.B Independently, a very proven of various catalysts of halogenations
similar conclusion on the mechanism appeared in Žhalogenides of Al, Fe, Sb. for fast isotopic ex-
other papers of that time w9,10x. An oxidation mecha- change with organic halogenides and, there was also
nism upon which lattice oxygen enters the des- a certain parallelism found between the reactivity of
orbable products was later much more explicitly halogenides in the exchange and in halogenation, as
formulated by Kroeger w11x. However, the broad well as in isomerization of halogenated organic mo-
C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32 21
lecules.B However, in the same paper w23x, Roginsky Exchange of isotopes among dioxygen molecules
was much skeptical about an analogous behavior of catalyzed by oxides revealed some phenomena, which
oxides. He seemed to be supported by the early first surprised the experimentalists very much but
experiments with labeled oxygen w25x. It did not last later were perfectly explained just by the operation
long and several reports appeared with results of the MvK mechanism. The surprising aspect was
strongly supporting the MvK mechanism in oxida- that the apparent equilibrium constant of the ex-
tions. A perfect analogy with halogenations was thus change dropped in the initial stages of the exchange
confirmed w26–30x. The oxidation mechanism has reaction from its theoretical value of ca. 4 to ca. 2
been revealed in further details. With Bi`Mo oxides, and slowly returned to its theoretical value. The
different metal`oxygen pairs appeared to be in- corresponding description of the reaction kinetics
volved in either the dehydrogenation of propene and w36x assumed the existence of three ‘ visible’ ex-
the insertion of oxygen steps. This implied a trans- change modes characterized by three reaction rates
port of oxygen ions through the lattice, a step that R, having the following meaning: R 0 — the ex-
can in principle complicate the application of iso- change occurs without any participation of the lattice
topes in the studies of mechanism w31,32x. oxygen; R 1 — upon each sojourn of a dioxygen
The just mentioned isotopic experiments are the molecule on the surface, one of the oxygen atoms is
most reliable evidence for the MvK mechanism, if exchanged for lattice oxygens; and R 2 — both atoms
the side reaction like fast isotopic scrambling does of gaseous dioxygen are exchanged upon a single
not spoil the play. However, a rather strong support sojourn on the catalyst. The last two exchange rates
for this mechanism has been obtained from other can be called single and multiple exchange, respec-
experiments also. tively. It appeared that the results on the oxygen
Operation of the MvK mechanism can be detected exchange on oxides simply can not be explained
in the ‘swing’ type experiments, with alternating without the assumption that the lattice oxygen partic-
oxidation and reduction steps, with pure reductant or ipates in the exchange, i.e. without the assumption
oxidant in the feed. When the rates and selectivities that the MvK mechanism operates w36–39x. It is
of the swing and the continuous catalytic reactions interesting to notice that the kinetics derived by Klier
are similar, this observation can be a good indication et al. w36x has been with success applied also to the
that the MvK mechanism operates w11–13x. When a exchange of deuterium and hydrogen on hydrides
valid kinetic equation can also be derived on the w40x or to the same reaction on EDA-complexes
basis of the MvK mechanism, the support becomes Žalkali metals on aromates., confirming that, with
still stronger w11–13x. these systems too, the MvK mechanism operates
When a reaction really runs with the MvK mecha- w41x.
nism, one can reasonably expect that there is some
relation between the rate of the catalytic reaction and
the metal ` oxygen, metal ` halogen or the 3. Some recent results indicating the operation of
metal`sulfur bond strength. Such a correlation has the MvK mechanism
been looked for and indeed found for the M`X
ŽX s O, Cl, S. bond strength averaged over the In the course of time, a large volume of experi-
lattice. The latter is conveniently defined as, for mental results had been obtained on the oxygen
example, the heat of the highest oxide formation Žof exchange reaction. Together with an elucidating dis-
the element in question. normalized per one oxygen cussion, results are summarized in several compre-
of the stoichiometric formula. One can not expect hensive reviews w36–40,42x. Notwithstanding all
too much from these correlations; they are suitable to these efforts, a close look revealed that the informa-
indicate the trend, and not to answer subtle ques- tion available was still insufficient to make a reliable
tions. However, they can be useful w14,18,33–35x. conclusion on, for example, the similarity or differ-
Also, some other correlation has been suggested and ence in the variation of the R 1 and R 2 along the
rationalized, as for example, a correlation with the period of elements, on their possible relation with,
virtual pressure of oxygen or chlorine etc. w14,35x. respectively, the deep and the selective oxidation etc.
22 C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32
Some speculations therefore appeared to be doubtful to which factors determine the selectivities in the
w43x. One of the shortcomings of the early reports is deep and selective oxidations, respectively. The liter-
that they often report on the total rate, R 0 q R 1 q R 2 , ature already strongly indicated w46x that there is
and not on the individual rates. Therefore, the oxy- probably a relation between the parameter q ŽM`O.
gen exchange experiments on various oxides have and the rates of deep oxidations of hydrocarbons and
been repeated and the relevant results are presented those of the oxidation of hydrogen, but a similar
in Fig. 1 w44,45x. reliable information on selectiÕe oxidations was
From Fig. 1, interesting conclusions can be drawn missing.
immediately: Ži. the two rates vary along the periods Let us mention in this place another interesting
of elements, with Z being the atomic number, in a and elucidating information w47x. The rate of oxida-
very similar way; Žii. variation in the reciprocal of tion of hydrocarbons can be correlated with the mean
the average bond strength shows the same periodic- bond strength q ŽC`H. in the hydrocarbon. On one
ity which suggests that the three parameters are and the same oxide, the higher the rate, the lower is
mutually related. Further, point Ži. contradicts the the parameter q ŽC`H.. An antipathic correlation is
speculations made in w43x with regard to the relation also found for one given reaction and the q ŽM`O.
of the rates with the selectivity in oxidations. parameter of oxides used as catalysts. In the just
Experiments in w44x have been performed as an mentioned reactions, hydrocarbons act as reductants
attempt to gain more information on the problem as of the oxide and both the hydrogens and the carbons
of the hydrocarbon transport oxygen of the oxide
ŽMvK. in the gas phase.
Doornkamp also followed w44x the oxidation of
allyl iodide by dioxygen, with oxides as catalysts.
The reason for choosing this molecule was the fol-
lowing one. The selective oxidation of propene to
acrolein is initiated by splitting off of the allylic
hydrogen and formation of adsorbed allylic species.
On many oxides, the splitting needs such a high
temperature that the fragment then reacts immedi-
ately further, up to carbon oxides and water. How-
ever, the formation of adsorbed allyl from allyl
iodide is easy and requires a much lower tempera-
ture, under which the intermediates and the products
of selective oxidation can persist. Using allyl iodide,
one can thus study a larger number of oxides in the
selective oxidation reactions. Some results of this
study are shown in Fig. 2. We can see there that the
variation in the rates reminds one of that in Fig. 1.
Analyzing the data in more detail reveals the
following: Ž1. the rate of the deep oxidation and the
sum of the oxygen exchange rates all vary in phase,
with Z; Ž2. the selectivity in acrolein formation
varies in antiphase, with regard to the two other
Fig. 1. Exchange reaction of dioxygen Ž16 O 2 q18 O 2 . over oxides; parameters. We can see it in Fig. 3.
compared at T s 573 K. The variation in rates of R1 Žsingle-ex- The message from Figs. 2 and 3 is as follows.
change mechanism and R 2 Žmultiple-exchange mechanism. are The ratio of the two rates, that for deep oxidation to
given as a function of atomic number Žposition in the first long
period of the periodic table.. On the right-hand side is given the
that for selective oxidation is high on those oxides
reciprocal of the q ŽM ` O., the average M ` O bond strength in which show a high rate of oxygen exchange and
oxides w45x. have a low bond strength q ŽM`O.. Obviously, the
C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32 23
Fig. 2. Rate of the allyl iodide total consumption Žoxidation. and that of CO 2 production at 523 K Ža measure of deep oxidation., both as a
function of atomic number, along the first long period of elements w44x.
non-selectiÕe oxides haÕe a higher portion of actiÕe Notwithstanding the presence of labeled oxygen
lattice oxygen for participation in the catalytic reac- in the gas phase, the products of the initial stage of
tions. Such a correlation has been predicted under oxidation contain only the non-labeled oxygen from
the assumption of operation of the MvK mechanism the oxide. This holds for both the deep and the
already by Sachtler et al. in 1968 w48x. These authors selective oxidation, so that both of them evidently
also brought an experimental support for their as- run with the MvK mechanism.
sumption: when benzaldehyde was admitted into the An interesting point concerning the correlations of
catalyst at rather low temperatures, the infra-red the rates with atomic number Z of the catalysts’
absorption bands corresponding to benzoic acid ap- cation is the shape of these correlations and the size
peared immediately. of the ups and downs in fluctuations in the rate.
Doornkamp et al. w44x studied the allyl iodide From the literature and from our own data, we know
oxidation in the presence of isotopically labeled that the dioxygen exchange reaction, the deep oxida-
dioxygen 18 O. The oxide contained only 16 O. These tion of saturated hydrocarbons, oxidations of olefins
experiments clearly confirmed the operation of the and acetylenes, as well as the deoxygenation Žsee
MvK mechanism, even on an oxide with a rather low below. of nitrobenzene ŽPh`NO 2 . and of benzoic
activity — vanadium pentoxide. This can be seen in
Fig. 4.
Fig. 3. Allyl iodide oxidation at 523 K; selectivity to acrolein Ž^. Fig. 4. Temperature-programmed oxidation of the allyl iodide on
and CO 2 Ž`. as a function of the atomic number. In the same V2 16 O5 , in the presence of 18 O 2 . Concentration of various com-
graph is given the total exchange rate Ž R1 q R 2 . of dioxygen at pounds in the gas phase. Notice the early production of 16 O-Žex
573 K w44x. oxide. — acrolein w44x.
24 C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32
acid ŽPh`COOH., they all show a similar saw-tooth copper, one can detect an intermediate of this reac-
like correlation with Z. The two initially mentioned tion — phenyl hydroxyamine — in the solution
reactions show, however, large differences between above the catalyst. Reaction to nitrosobenzene is less
the minimum and maximum rates, up to seven orders easy. The classical technology is a two-step process:
of magnitudes. The rates of the last two mentioned nitrobenzene is first converted into phenyl hydrox-
reactions vary with Z within only one order of yamine by adding to it Zn and HCl, and subse-
magnitude. This can be probably explained as fol- quently, this intermediate is oxidized to nitrosoben-
lows. The rate of oxidation that comprises extraction zene by chromates. This batch-wise production does
of oxygen out of the lattice depends on the not require much investment, but it is environmen-
metal`oxygen bond strength. Oxidation of organics tally very unfriendly. With each kilogram of ni-
requires, however, also splitting of the carbon`hy- trosobenzene, about 3 kg of inorganic waste are pro-
drogen bond and the simultaneous association of duced simultaneously. Therefore, there is a high
both fragments with the pair M`O of the catalyst, demand for waste-free technology. This can already
which is again a kind of oxygen extraction step, the be provided now in the form of deoxygenation of
rate of which depends on the M`O bond strength. nitrobenzene on oxides. The MvK mechanism plays
When the splitting of the C`H bond is difficult Žalso a dominant role in it. Let us take a close look at the
the splitting of the O5O bond upon the dioxygen deoxygenation of nitrobenzene described in the patent
exchange reaction is difficult., the dependence of the literature; see e.g. w49,50x.
rate on the q ŽM`O. is then more pronounced and When we start with manganeseŽIV. dioxide and
the differences between the maxima and minima on pure nitrobenzene Žno dihydrogen., the oxide is first
the correlations with Z are particularly large. In reduced by the ring as reductant up to Mn 3 O4 ,
contrast to it, the hydrogen of the ring in nitroben- producing only carbon oxides and water. Then, a
zene and in benzoic acid is activated by the sub- rather selective formation of nitrosobenzene sets in.
stituent, its splitting off is easy, and consequently, We can also prereduce the catalyst up to MnO by
the fluctuations in rates as functions of Z are less dihydrogen or CO, and then in the stream of ni-
pronounced. With allyl iodide, the formation of the trobenzene, the catalyst is first reoxidized into its
reactive intermediate is easy, much easier than from steady state of Mn 3 O4 , whereafter a steady produc-
propene. In this respect, the acetylenic hydrocarbons tion of nitrosobenzene takes place w51x. Such a be-
are near allyl iodide, while olefins represent an havior alone is already a strong indication that the
intermediate case. MvK mechanism operates. This conclusion has been
confirmed by experiments with labeled molecules. In
the study w52x, Mn oxide catalyst was labeled by 18 O
4. Deoxygenations by the Mars and Van Krevelen and nitrosobenzene was admitted at various tempera-
mechanism tures Žbatch reaction.. Both nitrobenzene and the
products of deep oxidation initially contained oxygen
In chemical technology, it is sometimes easier to from the catalyst. On oxides with a high M`O bond
produce, or to isolate from natural products, mole- strength, like aluminum oxide, nitrosobenzene under-
cules that contain more oxygen than desired and to goes disproportionation, and in the gas phase, ni-
remove in a separate step one of the oxygens Žselec- trobenzene appears with only light oxygen, from
tive deoxygenation.. Examples of such reactions al- other nitrosobenzene molecules, most probably, ac-
ready studied are the above-mentioned conversion of cording to the following reaction:
nitro- into nitrosobenzene, or the production of alde-
hydes from carboxylic acids. These reactions are 2PhNOs PhNO 2 q Ž PhN . ads
commercially quite interesting.
Reduction of nitrobenzene to aniline is used in the The adsorbed fragment most likely dimerizes.
dye industry for a long time already. It is a straight- The thermal programmed desorption from the
forward addition of hydrogen catalyzed by metals, at layer of adsorbed nitrosobenzene on manganese ox-
moderate temperatures. On a less active metal like ide revealed how the temperature determines the
C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32 25
Fig. 6. A scheme of reactions occurring on oxides with acetic acid and dihydrogen mixture.
26 C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32
ture, MvK pathway 1 can prevail w59x. Vice versa, a the aromatic ring is obviously not blocked by the
preoxidized surface of an oxide with a high M`O adsorption of acid on the metal. With the aliphatic
bond strength would strongly stimulate the ketoniza- acids, hydrogen too is present on the metal, next to
tion ŽSabatier reaction.. The C`H bond dissociation the adsorbed acid, but the competing reaction is not
in step 2 is suppressed when the surface is covered hydrogenation now but hydrogenolysis which re-
by hydrogen. A lower M`O bond strength and a quires a higher temperature than deoxygenation on
higher dihydrogen pressure are beneficial for it. Ter- the oxidic component of the catalyst.
tiary aliphatic acids and the benzoic acid have no The presence of platinum on titanium dioxide is
alpha-hydrogen and this closes the way along path 2 beneficial for the deoxygenation of acetic acid and it
w58x. Benzoic acid forms, however, other side prod- improved the performance of the catalyst so dramati-
ucts, which decrease the yield of aldehyde w60x. cally that it became desirable to investigate the spe-
Let us now leave the description of individual cific roles of the individual catalysts’ components
reactions and turn our attention to various compar- w56,57x. In this study, a given amount of Ptrtitanium
isons and generalizations. There are some similarities oxide was taken and a varying amount of additional
among the various deoxygenations, but let us start TiO 2 added to it. Addition of titanium dioxide did
with the differences, for example, those between the not change the apparent activation energy but clearly
aliphatic and aromatic acids on one side and the nitro increased the rate, obviously by increasing the num-
compounds on the other side. The nitro substituent ber of active sites. The deoxygenating sites are thus
activates the rest of the molecule, the benzene ring, on the oxide. This result is illustrated by Fig. 7
so strongly that the reaction can proceed well with- w56,57x.
out external reductant, as autoreduction. With acids, When a pure titanium dioxide is severely prere-
no deoxygenation by autoreduction is possible. duced, aldehyde formation is stimulated. This obser-
Nitroalkanes show still another interesting reac- vation too indicates the role of oxygen vacancies in
tion, which, however, prevents their heterogeneous the activity and selectivity of an oxide. Moessbauer
deoxygenation to nitroso compounds on reducible spectra supplied another argument for the idea that
oxides. Upon adsorption on oxides, the alpha-hydro- the oxygen vacancies induce the MvK deoxygena-
gen, when present in the compound, is split off and
an adsorbed nitronate ion with a very reactive bond
C5N is formed. This bond induces a destructive
oxidation of the adsorbed nitronate ion by lattice
oxygen and no nitroso compound is formed. The
carboxylic acids show a certain analogy to this by
their reactions to ketenes, but ketenes are less sus-
ceptible to subsequent oxidations.
The two groups of acids differ markedly in their
reactions on metal-containing catalysts. With
aliphatic acids, the performance of e.g. titanium
dioxide is improved, and its activity and selectivity
to aldehydes enhanced, when a metal is added to the
oxide. Obviously, because a higher concentration of
hydrogen on the surface leads to a higher concentra-
tion of oxygen vacancies and simultaneously reac- Fig. 7. Reaction of acetic acid on PtrTiO 2 catalysts at 673 K. A
tion, step 2 of Fig. 6 is suppressed. However, the yield of acetylaldehyde as a function of the catalyst composition is
presence of a metal is detrimental for the selectivity given. Black bars: a constant amount of PtrTiO 2 is diluted by the
to benzaldehyde in the deoxygenation of the benzoic TiO 2 added. The total amount of Pt in the reactor is constant, but
the amount of TiO 2 increases from the left to the right. Empty
acid. The ring is activated by adsorption on the metal bars: the total amount of TiO 2 is kept constant, and the amount of
and hydrogenated subsequently. The situation is quite Pt in the reactor varies — it increases when going from right to
different with aliphatic acids. The hydrogenation of the left.
C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32 27
tion of acids. An iron catalyst strongly prereduced MvK mechanism would certainly also deserve more
showed the deoxygenation activity only after de- attention of quantum chemists.
tectable amounts of an oxide had formed on its
surface by reaction with the acid in the feed w59x.
The above-described role of oxygen vacancies is 5. Hydrodesulfurization (HDS) reactions
itself an indication that the deoxygenation reaction is
an MvK reaction. Oxidation of benzaldehyde, the Hydrotreatment of crude oil, comprising the
reversed reaction, can run with only the oxide lattice desulfurization step, is one of the most important
oxygen, as has been seen in IR spectra w48,61x. The processes in the petrochemical industry. Thanks to
IR spectra of adsorbed acetic acid were studied and the ever-improving technology of oil and coal desul-
they provided an indication that acetic acid interacts furization, the disastrous deterioration of woods in
with oxygen vacancies upon formation of an asym- middle and west Europe has been stopped. In the
metric bidentate adsorption complex w62x. With re- same period of time, the fundamental knowledge on
gard to the mechanism of benzoic acid deoxygena- desulfurization has increased amazingly. An inter-
tion, the following is of importance. The selectivity ested reader can admire the progress made in one of
to benzaldehyde depends very much on the reaction the excellent reviews on this subject now available
conditions and the catalyst used. This dependence w33,65x. The volume of the literature on the subject is
can be understood on basis of the MvK mechanism enormous; one w33x of the reviews gives 1514 quota-
and the assumed role of oxygen vacancies in it. At tions. However there are still some unsolved prob-
higher pressures of hydrogen, higher temperatures lems!
and with oxides of lower M`O bond strength, the The exact nature of the adsorption site for sulfur-
steady-state concentration of oxygen vacancies is too containing molecules is still being discussed Žis there
high, and consequently, the selectivity shifts from always only one type of adsorption site?. so that it
benzaldehyde to toluene. With an oxide of a higher does not surprise that we do not know enough about
M`O, this shift occurs at higher temperatures. For- the adsorption modes most important in dehydrosul-
mation of toluene can also be suppressed by using furization. A collection of possible modes can be
higher pressures of benzoic acid or by adding water found in the reviews; the most important of them
vapor to the feed w57,60,63x. In full analogy with remind of those of Fig. 5. Essentially, a sulfur-con-
benzoic acid, too high a concentration of oxygen taining molecule can stay perpendicularly to the
vacancies Žcaused by too high a pressure of hydro- surface, with its sulfur atom in a sulfur vacancy or,
gen in the reaction mixture or too severe a prereduc- less probably, through a sulfur`sulfur bond. It can
tion of the oxide. shifts the selectivity in the deoxy- also be oriented parallel to the surface, being held
genation of nitrobenzene, from nitrosobenzene to through its pi-system. Impression from the literature
aniline. is that the first mode is most important with small
The acids play a role in the feedback control of and with aliphatic molecules.
the state of the catalysts’ surface, either, as men- The following is a much discussed problem: which
tioned above, by annihilating some oxygen vacancies is the exact sequence of elementary steps? Is it the
or, when a metal is present in the catalyst, by sulfur extraction first, followed by hydrordehydro-
blocking most of the other reactions on the metal but genation steps or is dehydrosulfurization initiated
allowing hydrogen adsorption to occur w64x. With by hydrogenolysisrhydrogenation steps? Probably
benzoic acid, however, the last mentioned effect is w33,65x, the small molecules strongly prefer the first
insufficient to secure a high selectivity to benzal- alternative, while for the large aromatics, the oppo-
dehyde. site is true.
The message of what is said above is clear. The Dehydrosulfurization rate of dibenzothiophene
information on the solid-state reactions of oxides ŽDBT. shows a significant correlation with the
and, on their redox properties in relation to their metal`sulfur bond strength in the catalysts used.
composition, can be used for future improvements of However, it does not mean that sulfur extraction is
deoxygenation catalysts. These reactions and their the rate-determining step. Hydrogenation steps re-
28 C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32
Fig. 12. The HDS rates for DBT, as a function of the M ` S bond
strength, calculated theoretically w33x.
Fig. 11. The catalytic activity in nitrobenzene deoxygenation of the 3d Ž`. 4d Ž=. and 5d Ž). transition metal oxides as a function of the
heat of oxide formation ŽkJrmol., normalized per one oxygen atom of the stoichiometric oxide formula w74x.
30 C. Doornkamp, V. Ponec r Journal of Molecular Catalysis A: Chemical 162 (2000) 19–32
Evidence for the MvK mechanism operating some activity already at lower temperatures. How-
widely is strong and the mere existence of such a ever, when the temperature was increased, they lost
mechanism indicates that there should be some rela- their selectivity to benzaldehyde easier than the ox-
tion between the catalytic rates and the thermody- ides with a higher M`O bond strength, like dioxides
namic parameters of the solid catalyst. However, of Ti, Zr and Hf. Therefore, the highest possible
how to understand and use the correlations properly? yield of benzaldehyde was obtained just with the last
We can learn from the literature that the exact mentioned group of oxides. Namely, when the bond
value of the M`X bond strength is difficult to assess strength is too low, then the steady-state concentra-
and one has to use one or another substitute. Thus, tion of oxygen vacancies is too high and this induces
the first difficulty is how good is this choice and in too high a production of toluene and other side
which detail one can then trust the correlation ob- reactions. Within the group of Ti, Zr and Hf oxides,
tained? Let us assume that the choice is a good one; the antipathic correlation between the activity in the
what can we expect then from the correlation? deoxygenation of the acid and the bond strength is
Since the 17th century, scientists know that a exactly valid, in a way similar to the sympathetic
valid theory should lead to verifiable and valuable correlation between the selectivity and the bond
predictions. When the correlations between the cat- strength. Here, the reference to the correlation helps
alytic rates and thermodynamic parameters of solid us to understand and to order the empirical knowl-
catalysts became a part of the theory of catalysis, edge, notwithstanding all the correct criticism in the
scientists began to speak so often about using these literature on the parameter used and the correlation
correlations for finding still better catalysts that an obtained with it. We express in conclusion the hope
impression was created as if it were better to define that a proper way of considering the above-men-
ever better parameters and to look for ever better tioned correlations and the regularities in catalytic
ways to assess them, than to perform catalytic exper- activities already established can perhaps lead to a
iments directly Žwhich are often easier to perform design of new catalysts in a faster procedure than a
than to establish some of the parameters.. This was combinatorial search.
not correct and it only brought the use of correlations
in discredit. We can not ignore the following. The
parameters averaged over the whole lattice mask the Acknowledgements
large differences between individual bonds, but the
molecules interact with individual bonds that are, for
example, crystal face specific. Using the plot activity The authors wish to thank Academic Press and
versus q ŽM`O. instead of plots with Z as the Springer Verlag for the permission to reproduce
parameter, we can mask meaningful differences Figs. 1, 5, 9, 10 and 12.
among the periods of the periodic table. It should be
expected that a simple correlation with a single
averaged bond strength can not answer such a subtle References
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