Applied Catalysis A: General 229 (2002) 75–91

Selectivity in hydrocarbon catalytic reforming:

a surface chemistry perspective
Francisco Zaera∗
Department of Chemistry, University of California, Riverside, CA 92521, USA
Received 15 May 2001; accepted 25 July 2001

Abstract
A brief overview of the recent advances in the understanding of the reaction mechanisms of hydrocarbon reforming processes
is provided. Emphasis is placed on the knowledge developed by studies using model single-crystal metals and modern surface
analytical techniques. An argument is presented for the early definition of reaction selectivities in these processes because
of subtle relative changes in dehydrogenation rates. Specifically, the ability of platinum to promote ␥-hydride elimination
steps from chemisorbed alkyl groups is proposed to be the reason for its unique behavior in isomerization and cyclization
reactions. Nickel, in contrast, facilitates dehydrogenation preferentially at the ␣-position, and catalyses hydrogenolysis instead.
Nevertheless, by far the most favorable reaction of alkyl moieties on transition metals is ␤-hydride elimination. It is this
step the one that accounts for the fast equilibrium reached between alkanes and alkenes under most reaction conditions.
Additional mechanistic complications in hydrocarbon reforming under catalytic conditions are introduced by the strongly
bonded carbonaceous deposits that cover the surface of the active catalyst. The role that those deposits play in reforming
is not yet entirely clear, but it is believed to involve passivation of the surface to facilitate the adsorption of ␲-bonded
olefins and other weakly adsorbed intermediates, and also the provision of a reservoir for hydrogen. The working reforming
catalysts is therefore likely to display bifunctional character, with rapid hydrogenation–dehydrogenation steps taking place
on the hydrocarbon-covered surface, and more demanding skeletal rearrangement steps occurring on patches of bare metal.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydrocarbons; Catalytic reforming; Molecular models; Surface chemistry; Single crystals; Alkyls; Platinum

1. Introduction isomerization, hydrogenation, and polymerization of

It could be said that heterogeneous catalysis started
with the report by Davy in 1818 on the rapid oxida-
tion of hydrogen over a platinum surface [1]. The ad-
vance of hydrocarbon processing using heterogeneous
catalysis followed soon thereafter. Sabatier proposed a
catalytic process for the hydrogenation of ethylene as
early as 1902, and Ipatieff reported the use of clays as
catalysts for several hydrogenation, dehydrogenation,
∗ Tel.: +1-909-787-5498; fax: +1-909-787-3962.
E-mail address: francisco.zaera@ucr.edu (F. Zaera).
organic compounds in 1905. However, it was with the
discovery of cheap oil in the early 1950s that the de-
velopment of catalytic processes to convert crude oil
to fuels and chemicals really took off. Catalysts con-
taining sulfides of molybdenum and other metals were
designed to remove sulfur, oxygen, nitrogen, and other
impurities from oil feedstocks [2]. Zeolites and other
aluminosilicates were introduced for the cracking of
large petroleum molecules into smaller hydrocarbons
[3]. Titanium and zirconium complexes became the
basis for several polymerization catalytic processes
[4].

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 0 1 7 - 0
76 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
Fig. 1. Possible reactions for the conversion of n-hexane during reforming processes [2]. The key to an efficient reforming catalyst is the
promotion of isomerization, cyclization, and aromatization at the expense of undesirable hydrogenolysis (C–C bond scission) steps.
One of the fundamental oil refining processes
nowadays is catalytic reforming [5]. In reforming,
gasoline-range molecules are reconstructed without
changing their carbon content in order to improve
the quality of the fuel, as measured by their octane
number. Reforming processes involve many reactions,
including isomerizations, hydrogenations, dehydro-
cyclization, and dehydrogenation. An example of the
relevant reactions in reforming is provided in Fig. 1
for the case of n-hexane. Reforming catalysis was
originally conducted on molybdenum oxide dispersed
on alumina, but a significant advance was made by
the Universal Oil Products Company in 1949 with the
introduction of the use of platinum for this process
[6]. A number of platinum-based catalysts, mostly al-
loys with a second metal such as rhenium or iridium,
have been developed ever since [7].
The modern reforming catalysts consist of small
metal particles finely dispersed on a high surface-area
support such as alumina. These catalysts are bi-
functional, possessing two types of sites [8]. On the
one hand, the acidic nature of the surface of the
alumina support, a property enhanced by treatment
with chlorine-containing compounds [9], helps pro-
mote skeletal rearrangements in carbonium ions [10].
Transition metals, on the other hand, are excellent
hydrogenation–dehydrogenation catalysts. It is be-
lieved that hydrocarbon reforming requires multiple
reactions involving both types of sites. However, even
though many metals promote hydrocarbon hydro-
genation, only platinum-based catalysts lead to the se-
lective production of reforming products. Nickel, for
instance, favors undesirable cracking instead. More-
over, unsupported platinum is capable of carrying out
reforming catalysis by itself, without the presence of
any acidic sites [11,12]. Clearly, the metal itself plays
a central role in all the steps of reforming.
Extensive research has been carried out in the last
century to develop a better basic understanding of
the unique behavior of platinum for reforming. Re-
searchers like Bond, Horiuti, Polanyi, and Wells pro-
vided fundamental ideas early on about the specific
mechanistic details of the catalytic hydrogenation of
unsaturated hydrocarbons on transition metals [13,14].
Additional concepts associated with the conversion
steps involving hydrocarbons on solid surfaces have
come from Anderson, Avery, Boudart, Gault, Kemball,
Paál, Rooney, Sachtler, Sinfelt, Tétényi, and many oth-
ers [2,15–20]. Professor Guczi, to whom this article
is dedicated, has been a major player in this endeavor
as well [21–28]. The collective work of those research
groups have provided a useful, if limited, picture of
the microscopic details of the chemical surface reac-
tions involved in catalytic reforming.
The main difficulty with most of the traditional
catalytic investigations cited above is that it has in
many cases been based on kinetic studies, and, con-
sequently, has relied on indirect evidence. A few
 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
spectroscopic techniques such as infrared and NMR
have long been available for the direct characterization
of surface intermediates [29,30], but the heteroge-
neous and complex nature of the surface of supported
catalysts makes the interpretation of the results of
those studies less than straightforward. It was only
with the advent of new modern surface-sensitive tech-
niques in the 1960s that the detailed characterization
of basic chemical transformations on model systems
became possible [31–33]. The use of this approach
for the study of hydrocarbon catalysis was pioneered
by Somorjai and co-workers [1,11,34–36], and has
been one of the main directions of research in our
group for the last couple of decades.
The purpose of this report is to summarize some
highlights from the results obtained using such a
modern surface-science approach to the study of hy-
drocarbon reactions on transition metal surfaces, in
particular to reactions related to hydrocarbon reform-
ing. Ours does not pretend to be a comprehensive re-
view, but rather one that focuses on our contributions
to this field, although key advances from other groups
are also included. This article is divided as follows.
Section 2 provides a discussion on the initial adsorp-
tion and activation of alkanes as the rate-limiting step
in reforming. The chemistry of the resulting surface
alkyl intermediates and its relevance to reforming se-
lectivity are addressed in Section 3. Section 4 focuses
on the preferred ␤-hydride elimination step from
alkyls that leads to the formation of olefins. In Section
5 a look is taken at the alternative dehydrogenation
reactions from the ␣- and ␥-position as the ones that
define selectivity between hydrogenolysis and iso-
merization. Bond forming reactions are addressed in
Section 6. Section 7 discusses the complications to the
understanding of reforming mechanisms introduced
by the atmospheric pressure environments required
for hydrocarbon catalysis. Finally, Section 8 provides
some concluding remarks on how the knowledge sum-
marized in the previous sections can be put together
in a model for the working reforming catalyst.
2. Alkane activation as the rate limiting step
in reforming
The feedstock for oil reforming processes is
a low-octane mixture of hydrocarbons mainly
77
comprised of straight-chain paraffins in the range of
five to eight carbons long [2]. Because saturated alka-
nes are quite stable, the step that limits the activity
of reforming catalysts is typically associated with the
scission of one of the C–H bonds in those molecules.
With this in mind, surface chemists have spent a great
deal of effort on the study of the activation of alkanes
on single crystals and other model surfaces.
Both molecular beam and adsorption–desorption
techniques have indicated that the promotion of C–H
bond-scission steps in alkanes by metal surfaces may
occur either directly upon collision of the incoming
gas molecule with the solid or, alternatively, via the
formation of a weakly adsorbed intermediate trapped
on the substrate [37,38]. It has been shown that the
critical factor for alkane activation is the efficiency
with which energy is transferred from the translational
and internal degrees of freedom of the gas molecules
to the particular C–H bond to be broken; the energy
stored by the surface seems to be of little importance
for this process [37–39]. In addition, an early study by
Stewart and Ehrlich revealed that vibrational modes
are the most likely internal source of energy for the
dissociation of methane [40]. Later work has indi-
cated that most often it is the normal component of
the translational energy of the alkane that is important
for the C–H bond-breaking step [41,42].
Direct alkane activation may occur via a tunneling
mechanism [43], at least at the high kinetic ener-
gies associated with supersonic beam experiments.
Alkane sticking probabilities often increase mono-
tonically with increasing kinetic energy, not suddenly
after a given threshold as expected if the kinetics
were dominated by an activation barrier. Also, the
observed shifts in the translational energy needed to
activate CH4 versus CD4 (or C2 H6 versus C2 D6 ) are
usually on the order of 5 kcal/mol, much larger than
the differences in the zero-point energy due to iso-
topic substitution [42]. On the other hand, the energy
and angle dependencies of the sticking coefficient of
methane observed on some metals may be explained
by a classical model based on the microscopic re-
verse of the reductive elimination of methyl with
hydrogen [44]. In any case, supersonic beams probe
only a small fraction of the gas molecules in a typical
catalytic mixture, those at the high-energy tail of the
Boltzmann distribution. Consequently, the probability
of alkane activation under normal catalytic conditions
78 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
by the same direct collision processes observed in
molecular beam experiments is predicted to be quite
low. This has been confirmed by regular high-pressure
catalytic studies, which have yielded methane sticking
probabilities as low as 10−12 [45].
Other molecular beam work has provided evidence
for a precursor-mediated alkane activation mechanism.
The trapping probability of ethane on Ir(1 1 0)-(1 × 2),
for instance, shows only a weak dependence on the
angle of incidence of the beam, suggesting that the
momentum of the incoming molecules is rapidly trans-
ferred to the surface [46]. In some cases, the dissoci-
ation of alkanes is also assisted by a reverse energy
transfer from the surface to the molecule. On both
platinum and rhodium, for example, the sticking prob-
ability of methane displays an Arrhenius temperature
dependence in the limit of low kinetic energy, with
an activation energy between 5 and 10 kcal/mol [47].
Some heavier chemisorbed alkanes can also be made
to react directly by heating of the substrate [48–50],
and physisorbed methane can be activated via colli-
sions with other impinging molecules as well [51].
The bonding of the intermediate precursor in
the trapping-mediated dissociative adsorption of
alkanes to the surface most likely involves a
three-center two-electron interactions similar to that
in organometallic systems [52,53]. Several pieces of
evidence have been put forward to support this hy-
pothesis. For one, the activation barrier associated
with the decomposition of alkanes on metal surfaces
amounts in most cases to less than one-fifth of the
C–H bond energy in hydrocarbon molecules [54–56],
suggesting that those bonds are weakened by an elec-
tronic interaction between the alkane and the surface.
In fact, infrared C–H stretching soft modes are some-
times observed in adsorbed alkanes [57]. Also, alkane
activation is facilitated by electron deficiency at the
metal center: early transition metals are particularly
efficient in dissociating medium-size alkane chains
[58], and iridium activates both methane and ethane
more efficiently than platinum [59]. Rough surfaces
are in general more active than close-packed ones
too [59]. Finally, co-adsorbed additives such as alkali
metals or chalcogens can promote alkane decomposi-
tion on nominally inert substrates [60].
All these studies support the basic idea that the
overall rate of reforming processes may be controlled
by the initial activation of the reactants on the surface
of the catalysts. Alkane activation appears to be
mainly dependent on entropic factors, hence the low
probabilities of reaction at all temperatures. However,
alkane activation also displays low activation energies,
implying that reforming activity should only change
moderately with temperature. Other steps must con-
tribute to the overall temperature dependence of the
reaction rates.
3. The chemistry of alkyl surface species and
its role in reforming selectivity
The initial activation of alkanes may be respon-
sible for determining the overall rate of reforming
processes, but the selectivity towards high-octane
products is defined by the subsequent surface reac-
tions. Specifically, the scission of the first C–H bond
in the reacting alkanes leads to the formation of sur-
face alkyl intermediates. Alkyl surface moieties can
then follow a number of subsequent reactions, hy-
dride, alkyl, and reductive eliminations, insertions,
and homolytic bond scissions, among others (Fig. 2).
However, it is our contention that it is the regiose-
lectivity of a second dehydrogenation step on those
species (a hydride elimination in the terminology of
organometallic chemistry) what seals the faith of the
final products. In order to better understand this issue
of selectivity in reforming, we in our laboratory have
embarked into a detailed research of the chemistry
of alkyl species on transition metal single-crystal sur-
faces [52,61–73]. Some of the main conclusions from
those studies are summarized below.
As mentioned in the previous section, alkanes are
fairly unreactive, and usually display significantly
low reactive sticking probabilities when dosed on
metal surfaces. This makes the production of alkyl
surface species directly via activation of saturated
hydrocarbons under controlled vacuum conditions
virtually impossible. In addition, because of the se-
vere conditions often required for the initial scission
of the C–H bonds in alkanes, those reactants tend
to decompose extensively on metal surfaces once
dissociatively adsorbed. In order to address these
difficulties, a number of alternative procedures have
been developed over the years for the preparation of
hydrocarbon surface intermediates in general, and for
the deposition of alkyl surface moieties in particular,
 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91 79

Fig. 2. Potential elementary steps available to alkyl moieties (sec-butyl in this example) when chemisorbed on metal surfaces. All these
reactions, with the exception of ␤-methyl elimination, have been seen in surface science studies [66,70,74,100,183]. However, it is mostly
the regioselectivity of the hydride elimination steps what defines selectivity in reforming.

on clean single-crystal surfaces [66,74]. Fig. 3 depicts
schematically some of the methods reported for the
production of surface methyl groups. They include
dosing surfaces with gas radicals produced by py-
rolysis of appropriate precursors (azomethane in the
case of methyl groups) [75], activating of adsorbed
alkanes via hyperthermal atom [51] or electron [76]
bombardment, soft-landing gas-phase cations [77],
and photoactivating of adsorbed precursors [78]. Un-
fortunately, it has not been possible to extend any
of those procedures to the general study of alkyl
chemistry. By far, the most popular method for the
preparation of surface alkyls under vacuum nowadays
is the thermal activation of adsorbed alkyl halides, an
approach that we pioneered in the late 1980s [61,66].
It is well known that alkyl radicals can be pre-
pared efficiently in gas or liquid phases via the py-
rolysis of suitable precursors such as alkyl halides,
azo compounds, and peroxides [79]. Perhaps more to
the point, alkyl halides have also been shown to un-
dergo oxidative addition reactions in solution to form
organometallic products with alkyl ligands attached
directly to the metal center [80,81]. We have shown
that the cleavage of the carbon–halogen bonds in alkyl
halides adsorbed on metal surfaces requires activation
energies of 5 kcal/mol or less, about the same as in so-
lution [82], and that that reaction usually occurs at tem-
peratures below 200 K [83,84]. The carbon–halogen
bond scission is easier with heavy halogens, hence the
preference for using alkyl iodides and alkyl bromides
precursors.
We have also proven that the initial decomposition
of alkyl halides on metals leads to the formation of
chemisorbed alkyl moieties. Examples of the data sup-
porting this conclusion are shown in Fig. 4. The alkyl
chains initially orient themselves flat on the surface
in order to maximize their interaction with the metal,
but reorient to a perpendicular configuration at higher
80 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91

Fig. 3. Schematic representation of some of the methods reported in the literature for the preparation of methyl surface groups on
solid surfaces [52,66,74]. From left to right: deposition of gas methyl radicals prepared by azomethane pyrolysis [75], activation of
adsorbed methane by hyperthermal atoms [51], soft-landing of gas-phase methyl cations [77], electron activation of adsorbed methane
[76], photoactivation of adsorbed methyl bromide [78], and thermal activation of methyl iodide [63,65]. From these, the latter is by far
the most versatile and widely used procedure for the isolation of hydrocarbon intermediates on metals.

coverages, presumably because of the prevalence of
van der Waals interactions among the hydrocarbon
chains in that regime [67,72,85]. Unfortunately, there
is no direct information on either the bonding geom-
etry or the coordination of alkyl groups to the surface
available to date. Both the low metal–carbon stretch-
ing frequency observed in vibrational studies [38,86]
and some theoretical calculations [87,88] suggest that
alkyls may adsorb on hollow sites, but other computer
estimates explain the experimental results by an on-top
configuration instead [89].
The activation of chemisorbed halohydrocarbon
precursors has been successfully extended to the pro-
duction of surface carbenes [90–93], vinyls [94,95],
allyls [96–99], metallacycles [100–104], and oxamet-
allacycles [105,106]. It should be pointed out, how-
ever, that ease of activation of potential precursors in
the gas or liquid phases does not guarantee success
on surfaces. For instance, azo and diazo compounds
contain low-energy C–N bonds and are used exten-
sively as precursors in gas and liquid phase studies,
but display fairly complex surface chemistry which
do not lead to the clean production of adsorbed alkyl
groups [107,108].
4. ␤-hydride elimination: olefin formation
The thermal chemistry of alkyl groups on transition
metal surfaces is dominated by the elimination of a
hydrogen atom from the ␤-position, that is, the carbon
adjacent to that bonded to the surface [52,69,74,109].
One of the earliest indications of the occurrence of
this step came from temperature-programmed desorp-
tion studies on the decomposition of partially labeled
ethyl iodides on Pt(1 1 1) [110]. That work showed that
the dehydrogenation of CH3 CD2 I only removes nor-
mal hydrogen atoms, while the thermal activation of
 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91 81

Fig. 4. Evidence for the production of alkyl groups on metal surfaces by thermal activation of chemisorbed alkyl iodides. Left:
reflection-absorption infrared spectra (RAIRS) from methyl, ethyl, 1-propyl, and 2-propyl moieties on Cu(1 1 0), prepared by annealing of
the corresponding adsorbed alkyl iodides at 180 K [69]. Right: static secondary ion mass spectra (SSIMS) from perdeutero methyl and
ethyl fragments chemisorbed on Ni(1 0 0), again prepared by thermal activation of the appropriate alkyl iodide precursors [65,68,135].

CD3 CH2 I leads to the exclusive release of a deuterium
atom instead. More direct evidence is now available
for this reaction in the form of the detection of the
resulting olefin, both adsorbed on the surface (Fig. 5)
and in the gas phase after desorption.
In terms of the details of the transition state during
the ␤-hydride elimination step, an elegant series of ex-
periments using fluorine-substituted propyl groups on
Cu(1 1 1) was used to demonstrate the anionic nature
of the leaving hydrogen [111]. The fact that the posi-
tive charge that develops on the ␤-carbon in the tran-
sition state is stabilized by electron donating groups
was also proven by the results from experiments
with 2-iodohexane on Cu(1 0 0), where the selective
production of 2-hexene over 1-hexene was observed
[73,112]. The activation barrier for ␤-elimination
from chemisorbed alkyl groups was determined to be
less than 10 kcal/mol on most transition-metal sur-
faces [70,113], and to display a large normal kinetic
isotope effect, on the order of a factor of 10 when sub-
stituting normal hydrogen by deuterium atoms [114].
This implies that either tunneling or secondary effects
must play a role in the dehydrogenation step. Some
other significant trends have been observed for the
82 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
Fig. 5. RAIRS evidence for the formation and subsequent ther-
mal chemistry of propene from ␤-hydride elimination in 1-propyl
groups adsorbed on Pt(1 1 1) surfaces [71]. The bottom three traces
correspond to the progression of the intermediates that form dur-
ing the thermal activation of propyl surface species, propylene first
and propylidyne above room temperature. The spectra for low and
high propylene coverages are also provided to illustrate the possi-
bility of formation of two types, di-␴- and ␲-bonded of adsorbed
olefins [177].
␤-hydride elimination reaction, as illustrated by the
data in Fig. 6 [52,70,74,112]: (1) The desorption tem-
perature of the alkenes produced by alkyl dehydro-
genation shifts to higher temperature with increasing
chain length, perhaps because of the increase in ad-
sorption energy of the products. (2) The alkene yield
is higher (relative to alkane production by the com-
peting reductive elimination reaction) for branched
than for linear alkyls. Also, the products desorb at
lower temperatures in the former cases. These effects
can be explained at least in part by steric and entropic
arguments. (3) Open surfaces are normally more ac-
tive than close-packed ones, a difference that may be
correlated to the requirement of low coordination for
␤-H elimination in organometallic complexes. (4) ␤-H
elimination is easier on earlier and lighter transition
metals: it occurs below 200 K on nickel, palladium,
and platinum surfaces, at around 230–250 K on cop-
per, and at about 260–310 K on gold. (5) Most metals
are efficient at promoting ␤-hydride elimination reac-
tions, but a few late transition metals tend to favor the
reductive elimination route instead [115,116]. On sil-
ver in particular, alkyl groups couple with 100% effi-
ciency [117], perhaps because the low affinity of silver
for hydrogen inhibits any hydride elimination steps.
␤-hydride elimination explicitly explains olefin
production during reforming. This is a facile reaction,
commonly leading to a rapid alkane–alkene equilib-
rium [13,118]. Together with the reverse C=C insertion
into metal–hydrogen bonds (the half hydrogenation
of adsorbed olefins to alkyls) and the reductive elim-
ination between alkyl and hydrogen adsorbates (the
second hydrogenation of alkyls to alkanes), it also
accounts for other catalytic processes such as H–D
exchange and double bond migration [71,90,96,99,
100,118–130]. H–D isotope exchange in particu-
lar may not be particularly important in practical
catalysis, but plays a central role in mechanis-
tic studies of hydrocarbon conversion processes
[12,13,21,131–133], and has provided a conve-
nient way to estimate metal–carbon bond energies
in surface-science studies [52,66,74,113,123,126,
134,135]. It has also allowed for the calculation of
relative rates between hydrogenation and dehydro-
genation steps [100].
It is worth emphasizing here that selectivity in hy-
drocarbon reforming is frequently controlled by the
relative rates among a number of alternative path-
ways. In particular, the nature of the final products is
typically determined by competition among different
hydrogenation and dehydrogenation steps. It is here
where seemingly simple reactions such as isotope ex-
change can help. It has consistently been reported that
H–D scrambling in alkanes and alkenes, which takes
place via the interconversion of alkyls and olefins,
is much more extensive on platinum than on nickel
[12,13,132]. Given that the rate of ␤-hydride elimi-
nation, although somewhat dependent on the nature
of the catalyst, is quite facile on most late transition
metals [52,61,67,68,71,109,113,118,129,130,136], it
must be concluded that the final exchange product
distribution is determined by the relative rates of
 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91 83

Fig. 6. Dependence of surface alkyl dehydrogenation rates on the nature of the surface (left) and of the reactants (right) [52,66,74]. Left:
temperature maxima for methane (clear bars) and ethylene (filled bars) desorption as a function of metal and crystallographic orientation.
Those data provide an indication of the relative reactivity for ␣- and ␤-hydride eliminations, respectively, across the series of surfaces
reported. Right: TPD temperature maxima for the production of olefins from surface alkyls as a function of hydrocarbon chain length and
degree of branching. Data are shown for reactions on Ni(1 0 0) (filled bars) [70] and Cu(1 0 0) (clear bars) [112]. In general, increases in
reactivity are seen with early transition metals and with decreasing hydrocarbon chain lengths.

olefin re-hydrogenation versus further decomposition.
Therefore, it is the particular ease with which nickel
promotes further dehydrogenation steps what limits
H–D exchange on that metal. Conversion on platinum,
on the other hand, yields extensive H–D scrambling,
as manifested not only by the high degree of deu-
terium substitution in the final products, but also by
the low temperatures at which the reaction proceeds
[113,130]. Fig. 7 displays laser-induced desorption
data for the case of ethylene exchange with adsorbed
deuterium on a Pt(1 1 1) surface [129]. It is shown
there that extensive exchange can be induced at tem-
peratures as low as 215 K. Similar arguments also
apply to exchange at the ␣- and ␥-position (see later).
5. ␣- and ␥-hydride eliminations: prelude to
hydrogenolysis and isomerization
␤-hydride elimination may be the dominant step
in the conversion of alkyl surface species, but other
dehydrogenation steps are required to explain the more
demanding reforming processes. A number of studies
have been carried out by us and others to tackle this
issue. The results from that work lead us to believe
that the selectivity in reforming processes is defined
by the regiospecificity of the removal of the next hy-
drogen atom from alkyl surface intermediates. While
dehydrogenation at the ␣-position is likely to lead to
eventual C–C bond scissions [15], reactivity at the
␥-carbon may be responsible for isomerization and cy-
clization steps [20,137,138].
Hydride elimination from the ␣- and ␥-position are
generally much less favorable than from the ␤-carbon,
but can still be probed by using adsorbates with no
␤-hydrogens such as methyl, neopentyl, and benzyl
moieties. The simplest case of ␣-H elimination is the
conversion of methyl to methylene groups, a reaction
first established on Pt(1 1 1) by reflection-absorption
infrared spectroscopy [63]. The multiple H–D ex-
change seen for methyl groups on Pt(1 1 1) suggests
an activation barrier of less than 10 kcal/mol for the
84 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
Fig. 7. Typical mass spectra from laser-induced thermal desorp-
tion/Fourier transform mass spectrometry (LITD/FTMS) experi-
ments designed to characterize the kinetics of H–D exchange re-
actions between C2 D4 and H atoms on Pt(1 1 1) [129]. In this
case, the adsorption of 0.13 ML of C2 D4 was followed by a dos-
ing of 20 L of H2 , and the reaction was carried out at 225 K. The
exchange is manifested by both a decrease in signal intensity for
32 amu (C2 D4 ) and a simultaneous growth of the 31 (C2 D3 H)
and 29 and 27 (multiply-exchanged C2 X4 ) amu peaks during the
course of the reaction.
initial a dehydrogenation from those moieties [122].
In the case of the thermal activation of methyl iodide
on either Ni(1 0 0) or Ni(1 1 1) surfaces, experiments
both with labeled methyl iodide and with methylene
iodides co-adsorbed with hydrogen provided a lower
limit for the temperature of the ␣-hydride elimination
reaction in the conversion of methyl to methylidyne at
above 200 K [90], over 40 K higher than that needed
for ␤-hydride elimination from ethyl groups. This
represents a difference of about 2 kcal/mol in activa-
tion energy, or about a 25% increase in barrier height
[65,124,135]. Additional comparisons between ␣-
and ␤-hydride elimination have been achieved indi-
rectly by isotope scrambling during high-temperature
ethylidyne formation [139] and by catalytic studies
with ethane on platinum [127]. Those experiments
indicated a difference in rate between the two steps
of over four orders of magnitude at low temperatures,
but of only about a factor of five around 600 K. Again,
this works out to a barrier difference of approximately
2 ± 1 kcal/mol.
Hydrogenolysis after ␣-hydride elimination has
been corroborated in the case of neopentyl iodide con-
version on Ni(1 0 0) [140]. In that system, the initial
elimination of one of the a hydrogen atoms from the
neopentyl moiety occurs below 200 K. The resulting
neopentylidene intermediate is quite stable, react-
ing further only above 350 K to ultimately produce
isobutene. The mechanism by which neopentylidene
decomposes to isobutene appears to involve the con-
certed scission of the C␣ –C␤ bond in conjunction with
the elimination of hydrogen atoms from the ␣- and
␥-positions. The interesting observation here in terms
of selectivity in reforming is that the hydrogenolysis
of alkyl intermediates may be rate limited by the C–C
bond breaking step, but is decided by a much earlier
and facile dehydrogenation reaction.
As stated above, elimination at positions fur-
ther along the carbon chain, whenever possible, are
believed to yield the cyclic products proposed in iso-
merization reactions (Fig. 8). The selectivity between
␥- and ␣-hydride elimination depends on the nature
of the metal surface: both steps are possible on plat-
inum [141], but only the latter is observed on nickel
[140]. This trend explains the unique ability of plat-
inum for catalyzing reforming processes, as opposed
to nickel, which leads to exclusive cracking instead
[100]. It should be emphasized again that it is the
relative rates among the different available paths on
a given surface what matters in terms of defining se-
lectivity. All dehydrogenation steps follow the same
qualitative trends, that is, they become faster on early
transition metals or with heavier hydrocarbon chains.
Some examples of this are provided for ␣- and
␤-hydride elimination reactions in Fig. 6. However,
the relative rates for ␣-, ␤-, and ␥-dehydrogenation
within the same metal also change across the periodic
table, because the magnitude of the variations in rate
for each of those steps can be quite different on differ-
ent metals. Notice, for instance, the large difference
in maximum temperature in temperature programmed
desorption (TPD) experiments for ␣ (>450 K) versus
␤ (∼250 K) eliminations on copper reported in Fig. 6.
A significantly smaller difference between the two
(<100 K) is seen on platinum, palladium, or nickel
crystals. It is also for this reason that while only
 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91 85

Fig. 8. Schematic representation of the elementary surface reaction steps proposed for the hydrogenolysis and isomerization of hydrocarbons
during catalytic reforming [15,20]. The example provided here corresponds to neopentyl intermediates. The arguments is made that while
␣-hydride elimination eventually leads to C–C bond scission and yields hydrogenolysis products, hydride elimination at the ␥-position
results in isomerization and cyclization instead. The steps identified in studies with Pt and Ni single crystal surfaces are indicated in the
figure as well [100,140,141].

␣-hydride elimination can be detected from neopentyl
groups on Ni(1 0 0), both ␣- and ␥-hydride elimina-
tions display comparable rates on Pt(1 1 1). The same
argument holds true when contrasting hydrogenation
versus dehydrogenation steps, as mentioned in the
previous discussion on isotope exchange.
6. Bond forming steps
So far in this review we have addressed dehy-
drogenation reactions, that is, C–H bond-breaking
steps. Reforming catalysis also involves bond-forming
processes. In general, though, those are much more
difficult to emulate under vacuum conditions. In this
section, we summarize what we have learned about
reductive eliminations and coupling steps in the last
decade.
Hydrogenation reactions, the reverse of C–H bond
scissions, are possible under vacuum as long as the
surfaces are predosed with large coverages of hy-
drogen [118]. Indeed, most olefins are capable of
hydrogenating to their corresponding alkanes dur-
ing temperature-programmed desorption experiments
[118,120,142]. Extensive information has been ob-
tained on the mechanism of that reaction by a com-
bination of experiments with deuterium isotopic
labeling and with alkyl and other potential interme-
diates [113,126,143]. It has become quite clear that
alkenes hydrogenate in a stepwise manner, via the
86 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
slow formation of an alkyl intermediate [119,139]. In
analogy with organometallic chemistry, the first step,
the hydrogenation of the olefin to an alkyl moiety,
can be described as the insertion of an olefin into
a metal–hydrogen bond, while the second, the con-
version of the alkyl to an alkane, corresponds to the
reductive elimination of alkyl groups with hydrogen
atoms. In the case of platinum, the reversibility of the
first step (the ␤-hydride elimination from alkyls dis-
cussed before [61,66]) leads to the rapid interchange
of hydrogen atoms within the adsorbed hydrocarbons.
Therefore, when deuterium is used instead of nor-
mal hydrogen in TPD experiments, extensive H–D
exchange is observed [119,120].
Similar conclusions can also be reached in refer-
ence to alkanes incapable of direct dehydrogenation
to olefins such as methane or neopentane. In those
cases, the relative rates of hydrogenation versus de-
hydrogenation and the selectivity in dehydrogenation
from the different positions still control both the type
of intermediates that forms on the surface [100] and
the extent of the H–D exchange [90,121,122]. For in-
stance, neopentyl groups dehydrogenate exclusively
to neopentylidene on Ni(1 0 0) [140,144] but are able
to also loose hydrogen atoms from the ␥ position
(and presumably form a metallacyclic surface moi-
ety) on Pt(1 1 1) [141,145], and the re-hydrogenation
of those intermediates is easier in relative terms on
platinum than on nickel. Consequently, more exten-
sive exchange is seen for neopentane on the former
metal [146–148].
There have been only a handful of clean examples
for C–C bond forming steps under vacuum. Methylene
insertion and alkyl coupling steps have been identified
on late transition metals, most noticeably on coinage
metals [52,74,115,149]. Alkyl coupling takes place
with 100% selectivity on silver [117], but competes
with hydride elimination steps, especially at low alkyl
coverages, on palladium [150], copper [73,74,115],
and gold [116,151]. It appears that the selectivity to-
wards reductive elimination reactions may at least in
part be determined by the ability of the metal to acti-
vate dehydrogenation reactions: only when dehydro-
genation is slow it is possible for the metal to promote
such bond forming steps [152]. Also, coupling reac-
tions are bimolecular, and therefore display kinetics
strongly dependent on the concentrations of the sur-
face reactants. For instance, the thermal activation of
methyl moieties yields ethylidyne moieties on Pt(1 1 1)
[153] and Ru(0 0 0 1) [154] surfaces only at high cover-
ages. It is also conceivable that, at least in some cases,
the actual C–C surface recombination step is fast, and
that the rate for alkyl dimerization is controlled by the
diffusion of the reactants on the surface.
Thermal activation of surface metallacycles can also
lead to a C–C coupling, in that case to eliminate cyclic
hydrocarbons. Such steps have been reported on sil-
ver [117] and nickel [102,103], but were not seen on
aluminum [155], palladium [156], or platinum [104].
The particular fact that cyclopropane is produced from
thermal activation of 1,3-diiodopropane on Ni(1 0 0)
[102] but not on Pt(1 1 1) [102] is somewhat odd,
since platinum is a better cyclization catalyst than
nickel. However, benzene formation from nickellacy-
cloheptane intermediates appears to require an exten-
sive prior dehydrogenation of those surface moieties
[103]; again, nickel is a particularly able surface when
it comes to dehydrogenation steps, ␣-H elimination in
particular. Perhaps the most interesting C–C coupling
reaction on single-crystal surfaces reported so far is the
trimerization of acetylene on Pd(1 1 1) [157], a reac-
tion takes place via an initial oxidative coupling of two
acetylene molecules to form a Pd–C4 H4 metallacycle
[158]. Acetylene trimerization has also been observed
on nickel [159], copper [160], and tin-modified plat-
inum [161] surfaces, but no mechanistic details were
provided in the reports of those cases.
In terms of relative rates for C–H versus C–C
bond-forming reactions, it has been reported that
co-adsorption of hydrogen with phenyl groups on
Cu(1 1 1) completely inhibits biphenyl formation at
the expense of benzene production [162]; C–H reduc-
tive elimination steps are clearly favored in that case.
We believe that this conclusion may be quite general,
applying to most metals relevant to reforming. In ad-
dition, phenyl groups act as efficient traps for alkyl
radical intermediates, an indication that alkyl–aryl
coupling is favored over alkyl–alkyl formation [163].
7. Added complications from the use of
atmospheric pressures in catalysis
An additional level of complication is added to
the study of hydrocarbon conversion when atmo-
spheric pressures are considered. This is so because
 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91 87

hydrocarbon catalysis does not occur on clean metal
surfaces, but rather on metals covered with strongly
bonded carbonaceous residues [11,164]. In fact, the
initial dehydrogenation steps discussed above take
place at quite low temperatures, at least on clean metal
surfaces, and are followed by additional decomposi-
tion reactions. In particular, the olefins produced via
␤-hydride elimination react around room temperature
to yield alkylidyne species (Fig. 5). The mechanism
for this reaction has been highly contested and is
not yet fully understood [165–168], but appears to
involve an alkylidene intermediate [139,169,170].
Regardless, the same alkylidyne surface moieties ap-
pear to form during the catalytic hydrogenation of
olefins [12,118,171–173].
In retrospect, it is easy to understand why such a
hydrocarbon layer is needed to passivate the surface;
otherwise, dehydrogenation steps would dominate the
conversion of hydrocarbons even on platinum sur-
faces. It has also become clear that strongly bonded
carbonaceous species only play an indirect role in
hydrogenation and dehydrogenation processes. TPD
and 14 C isotope labeling experiments have indicated
that their residence time and composition depend
on temperature, becoming more hydrogen deficient
and strongly held with increasing temperature, but
that they always turn over at rates orders of mag-
nitude slower than those of the catalytic conversion
[118,174,175]. Indirect evidence suggests that similar
species may also be present on the surface during
more demanding hydrogenolysis and reforming pro-
cesses, but that they may be more directly involved
in the mechanism of those reactions [127,176].
The net result from all of this is that clean metal
surfaces become covered with carbonaceous species
right at the beginning of most reforming reactions,
changing the chemisorption characteristics of the
reactants. In order to understand the hydrogena-
tion of unsaturated hydrocarbons in particular, olefin
␲-bonding needs to be considered in the mechanistic
picture. Such species have indeed been identified by
vibrational spectra both in vacuum [177] and in situ

Fig. 9. Left: typical isothermal kinetic raw data obtained for the conversion of ethylene on Pt(1 1 1) at 270 K by using a molecular beam
technique [128]. The rates of ethylene consumption, hydrogenation to ethane and ethylidyne formation were measured as a function of time
by following the mass spectroscopy signals for 25, 30, and 2 amu, respectively. The initial uptake of ethylene is followed by an additional
small reversible adsorption of weakly-bonded olefins, as manifested by the spikes observed right after blocking (flag up) and unblocking
(flag down) of the beam. Right: dependence of the initial rate of ethane formation on the coverage of weakly-adsorbed ␲-ethylene. The
solid line through the data points, a polynomial fit corresponding to a kinetic order of 1.2 ± 0.3, indicated that it is the weakly adsorbed
ethylene the one involved in the hydrogenation reaction.
88 F. Zaera / Applied Catalysis A: General 229 (2002) 75–91
under reaction conditions [178–181]. Infrared spectra
for both (strongly bonded) di-␴- and (weakly bonded)
␲-propylene on Pt(1 1 1) are shown in Fig. 5. Addi-
tional molecular beam kinetic work on the ethylene
hydrogenation/Pt(1 1 1) system has revealed that: (1)
weakly-bonded ␲-olefins are indeed the ones that
intervene directly in the hydrogenation process; (2)
the dissociative adsorption of hydrogen on the sur-
face is rate-limiting for the overall reaction; and (3)
strongly-adsorbed alkenes and other carbonaceous
deposits inhibit the latter step [128]. Key kinetic data
for this ethylene/Pt(1 1 1) system are shown in Fig. 9.
Hydrogen also plays a unique role in hydrocar-
bon conversion processes. It has been long recognized
that one of the key functions of metals as catalysts
in hydrogenation–dehydrogenation and skeletal rear-
rangement reactions is to activate molecular hydrogen
to produce chemisorbed hydrogen atoms [13]. How-
ever, the exact manner in which the resulting atomic
hydrogen participates in the hydrocarbon conversion
steps remains unsettled. In fact, it is quite possible that
hydrogen transfer from the metal to the reactants may
be mediated by the surface carbonaceous deposits.
What is clear is that hydrogen pressures affect the se-
lectivity of many reactions, as well as hydrogenation
versus dehydrogenation and more complex reforming
networks, in a significant way [12]. For instance, it has
been shown that the selectivity during the conversion
of cyclohexene on Pt(1 1 1) changes dramatically with
pressure, with the benzene (dehydrogenation) to cyclo-
hexane (hydrogenation) production ratio going from
about 100:1 below 10−7 Torr total pressure to 1:100 at
10 Torr [182]. In that case, it was argued that this selec-
tivity change is a reflection of an approximately con-
stant reaction probability with changing pressure for
hydrogenation, in contrast to the strong dependence
of dehydrogenation rates on pressure due to the fact
that those reactions require large surface ensembles
of empty sites which become blocked by other adsor-
bates at high pressures. Hydrogen adsorption may also
be inhibited by competition with gas-phase hydrocar-
bons, hence the often negative dependence of reaction
rates on hydrocarbon partial pressures [12,118].
8. Conclusions
A molecular model of the working reforming cat-
alyst has been advanced based on the information
discussed above where the surface is mostly covered
with three-dimensional carbonaceous islands but still
retains some patches of uncovered bare metal [164].
The initial and final hydrocarbon hydrogenation and
dehydrogenation steps are likely to involve weakly
adsorbed species, ␲-bonded in the case of olefins, and
to be aided by the strongly-bonded deposits. Those
moieties not only moderate the dehydrogenating high
activity of the clean metal surface, but also act as a
reservoir of hydrogen atoms [11]. The more demand-
ing intermediate processes, on the other hand, are
likely to occur directly on the exposed metal sites.
There, the selectivity between the C–C scission steps
that lead to undesirable hydrogenolysis and the skele-
tal rearrangements involved in reforming is defined
by the relative rates of the initial dehydrogenation
of alkyl intermediates between the ␣-position versus
␥-position.
Acknowledgements
Financial support for this research was provided by
a grant from the National Science Foundation, Chem-
istry Division (CHE-9819652).
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