ch1.
1
Introduction
1.1
Principles of Heterogeneous Catalysis1
James A. Dumesic∗ , George W. Huber and Michel Boudart
1.1.1
Introduction
Heterogeneous catalysis is of vital importance to the
world’s economy, allowing us to convert raw materi-
als into valuable chemicals and fuels in an economical,
efficient, and environmentally benign manner. For ex-
ample, heterogeneous catalysts have numerous industrial
applications in the chemical, food, pharmaceutical, au-
tomobile and petrochemical industries [1–5], and it has
been estimated that 90% of all chemical processes use het-
erogeneous catalysts [6]. Heterogeneous catalysis is also
finding new applications in emerging areas such as fuel
cells [7–9], green chemistry [10–12], nanotechnology [13],
and biorefining/biotechnology [14–18]. Indeed, contin-
ued research into heterogeneous catalysis is required to
allow us to address increasingly complex environmental
and energy issues facing our industrialized society.
Discussing the principles of heterogeneous catalysis is
difficult, because catalysts are used for a wide range of
applications, involving a rich range of surface chemistries.
Moreover, the field of heterogeneous catalysis is highly
interdisciplinary in nature, requiring the cooperation
between chemists and physicists, between surface
scientists and reaction engineers, between theorists and
experimentalists, between spectroscopists and kineticists,
and between materials scientists involved with catalyst
synthesis and characterization. Furthermore, industrial
catalysts are complex materials, with highly optimized
chemical compositions, structures, morphologies, and
pellet shapes; moreover, the physical and chemical
characteristics of these materials may depend on
1 A list of abbreviations/acronyms used in the text is provided at the
end of the chapter.
∗ Corresponding author.
hidden or unknown variables. Accordingly, principles
of heterogeneous catalysis are typically formulated from
studies of model catalysts in ideal reactors with simplified
reactants under mild pressure conditions (e.g., 1 bar),
rather than from catalytic performance data obtained with
commercial catalysts in complex reactors using mixed
feed streams under industrial reaction conditions. The
principles derived from these more simplified studies
advance the science of heterogeneous catalysis, and they
guide the researcher, inventor, and innovator of new
catalysts and catalytic processes.
1.1.2
Definitions of Catalysis and Turnover
The definition of a catalyst has been discussed many
times [19]. For example, a catalyst is a material that
converts reactants into products, through a series of
elementary steps, in which the catalyst participates while
being regenerated to its original form at the end of each
cycle during its lifetime. A catalyst changes the kinetics
of the reaction, but does not change the thermodynamics.
Another definition is that a catalyst is a substance
that transforms reactants into products, through an
uninterrupted and repeated cycle of elementary steps
in which the catalyst participates while being regenerated
to its original form at the end of each cycle during its
lifetime [20].
The main advantage of using a heterogeneous catalyst
is that, being a solid material, it is easy to separate from
the gas and/or liquid reactants and products of the overall
catalytic reaction. The heart of a heterogeneous catalyst
involves the active sites (or active centers) at the surface
of the solid. The catalyst is typically a high-surface area
material (e.g., 10–1000 m2 g−1 ), and it is usually desirable
to maximize the number of active sites per reactor volume.
Identifying the reaction intermediates – and hence the
References see page 14
ch1.1
2 1.1 Principles of Heterogeneous Catalysis
mechanism – for a heterogeneous catalytic reaction is
often difficult, because many of these intermediates are
difficult to detect using conventional methods (e.g., gas
chromatography or mass spectrometry) because they do
not desorb at significant rates from the surface of the
catalyst (especially for gas-phase reactions).
Heterogeneous catalysts typically contain different
types of surface sites, because crystalline solids exhibit
crystalline anisotropy. Equilibrated single crystals expose
different faces with different atomic structures so
as to minimize total surface energy. It would be
surprising, in fact, if different crystallographic planes
exposing sites with different coordination environments
possessed identical properties for chemisorption and
catalytic reactions. Moreover, most catalytic solids are
polycrystalline. Furthermore, in order to achieve high
surface areas, most catalysts contain particles with sizes
in the nanometer length scale. The surfaces of these
nanoscopic particles contain sites associated with terraces,
edges, kinks, and vacancies [21]. If the catalyst contains
more than one component (as is generally the case), the
surface composition may be different from that of the bulk
and differently so for each exposed crystallographic plane.
Solids normally contain defects of electronic or atomic
nature; in addition, they contain impurities which are
either known or unknown in the bulk, but are mostly
unknown at the surface. Finally, the surface atomic
structure and composition may change with time-on-
stream as the catalytic reaction proceeds. In short, it
is normal to expect that a catalytic surface exposes a
variety of surface sites, in contrast to displaying a single
type of active site. Indeed, it is so normal today to
expect such complexity that it seems surprising that,
in 1925, when Taylor formulated his principle of active
sites or active centers, the report created so much
attention and remains one of the most often cited in
heterogeneous catalysis [22]. The relative importance of
surface structure – as influenced by crystalline anisotropy,
surface defects, and surface composition – underlines the
difficulty of identifying the active sites, either simple
or complex, that are responsible for turning over the
catalytic cycle. The identification and counting of active
sites in heterogeneous catalysis became the ‘‘Holy Grail’’
of heterogeneous catalysis in 1925, and the situation
remains the same today.
The activity of a catalyst is defined by the number of
revolutions of the catalytic cycle per unit time, given in
units of turnover rate (TOR) or turnover frequency (TOF).
In cases where the rate is not uniform within the catalytic
reactor or within the catalyst pellets, it is useful to report
the rate as a site time yield (STY), defined as the overall rate
of the catalytic reaction within the reactor normalized by
the total number of active sites within the reactor, again
in units of reciprocal time. Catalysis by solid materials
has been observed quantitatively at temperatures as low
as 78 K and as high as 1500 K; at pressures between
10−9 and 103 bar; with reactants in the gas phase or in
polar or non-polar solvents; with or without assistance
of photons, radiation or electron transfer at electrodes;
with pure metals as unreactive as gold and as reactive as
sodium; with multicomponent and multiphase inorganic
compounds and acidic organic polymers; and at STYs
as low as 10−5 s−1 (one turnover per day) and as high
as 109 s−1 (gas kinetic collision rate at 10 bar). TOFs of
commonly used heterogeneous catalysts are commonly
on the order of one per second. The life of the catalyst can
be defined as the number of turnovers observed before
the catalyst ceases to operate at an acceptable rate. Clearly,
this number must be larger than unity, otherwise the
substance used is not a catalyst but a reagent. Catalyst
life can either be short, as in catalytic cracking of oil, or
very long, corresponding to as many as 109 turnovers in
ammonia synthesis.
1.1.3
Steps in a Heterogeneous Catalytic Reaction
During an overall catalytic reaction, the reactants
and products undergo a series of steps over the
catalyst, including:
1. Diffusion of the reactants through a boundary layer
surrounding the catalyst particle.
2. Intraparticle diffusion of the reactants into the catalyst
pores to the active sites.
3. Adsorption of the reactants onto active sites.
4. Surface reactions involving formation or conversion
of various adsorbed intermediates, possibly including
surface diffusion steps.
5. Desorption of products from catalyst sites.
6. Intraparticle diffusion of the products through the
catalyst pores.
7. Diffusion of the products across the boundary layer
surrounding the catalyst particle.
Accordingly, different regimes of catalytic rate control
can exist, including: (i) film diffusion control (Steps 1
and 7); (ii) pore diffusion control (Steps 2 and 6); and
(iii) intrinsic reaction kinetics control (Steps 3 to 5) of
catalyst performance. In addition to mass transfer effects,
heat transfer effects can also occur in heterogeneous
catalysis for highly exothermic or endothermic reactions
(especially in combustion or steam reforming).
Figure 1 shows a general effect of temperature on
the reaction rate for a heterogeneous catalyst. At low
temperatures, diffusion through the film and pores is
fast compared to rates of surface reactions, and the
overall reaction rate is controlled by the intrinsic reaction
ch1.1
Slope = 3-5 kJ/mol
Slope = Ea/2R
Film diffusion
controlled regime
ln (rate)
Pore diffusion
Slope = Ea/R
controlled regime
Intrinsic
regime
Increasing
Temperature
1/ Temperature
Fig. 1 General effects of temperature on catalytic activity. The
intrinsic activation energy is equal to Ea , and R is the gas constant.
kinetics. As the temperature is increased, the rates of
surface reactions typically increase more rapidly than the
rates of diffusion, and the overall rate of the catalytic
process becomes controlled by intraparticle diffusion.
The apparent activation energy in this regime is equal
to the intrinsic activation energy divided by two. As the
temperature is increased further, mass transfer through
the external boundary layer becomes the controlling
step. The onset of diffusion limited regimes can be
altered by changing the reactor design, the catalyst pore
structure, the catalyst particle size, and the distribution
of the active sites in the catalyst particles. Values
of various dimensionless groups can be calculated to
estimate the extents to which transport phenomena
may control catalytic performance for specific operating
conditions [23–31]; however, these calculations are most
reliable for cases where the intrinsic reaction kinetics are
known. In these cases, it is possible to make catalysts
with structures designed to provide adequate rates of
diffusion and yet offering high surfaces areas, leading
to high rates of reaction per reactor volume, such as
the design of specific pore size distributions (e.g., bi-
modal distributions containing large pores leading to
high accessibility of the active sites within the interior of
the catalytic pellet, and small pores that branch from the
larger pores leading to high surface areas), the formulation
of unique pellet shapes (that lead to high accessibility of
the active sites but do not cause large pressure drops
through the catalytic reactor), and the synthesis of catalyst
pellets containing a spatial distribution of the active
material within the catalyst pellet [32]. In some cases,
transport effects can be used to improve the selectivity of
a catalyst, such as in the case of shape-selective catalysis
in zeolites [33–36]. In the following sections, we focus on
various factors controlling the intrinsic reaction kinetics
1.1.4 Desired Characteristics of a Catalyst 3
of catalysts, and we refer the reader to other articles for
further discussion on transport effects in heterogeneous
catalysis [23–31].
1.1.4
Desired Characteristics of a Catalyst
The following list provides several of the key attributes of
a good catalyst:
• The catalyst should exhibit good selectivity for produc-
tion of the desired products and minimal production of
undesirable byproducts.
• The catalyst should achieve adequate rates of reaction
at the desired reaction conditions of the process
(remembering that achieving good selectivity is usually
more important than achieving high catalytic activity).
• The catalyst should show stable performance at reaction
conditions for long periods of time, or it should be
possible to regenerate good catalyst performance by
appropriate treatment of the deactivated catalyst after
short periods.
• The catalyst should have good accessibility of reactants
and products to the active sites such that high rates can
be achieved per reactor volume.
The first three key attributes of a good catalyst are
influenced primarily by the interactions of the catalyst
surface with the reactants, products, and intermediates
of the catalytic process. In addition, other species may
form on the catalyst surface (e.g., hydrogen-deficient
carbonaceous deposits denoted as coke) that are not
directly part of the reaction scheme (or mechanism) for
the overall catalytic process.
The principle of Sabatier states that a good heteroge-
neous catalyst is a material that exhibits an intermediate
strength of interaction with the reactants, products, and
intermediates of the catalytic process [37, 38]. Interactions
of the catalyst surface with the various adsorbed species
of the reaction mechanism that are too weak lead to
high activation energies for surface reactions and thus
low catalytic activity, whereas interactions of the catalyst
with adsorbed species that are too strong lead to excessive
blocking of surface sites by these adsorbed species, again
leading to low catalytic activity.
The principle of Sabatier is elegant in its simplicity
and generality, but it is deceptively difficult to use in
practice. In particular, this principle applies to a catalyst
in its working state, and the nature of the catalyst surface
can be expected to be dependent on the nature of the
catalytic reaction conditions. For example, one may begin
the catalytic reaction with the heterogeneous catalyst
References see page 14
ch1.1
4 1.1 Principles of Heterogeneous Catalysis
in a given oxidation state (e.g., containing zero-valent
metal particles following treatment of the catalyst in
H2 at elevated temperature); however, the nature of the
surface can be changed dramatically upon interaction
with strongly adsorbed species, such as the formation of
carbonaceous deposits (coke), and formation of oxides,
carbides, nitrides, or sulfides upon interaction with O,
C, N, or S species, respectively [39–44]. In this case,
the interactions of these oxide, carbide, nitride, or
sulfide surfaces with the adsorbed species enter into
the reaction mechanism. Of even greater complexity
is the fact that a variety of different types of sites are
typically present on a catalyst surface (e.g., sites having
different coordination and/or chemical composition), and
a majority of the observed catalytic activity may be
caused by the contributions from a small fraction of
the sites present on the catalyst surface. In this case,
the adsorbed species interact with these special surface
sites (e.g., steps and defect sites on a metal nanoparticle,
or sites present at the metal–support interface of a
supported metal catalyst). Another factor that complicates
catalyst design is that the strengths of interaction of
the surface with adsorbed species typically depend on
the surface coverages by adsorbed species. For example,
the interaction of a transition metal surface with adsorbed
CO may be very strong at low surface coverages (e.g.,
binding energy of nearly 200 kJ mol−1 ), suggesting that
these surfaces would be completely covered and thus
poisoned by adsorbed CO at moderate pressures and
temperatures; however, these surfaces may carry out
catalytic reactions in the presence of gaseous CO at these
pressures and temperatures because the differential heat
of CO adsorption decreases significantly (e.g., to binding
energies near 100 kJ mol−1 ) as the surface coverage by
adsorbed CO increases [45, 46]. Accordingly, there is a
relationship between activity and the interaction of the
surface with adsorbed species at the surface coverage
regime appropriate for the catalytic reaction conditions.
The aforementioned complications caused by the
presence of different types of sites on the surface, and
the effects on the surface binding energies caused by
changes in surface coverages, clearly make it difficult to
interpret the performance of a heterogeneous catalyst
in quantitative detail. Tools are certainly available to
address these complications, such as kinetic Monte
Carlo simulations combined with results from density
functional theory (DFT) calculations [47–50]. Yet, from
a different point of view, the presence of different
types of sites and the effects of surface coverage may
well contribute to the robustness of the heterogeneous
catalyst for operation over a wide range of reaction
conditions. In general, the presence of different types
of sites and the effects of surface coverage both
contribute to surface non-uniformity (different types
of sites producing a prior non-uniformity, and effects
of surface coverage causing induced non-uniformity).
At a selected set of reaction conditions, an optimal
set of surface binding energies exists that satisfy the
principle of Sabatier (as discussed below). Accordingly,
the performance of a heterogeneous catalyst with a
non-uniform surface will be dominated by the subset
of the sites having surface binding energies closest to
the optimal values. At higher temperatures, other sites
having stronger binding energies with adsorbed species
will become the dominant contributors to the observed
catalytic activity, whereas sites having weaker binding
energies with adsorbed species will control catalytic
activity at lower temperatures. Thus, while the effects of
surface non-uniformity make it more difficult to predict
the performance of a heterogeneous catalyst from a
molecular-level understanding, these effects may serve
to broaden the range of reaction conditions over which
the catalyst can operate effectively. In this respect, our
desire to design catalysts having very high selectivity
is guided by the synthesis of uniform catalysts, where
each site has the optimal properties for production of
the desired reaction product. This strategy leads to the
idea of highly selective, single-site catalysis as discussed
by Thomas et al. [51]. In contrast, the design of catalysts
that operate over a wide range of reaction conditions is
guided by the synthesis of non-uniform catalysts, such
that different subsets of sites control catalyst performance
at different reaction conditions. The disadvantage of using
non-uniform catalysts, however, is that different sites may
display different selectivities for the production of various
products, and control over catalytic selectivity may thus
be limited [22].
1.1.5
Reaction Schemes and Adsorbed Species
We now explore further the principle of Sabatier using
a specific example: water-gas shift over a metal catalyst
(e.g., Cu). This reaction (CO + H2 O ← −−−−−
→− CO2 + H2 ) is
of importance for the production of H2 from steam-
reforming of fossil fuels, and for controlling the CO : H2
ratio in synthesis gas mixtures used in methanol and
Fischer–Tropsch synthesis processes. For this example,
we consider the reaction scheme shown in Fig. 2, where
* represents a surface site. The stoichiometric numbers,
σi,1 and σi,2 , indicate the number of times that step i
occurs to give the overall reaction for reaction schemes 1
and 2, respectively.
In this sequence of steps, the water-gas shift reaction
can take place via the formation of carboxyl species
(COOH) or through the formation of formate species
(HCOO) [52]. In the absence of a catalyst, the rate of water-
gas shift via this mechanism is negligible, because the
ch1.1

1.1.5 Reaction Schemes and Adsorbed Species 5

si,1 si,2 does not participate in the overall reaction. In this latter
1. CO + ∗ CO∗ 1 1 case, the spectator species inhibits the overall reaction
by blocking surface sites, and it serves no useful role in
2. H2O +∗ H2O∗ 1 1
the overall reaction scheme. For purposes of elucidating
3. H2O ∗ + ∗ OH ∗+H ∗ 2 1 catalytic reaction schemes it is essential to distinguish
between reactive intermediates and spectator species. This
4. CO ∗ + OH ∗ COOH ∗+ ∗ 1 0 distinction is of paramount importance in spectroscopic
CO2∗ + H2O ∗
studies of adsorbed species on catalyst surfaces, where
5. COOH ∗ + OH ∗ 1 0
the detection of a specific adsorbed species using a
6. CO2∗ CO2 + ∗ 1 1 spectroscopic method (e.g., the detection by infra-red
(IR) studies of adsorbed ethylidyne species on platinum
7. 2H ∗ H2 + 2∗ 1 1
surfaces during ethylene hydrogenation [53]) does not
8. CO ∗ + OH ∗ HCOO ∗∗ 0 1 guarantee that this species is a reactive intermediate.
Instead, these spectroscopic studies must be conducted
9. HCOO∗∗ CO2∗ + H ∗ 0 1 under dynamic conditions (e.g., so-called operando
CO + H2O CO2 + H2
measurements, where spectroscopic and reaction kinetics
overall
data are collected simultaneously) to determine that
the time constant for the formation or disappearance
Fig. 2 Assumed reaction mechanism for water-gas shift reaction
over Cu. Adapted from Ref. [52]. of the surface species is the same as the time constant for
the overall catalytic reaction [54, 55].
The overall catalytic reaction is given by a linear
reaction intermediates (e.g., OH∗ , H∗ , COOH∗ , HCOO∗ ) combination of elementary steps, and the enthalpy change
are at very low concentrations in the gas phase. For for the overall reaction, H , is given by:
example, the enthalpy change for step 3 in the gas phase


is approximately 500 kJ mol−1 . However, adsorption of H = σi Hi (1)
the reaction intermediates onto the catalyst surface allows i
these steps to take place with small enthalpy changes. In
the case of copper, the binding energies of H and OH where Hi are the enthalpy changes for elementary
are approximately 250 and 280 kJ mol−1 on Cu(111), such steps i. From the principle of Sabatier, it is now clear
that the enthalpy change for step 3 on the catalyst surface that the overall value of H should be composed of
is now slightly exothermic. According to the principle of approximately equal contributions from each of the
Sabatier, a good catalyst is a material that adsorbs reaction values of Hi , giving rise to a relatively flat potential
intermediates with intermediate strength. However, we energy diagram of energy versus reaction coordinate in
now must distinguish between reactive intermediates and moving from reactants, through adsorbed intermediates,
spectator species on the catalyst surface. to products. Specifically, any value of Hj that is very
In the above reaction scheme, we see that the water- negative must be balanced by a value of Hk that is
gas shift reaction can take place through adsorbed very positive, such that the surface will become highly
carboxyl species or formate species. Results from DFT covered (and poisoned) by the adsorbed species produced
calculations indicate that adsorbed formate species have in step j , and the activation energy for step k will be high.
lower energy compared to adsorbed carboxyl species on Both of these effects lead to low catalytic activity. We note
copper surfaces, suggesting that path 2 for water-gas that the reaction mechanism can certainly contain steps
shift (σi,2 ) would be favored versus path 1 (σi,1 ) based with positive values of Hi , because the intermediates
on thermodynamic arguments. However, the activation produced in such a step can be consumed by following
energy for step 4 is considerably lower than that for steps having negative values of Hi . This situation is
step 8, and the primary path for water-gas shift over termed ‘‘kinetic coupling’’, where the conversion of an
copper involves the formation and subsequent reaction of unfavorable step is increased by its combination with a
adsorbed carboxyl species. Accordingly, the most stable favorable step that consumes the unstable products of the
species on the catalyst surface are not necessarily the first step. The highest value of Hi for a surface reaction
most reactive species. This idea leads us to distinguish that can be tolerated can be estimated from transition
between a most abundant surface intermediate (MASI) and state theory. The value of Hi,max depends on the overall
a most abundant reactive intermediate (MARI). In certain rate of the reaction (TOF), the surface coverage by the
cases, the MASI and the MARI may be the same species, surface species that reacts in this step (θA ), a frequency
but in other cases (such as in this case of water-gas
shift on copper), the MASI is a spectator species that References see page 14
ch1.1

6 1.1 Principles of Heterogeneous Catalysis

factor ν (of the order of 1013 s−1 ), and the temperature T ,
as given by:
 
Hi,max
TOF = ν exp − θA (2)
RT
For a reaction operating at 500 K with a TOF of 1 s−1 ,
the maximum value of Hi that can be tolerated for a
species with high surface coverage (θA approaching unity)
corresponds to 125 kJ mol−1 , which is still a rather high
value. In practice, the highest value of Hi that could be
tolerated would be lower than this value of 125 kJ mol−1 ,
because the surface coverage by the reactive intermediate
would typically be lower than unity and the above analysis
assumes that the activation energy for the reverse of
step i (i.e., the exothermic direction for this step) is equal
to zero. This situation where the overall enthalpy change
is shared fairly equally between the various steps of the
reaction scheme is a necessary condition for high catalytic
activity, but it is not a sufficient condition, because we
have not yet considered the transition states for the various
elementary steps.
The aforementioned reaction scheme for water-gas shift
involving the formation of carboxyl species contains seven
steps, thereby requiring the determination (or estimation)
of 13 rate constants to describe the reaction kinetics
completely; that is, a forward and reverse rate constant for
each step (kfor,i and krev,i ) constrained by the relationship
that these rate constants must give the proper equilibrium
constant for the overall reaction, Keq , as given below:
  kfor,i σi
= Keq (3)
krev,i
i
However, it is a rare case that all of these rate
constants are kinetically significant. Thus, while we
generally have the desire to know the values for as
many rate constants as possible, we typically need to
know only the values of a limited number of these rate
constants to describe the performance of the catalyst
for the reaction conditions of interest. Unfortunately,
at the outset of research on a given catalyst process,
we usually do not know which rate constants will be
kinetically significant. Accordingly, an important objective
of research into a given catalytic process is to identify
which steps are kinetically significant, such that further
research can focus on altering the nature of the catalyst
and the reaction conditions to enhance the rates of these
kinetically controlling steps. This situation is illustrated
in Fig. 3 for the above case of water-gas shift involving
carboxyl species, according to which the rate is controlled
by steps 3 and 4, whereas steps 1, 2, 5, 6, and 7 are
quasi-equilibrated.
The net rate of step 3 in Fig. 3, is twofold faster than
the net rates of all other steps, because the stoichiometric
number of step 3 is equal to 2 whereas all other stoichio-
metric numbers are equal to 1. Importantly, the net rate of
each step divided by its stoichiometric number is equal to
the net rate of the overall catalytic reaction. This equality
is due to the principle of kinetic steady state, as stated by
Bodenstein (see Ref. [38]), according to which determin-
ing the rate of one single reaction (typically the overall
reaction) allows one to calculate the net rates of all the
other individual reactions. The Bodenstein principle is an
important foundation of our thinking about how catalytic
cycles turn over. This principle also shows that the notion
of a ‘‘slow’’ step in a catalytic cycle at the steady state is a
misnomer, because all steps proceed at the same net rate.
1.1.6
Conditions for Catalyst Optimality
It can be shown that the net rate of the overall catalytic
reaction is controlled by kinetic parameters which depend
only on the properties of the transition states for the
kinetically significant steps relative to the reactants (and
possibly the products) of the overall reaction [56]. The
overall rate is also controlled by an additional kinetic
parameter for each surface species that is abundant on

1. CO + ∗ CO∗
2. H O +∗
2 H O∗
2

3. H2O ∗+ ∗ OH ∗ + H ∗
4. CO ∗+OH ∗ COOH ∗+ ∗
5. COOH ∗+OH ∗ CO2∗+H2O ∗
6. CO2∗ CO2 + ∗
7. 2H ∗ H + 2∗
2

Fig. 3 Rates of forward and reverse steps in the water-gas shift reaction on Cu.
ch1.1

1.1.6 Conditions for Catalyst Optimality 7

the catalyst surface. Specifically, the net rate of the overall of adsorption of one of the reactants [57], the heat of
reaction is determined by the kinetic parameters as well formation of a bulk compound that can be correlated
as by the fraction of the surface sites, θ ∗ , that is available with a heat of adsorption [58], the position of the catalytic
for the formation of the transition states; the value of θ ∗ element along a horizontal series in the Periodic Table,
is determined by the extent of site blocking by abundant an electronic property of the catalyst such as Pauling’s
surface species. d-band character of the metal [59], or the d-band center of
To illustrate how to determine the optimal activity the metal [60]. The optimal catalyst can thus characterized
of a catalyst, we consider an example in which the by the following relationship:
reaction scheme contains a single rate-controlling step  o‡
 o‡
and a single abundant surface species. According to H1 dH1
−C1 exp −
results obtained using DeDonder relations (discussed drnet RT RT dx
in Section 5.2.1.10) [56], we may write this reaction =0=   o 2
dx H2
scheme in terms of a quasi-equilibrated step involving 1 + C2 exp −
the transition state for the rate-controlling step, TSi , and RT
   
a second equilibrated step involving the formation of the H1
o‡
H2o dH2o
most abundant surface species, A∗ , as given below and: 2C1 exp − C2 exp −
RT RT RT dx
+    (11)
1. Reactants + 2∗ −
←−−
−−
→− T Si (4) H2o 3
1 + C2 exp −
2. A+∗ − ←−−
−−
→−A
∗
(5) RT

The overall rate of the reaction, rnet , as will be discussed This relationship may be simplified to give:
in Section 5.2.1.12, is now given by:  
H2o dH2o
  o‡ 2C2 exp −
o‡ o‡ dH1 RT dx dH2o
ν‡ S1 H1 1/σ =    = 2θA
rnet = exp − F (ai )θ∗2 (1 − ztot 1 ) dx H2o dx
σ1 R RT 1 + C2 exp −
RT
(6) (12)
1 Thus, for the optimal catalyst, the surface coverage by
θ∗ =   (7)
S2o H2o the most abundant surface species is equal to:
1 + exp − aA
R RT o‡
dH1
‡
where F (ai ) is a function of the activities (ai ) of the reac- dx ω
θA = o = 1 (13)
tants and/or products of the overall reaction. Neglecting dH2 2ω2
entropy effects, as we change the nature of the catalyst 2
dx
for constant reaction conditions, the primary items in the
o‡
above equations that change are H1 and H2o . (Note, where the values of ωi are defined as:
we implicitly assume that the reaction mechanism does o‡
‡ dH1
not change.) Accordingly, the overall rate of the reaction ω1 = (14)
dx
for different catalysts is given by:
  dH2o
o‡ ω2 = (15)
H1 dx
C1 exp −
RT ‡
rnet =   2 (8) In the above derivation, we assume that ω1 and ω2
H2o have the same sign, such that variations in x change
1 + C2 exp −
RT the enthalpy of the transition state and the MASI in
  o‡
the same direction. We also assume that (d 2 H1 )/dx 2
ν‡ S1
o‡  
1/σ o‡
C1 = exp F (ai ) 1 − ztot 1 (9) and (d 2 H2 )/dx 2 are small or zero. This assumption
σ1 R
is valid if we are searching for improved catalysts over
 
S2o a small range of x, which typically occurs when testing
C2 = exp aA (10) catalysts. In fact, when we vary x over a large range, then
R
the mechanism of the catalytic reaction would probably
We next consider that the surface properties of the change.
catalyst are described in terms of some fundamental
catalyst property, x. This property x could be a heat References see page 14
ch1.1

8 1.1 Principles of Heterogeneous Catalysis

Case 1: w‡1 >> w2 Ratenet is maximum at w‡1 = 2qMASIw2

Ratenet
Intermediate energies

Intermediate energies
is maximum as
∆H‡tran → 0 Case 2: w‡1 ≈ w2 ∆HMASI
∆H‡tran

Rate

Rate
∆H‡tran
∆HMASI

x (Fundamental catalyst parameter) x (Fundamental catalyst parameter)

Ratenet is maximum at w‡1 = 2qMASIw2

Intermediate energies

Case 3: w‡1 << w2

Rate

∆H‡tran
∆HMASI

x (Fundamental catalyst parameter)

Fig. 4 Reaction rates and energies of transition state and most abundant surface intermediate (MASI) as functions of fundamental
catalyst parameter ‘‘x’’.

First, we will consider Case 1 shown in Fig. 4, where
‡
ω1  ω2 . In this case, a maximum rate does not exist
and the parameter x should be adjusted to its lowest
possible value (i.e., the strongest bonding to the surface)
which would decrease the enthalpy of the transition
state as much as possible. In this case the optimal
catalyst operates at high surface coverage. We now
‡
consider Case 2, where ω1 ≈ ω2 ; that is, x changes
the enthalpies of the transition state and the MASI
by similar amounts. This situation is probably more
physically realistic, and if the MASI is in fact a reactive
intermediate (i.e., if it is a MARI), then the family of
catalysts described by the variation of x follows the
Brønsted–Evans–Polanyi–Semenov relationship, which
relates the thermodynamics and kinetics of the system.
Here, there is a clear maximum in the rate versus x,
as shown in Fig. 4. The plot of rates versus x appears
as a volcano-type curve which decreases symmetrically
‡
on both sides. In the case where ω1 is equal to ω2 , the
surface coverage by the MASI on the optimal catalyst is
‡
equal to 0.5. For Case 3, ω1  ω2 , corresponding to the
situation where x changes the enthalpy of the MASI more
significantly than the transition state. The optimal catalyst
in this case has a low surface coverage by the MASI. A
maximum rate occurs in this case, as shown in Fig. 4,
‡
provided that ω1 > 0; however, the plot of rate versus x
is not symmetric with respect to x. We note that as x
increases for these three cases, the number of vacant sites
on the catalyst increases.
Cases 2 and 3 clearly illustrate the principle of Sabatier,
in which a maximum rate occurs at some moderate level
of interaction of the catalyst surface with the intermediates
and adsorbed species. While Case 1 appears to contradict
‡
Sabatier’s principle, the situation where ω1  ω2 is highly
unlikely. In particular, this situation corresponds to the
case where the catalyst interacts more strongly with the
transition state than with any of the reactive intermediates.
However, if the activation energies for the elementary
steps of the mechanism are positive, then the reactants
and/or products of the elementary step involving the rate-
controlling transition state are more strongly adsorbed
on the surface than is the transition state, leading to the
situation described by Case 2 or 3.
We may generalize the above expression for catalyst
optimality to the case where the surface contains several
abundant surfaces species, A∗ , B∗ , C∗ , and D∗ , leading to
the following expression:
‡
ω1 = 2(ωA θA + ωB θB + ωC θC + ωD θD ) (16)
In this case, the nature of the optimal catalyst is
controlled by the change in the binding energy of the
‡
transition state with respect to x (ω1 ) compared to the
changes in the bindings energies of species A, B, C, and
ch1.1

1.1.6 Conditions for Catalyst Optimality 9

D (ωA , ωB , ωC , ωD ) weighed by their respective surface
coverages at the steady state.
A bridge between the thermodynamics and kinetics
of a reaction is provided by the Brønsted–Evans–Pol-
anyi–Semenov relationship, which states that there is a
linear relationship between the activation energy Eact of
an elementary step and the heat of reaction if entropy
effects are neglected [38]:
Eact = E0 + αH
where H is the enthalpy of reaction, α is the transfer
coefficient that varies between zero and one, and E0
is a constant. In other words, if we neglect entropic
effects, the activation energy of an elementary step in
the exothermic direction is lower when the heat of
reaction becomes more favorable (i.e., H becomes
more negative). DFT calculations have recently shown
that Brønsted–Evans–Polanyi–Semenov relationships
are generally upheld in chemical reactions on catalyst
surfaces [61–64].
We now consider the following catalytic reaction:
A∗ −−−→ B∗ + C∗
If we use the gas phase A species as the zero energy
level (as shown in Fig. 5) we can define the activation
energy as:
Eact = E0 + α(HBgas + B.E.B + HCgas + B.E.C
− HAgas − B.E.A ) = E0 + α(B.E.B
+ B.E.C − B.E.A ) + αHgas
where the B.E. terms are the binding energies of the
various species on the surface.
dB.E.A dB.E.B dB.E.C
Agas → Bgas + Cgas Assume: = =
dx dx dx
Agas ∆H‡
0
Eact
a=0
B.E.A
A* a=1
A* B* + C*
B* + C*
Fig. 5 Schematic potential energy diagram of energy versus
reaction coordinate, showing the relationship between the energy
of transition state, H= , and changes in the energies of adsorbed
species.
We now define the standard enthalpy for the formation
of the transition state from gaseous species A as:
o‡
H1 = Eact + B.E.A = E0 + α(Hgas )
+ α(B.E.B + B.E.C ) + (1 − α)B.E.A (20)
and we differentiate the enthalpy of the transition state
with respect to x, leading to the following result:
 
(17) dH1
o‡
dB.E.B dB.E.C dB.E.A
=α + + (1 − α)
dx dx dx dx
(21)
This relationship shows how the change of the
‡
transition state enthalpy with respect to x(ω1 ) is related to
the changes in the binding energies B.E. of the adsorbed
species (ω2 ). If α is equal to zero, then the change of the
transition state enthalpy depends only on the change of
‡
the binding energy of A, and ω1 = ω2 . In this case, the
transition state is an early transition state that chemically
looks similar to A [65]. If α is equal to 1, then the transition
state is a late transition state that resembles the products
(18) of the reaction, and the change of the transition state
enthalpy is related to changes of the binding energies of B
and C. If (dB.E.A )/dx = (dB.E.B )/dx = (dB.E.C )/dx,
then the late transition state gives rise to the situation
‡
where ω1 = 2ω2 .
The above examples show how it is possible to maximize
the activity of the catalyst. However, it is often more
important to optimize the selectivity of the catalyst.
Similar types of analyses can be carried out for these cases.
(19)
In general, these situations are classified as being series
selectivity challenges, such as A → B → C, where B is
the desired product, and/or parallel selectivity challenges,
such as A → B coupled with A → C. In these cases, if we
want to optimize the selectivity of the catalyst, we search
Bgas + Cgas for some catalyst property, x, that decreases the enthalpy
of the transition state for the desired reaction more than
it decreases the enthalpies of the transition states for the
undesired reactions.
An undesired reaction that leads to progressive
blocking of surface sites leads to deactivation of the
catalyst with respect to time-on-stream. More generally,
various mechanisms exist by which a catalyst can
undergo deactivation, such as: (i) poisoning; (ii) thermal
degradation (sintering); (iii) leaching of the active site;
and (iv) attrition [66]. The first three of these mechanisms
are chemical in nature, whereas the last mechanism
is physical (e.g., the catalyst pellet breaks apart). Some
catalysts do not show any measurable deactivation over
periods of years, such as in ammonia synthesis. However,
other catalysts lose an important fraction of their activity
References see page 14
ch1.1
10 1.1 Principles of Heterogeneous Catalysis
after less than a minute of contact with feed, as in catalytic
cracking. In the latter case, if deactivation is caused by
coking, the catalyst must be regenerated by continuous
regeneration in an oxidizing atmosphere.
1.1.7
Catalyst Design
Given that the performance of a catalyst is controlled
by a limited number of kinetic parameters, it is unclear
why it is so difficult to design a catalyst from molecular-
level concepts. As noted above, during the early stages
of research into a catalytic process, first we do not know
which steps in the reaction mechanism are kinetically
significant, and which species are most abundant on the
catalyst surface under reaction conditions. Second, we
do not often know the structure of the active site and
its dependence on the nature of the reaction conditions.
Third, we do not usually know how the activity and
selectivity for the catalytic reaction depend on the structure
of the active sites. Fourth, we do not typically know during
these early stages the rates of various modes of catalyst
deactivation (e.g., sintering, phase changes, deposition
of carbonaceous deposits on the surface, etc.), and we
do not know whether the catalyst can be regenerated
following deactivation. Finally, we must ensure that the
texture of the catalyst and the geometry of the reactor are
designed in such a way that mass transport of reactants
and products to and from the active sites is sufficiently
rapid that high rates of reaction per unit volume of reactor
can be achieved.
Because of these difficulties, the field of heteroge-
neous catalysis is highly interdisciplinary in nature, and
Characterization studies:
catalyst structure, composition,
& texture, (ideally under
reaction conditions)
Catalyst performance level
Exploratory studies:
promising leads for new
catalytic materials & new
catalytic reactions
Surface studies:
surface composition and nature interactions of probe
of surface sites, (ideally under
reaction conditions)
Fig. 6 Levels of study in heterogeneous catalysis research.
involves close collaboration between experts in such areas
as catalyst synthesis, catalyst characterization, surface
spectroscopy, chemical kinetics, chemical reaction engi-
neering and, most recently, in theoretical calculations of
catalyst structure and performance using density func-
tion theory. These broad studies can be grouped into
three levels, as shown in Fig. 6.
All studies of heterogeneous catalysis begin at the
Materials Level. High-surface area catalytic materials
must be synthesized with specific structures and textures,
the latter referring to such features as the sizes of
the various phase domains and the details of the pore
structure. Clearly, the synthesis of catalytic materials
must be guided by detailed characterization studies to
determine the structures, compositions, and textures
of the materials that have been prepared. These
characterization studies should be conducted after the
catalyst has been subjected to various treatment steps
(such as those treatments employed during activation of
the catalytic material), and it is most desirable to carry
out characterization studies of the catalyst under the
actual reaction conditions of the catalytic process. Indeed,
the properties of a heterogeneous catalyst are inherently
dynamic in nature, and these properties often change
dramatically with changes in the reaction conditions
(e.g., phase changes, surface reconstructions, changes
in surface versus bulk composition, etc.) [67].
The central level of research and development of het-
erogeneous catalysts involves the quantification of catalyst
performance (this is known as the Catalyst Performance
Level). These studies can be carried out in a prelimi-
nary fashion over a wide range of catalytic materials (e.g.,
high-throughput studies) to identify promising catalysts
Materials level
Materials synthesis:
catalytic materials
with specific structures
& textures
Reaction kinetics studies:
activity, selectivity &
stability for various
reaction conditions
Elucidation level
Experimental studies: Theoretical studies:
stability & reactivity
molecules with of species on
well-defined sites well-defined sites
ch1.1
and reaction conditions for further studies. The perfor-
mance of the catalyst is then documented in greater detail
by determining catalytic activity, selectivity, and stability
with respect to time-on-stream for various reaction con-
ditions. These measurements must be made at various
conversions when multiple reaction pathways exist, be-
cause catalytic selectivities in these cases are different,
depending on whether the desired products are formed
in primary versus secondary reactions, or in series versus
parallel pathways. We note here that various definitions
of catalytic activity are used, depending on the nature of
the study. For practical studies, catalytic activities can be
reported as rates per gram of catalyst or per unit surface
area. However, for more detailed studies or for research
purposes, it is often desirable to report catalytic activities
as rates per surface site (i.e., TOFs), with the number of
surface sites measured most often by selective adsorption
measurements (e.g., adsorption of H2 or CO to titrate
metal sites, adsorption of ammonia or pyridine to titrate
acid sites). In some cases it is possible to report catalytic
activity as rate per active site (also called TOF), when it is
possible to distinguish active sites from the larger num-
ber of surface sites using special probe molecules (e.g.,
dissociative adsorption of N2 to titrate sites for ammo-
nia synthesis [68]; selective poisoning by adsorbates that
compete with the reactants of the catalytic reaction [69]);
or by transient isotopic tracing [70].
For the purposes of catalyst development, it is prob-
ably sufficient to work at the Materials Level and the
Catalyst Performance Level. However, research into het-
erogeneous catalysis is dominated by studies conducted
at a third level – the Elucidation Level – where the aim
is to identify the fundamental building blocks of knowl-
edge which can be assembled to build a molecular-level
understanding of catalyst performance in order to guide
further investigations to improve catalyst performance.
At the Elucidation Level the studies are designed to deter-
mine the surface composition and nature of the surface
sites on the catalyst [71–74]. Clearly, these investigations
must be conducted with the catalyst under controlled con-
ditions (e.g., under ultra-high vacuum, after treatment
with H2 , after calcination, etc.) and, where possible, such
measurements should be made with the catalyst under
reaction conditions. Moreover, the studies may be carried
out on real catalytic materials and on more well-defined
surfaces (e.g., single crystals, or model samples formed
by depositing known amounts of materials onto well-
defined supports) [73, 75, 76]. Most measurements at the
Elucidation Level involve studies of the interactions of
specific probe molecules with the catalyst surface. These
probe molecules may be the reactants, intermediates, or
products of the catalytic reaction, or they may be more
simple species chosen to monitor a specific functionality
of the surface. Alternatively, a molecule may be used as
1.1.8 Catalyst Development 11
a probe because it has an advantageous feature for spec-
troscopic identification (e.g., CO for infrared studies, a
13 C-containing molecule for NMR studies). These studies
of the interaction of probe molecules with surfaces are
designed to determine the surface concentrations of dif-
ferent types of surface site, to determine the nature of the
adsorbed species formed on the surface sites, and to de-
termine the reactivities of the surface sites by monitoring
the adsorbed species on the surface versus time, versus
temperature or, most commonly, during a temperature
ramp (e.g., temperature-programmed desorption).
The third pillar of studies at the Elucidation Level
involves the use of DFT calculations to assess the
structures, stabilities, and reactivity of species adsorbed
onto the surface sites (with the sites being composed of
clusters of atoms or as periodic slabs of atoms) [77–81].
These studies are used to help interpret the results
obtained from spectroscopic studies of catalyst surfaces
(e.g., to predict the vibrational spectra of species adsorbed
in different orientations on different sites), to calculate
heats of adsorption for various intermediates in a reaction
mechanism (e.g., to predict which species are expected to
be abundant on the catalyst under reaction conditions),
to estimate the energy changes for possible steps in a
reaction mechanism (thereby eliminating from further
consideration steps with very positive energy changes),
and to determine activation energy barriers for steps
that are suspected as being kinetically significant in the
reaction scheme. Indeed, a key feature of these theoretical
studies is the ability to predict how the surface properties
are expected to change as the nature of the surface is
altered (e.g., by changing the surface structure, or by
adding possible promoters). This in turn will provide
feedback to the Materials Level with regards to new
materials that should be synthesized and which are likely
to lead to an improved catalyst performance. In addition,
these theoretically based studies provide information
about highly reactive intermediates which might be
difficult to obtain by direct experimental measurements.
Most importantly, studies conducted at the Elucidation
Level provide a scientific basis about the working catalysis
that may, in future, be used to design different reaction
pathways.
1.1.8
Catalyst Development
Catalyst development typically involves testing a large
number of catalysts with a feedback loop, as it is currently
difficult to design catalysts a priori. In this respect, catalyst
development studies involve examining a large number
of catalysts, for which recent advances in high-throughput
References see page 14
ch1.1

12 1.1 Principles of Heterogeneous Catalysis

testing have attracted considerable attention [82–87]. 1.1.9

Catalyst development through the testing of a wide range Bridging Gaps in Heterogeneous Catalysis
of materials was first practiced in 1909 by Mittasch at
BASF who, according to Timm [88], issued the following The above description of research and development into
directive to his team who at the time were developing the heterogeneous catalysis as being interdisciplinary in na-
synthesis of ammonia: ture, involving studies at the levels of materials, catalyst
performance and elucidation, can also be cast in the form
• The search for a suitable catalyst necessitates carrying of building bridges between various types of studies and
out experiments with a number of elements, together different types of material. As depicted in Fig. 7, we often
with numerous additives. talk about bringing together the field of surface science
• The catalytic substances must be tested at high (which traditionally is focused on studies of single crystal
pressures and temperatures, just as in the case of surfaces at low pressures) with the field of heterogeneous
Haber’s experiments. catalysis (which traditionally is focused on studies of
• A very large number of tests will be required. high-surface area catalytic materials surfaces under high-
pressure reaction conditions). More recently, we have
talked about ‘‘bridging the materials gap’’, as we have
Ten years later, the number of tests conducted had
attempted to use experimental results from studies of well-
exceeded 10 000, and more than 4000 catalysts had been
defined model materials to interpret the performance of
studied. This extraordinary effort was also extraordinarily
more complex, high-surface area catalytic materials. Tra-
successful. What has changed since then, however, is
ditionally, these model materials have been single crystals,
the way in which the systematic search is assisted.
cut at various angles to expose surfaces containing differ-
Today, armed with an arsenal of principles, concepts,
ent types of sites, such as surfaces with different symme-
instrumentation and computers, it is possible to identify
tries and atoms present at terraces, steps, and kinks [89].
and to improve new catalytic materials in a much
More recently, however, these model materials have be-
shorter time and with a smaller number of trial samples,
come highly sophisticated, such as the deposition of
especially with the possibility of advanced characterization
nanoparticles with specific sizes and geometries on well-
methods (especially in-situ techniques) and insights from
defined support surfaces (e.g., metal nanoparticles sup-
theoretical calculations (e.g., DFT calculations). The
ported on thin films of oxides deposited on single crystal
practical merit of this ‘‘assisted catalyst design’’ is clear,
metal surfaces, or non-metallic nanoparticles supported
while its scientific dividend is the possibility of learning
directly on single crystal metal surfaces) [73, 75, 76]. We
as the design proceeds, with the building of a data bank
also talk about ‘‘bridging the pressure gap’’, as we at-
of rate constants and the formulation of more precise
tempt to use experimental results from studies conducted
models of active sites. With new theoretical insights
at low pressures (less than 10−6 Torr) to interpret the
or principles, quantitative bases of catalyst preparation
performance of catalysts under high-pressure reaction
and reproducibility of catalyst behavior, the future of
heterogeneous catalysis still looks very bright.
The path to the design of an optimal catalytic process
would be clear if the activity, selectivity and stability High m2
of the catalyst were to move in the same direction
upon an increase in a single process variable, such
as temperature. However, this simple behavior is not Heterogeneous
typically observed, and choices must be made in every catalysis
instance. For example, while the activity of a catalyst
Materials gap

may increase with temperature, its stability usually

decreases with temperature. In addition, the relationship Low P Pressure gap High P
between catalytic activity and selectivity is typically very
complex, and is not understood in detail until the surface Surface
chemistry of the catalytic process has been elucidated. science
Accordingly, selectivity, stability and activity must be
considered together, and trade-offs may have to be
negotiated, perhaps by using multi-functional reactors Low m2
with catalytic distillation or catalytic membranes. Success
in heterogeneous catalysis begins with chemistry, but Fig. 7 Bridging the gap between surface science and heteroge-
ends with catalytic reaction engineering. neous catalysis.
ch1.1
conditions. The origin for this pressure gap comes from
the fact that, whereas some spectroscopic techniques can
be employed to study the surface and bulk properties of
catalysts under high-pressure reaction conditions (e.g.,
FTIR, Raman, XRD, EXAFS, Mössbauer spectroscopy),
other spectroscopic and characterization techniques (e.g.,
XPS, TEM) are most easily conducted with the sample
at low pressures (e.g., <10−6 Torr) [90]. These latter tech-
niques are typically associated with use of electrons to
probe the sample, with the electrons interacting strongly
with molecules in the gas phase. This pressure gap can be
bridged directly by designing advanced instrumentation,
such that the distance traversed by the electrons in the
gas phase is minimized [91, 92]. In addition, the pressure
gap can be bridged indirectly by using molecular-based
models (e.g., kinetic Monte Carlo calculations, micro-
kinetic models), first to describe the experimental results
obtained at low pressures, and then to extrapolate this
information to high-pressure reaction conditions.
The past few years have witnessed an explosion in
the area of nanotechnology, in which researchers have
learned – and are continuing to learn – how to engineer
materials at the nanometer length scale. The field of het-
erogeneous catalysis has been involved in the synthesis
of nanomaterials for many years (e.g., the synthesis of
zeolites). Indeed, the scheme depicted in Fig. 6 shows
that essentially all studies of heterogeneous catalysis
begin at the Materials Level. Recent advances in nan-
otechnology offer new routes for catalyst synthesis (e.g.,
atomic layer deposition, self-assembly methods) [93–96]
and, importantly, also for catalyst characterization (e.g.,
Elucidation well
Sufficient insight gained
new catalytic processes
to guide the search for
Elucidation
Discovery
Desire to know more
about surface chemistry
Fig. 8 The catalyst ‘‘elucidation well’’ and catalyst discovery.
1.1.10 A Philosophical Note 13
techniques such as scanning tunneling microscopy that
allow atomic-scale imaging of materials at elevated tem-
peratures and pressures) [73, 97]. However, as an as
increasing number of research groups become involved
in nanotechnology, it is possible that an ‘‘applications
gap’’ will be created in heterogeneous catalysis, where
new materials are formed without clear applications for
catalytic processes. Clearly, this gap can be bridged by re-
alizing that research and development into heterogeneous
catalysis involves the combination of studies at the levels
of materials, catalyst performance, and elucidation. As ad-
vances in nanotechnology allow us to create new materials
(the Materials Level) and to characterize these materials
in greater detail (Materials and Elucidation Levels), we
are positioned to take full advantage of these advances by
conducting studies at the Catalyst Performance Level.
1.1.10
A Philosophical Note
Today, we live in an era in which it is possible to employ
a vast range of advanced experimental techniques and
theoretical methods to elucidate in detail the surface
chemistry of catalytic processes. This situation, with
respect to the hierarchy of theoretical methods that
can be employed to describe the reaction kinetics for
a catalytic process, is illustrated schematically in Fig. 8. At
the lowest level, we use empirical rate expressions to fit
reaction kinetics data over a range of process conditions;
References see page 14
Empirical rate expressions
Simplified rate expressions based
on assumed surface chemistry
Micro-kinetic rate expressions based
on results from DFT calculations
Kinetic monte-carlo analyses based
on results from DFT calculationsns
Quantum molecular dynamics calculations
for surface reactions
Future methods …..
ch1.1
14 1.1 Principles of Heterogeneous Catalysis
however, these models typically have questionable success
in predicting catalyst performance outside the range of
experimental conditions used to fit the model.
We then move to rate expressions based on assumed
surface chemistry. These models should have a better
predictive value, although it is often difficult to determine
which types of assumption should be made. Accordingly,
we turn to results from DFT calculations to build micro-
kinetic models that describe catalyst performance without
the need to make prior assumptions about which steps are
kinetically significant and which species are abundant on
the catalyst surface. These micro-kinetic models, however,
are typically based on the mean-field approximation, and
they thus make simplified assumptions about (or neglect)
the effects of surface coverage and lateral interactions
between adsorbed species. Accordingly, these restrictive
assumptions are relaxed when using kinetic Monte Carlo
methods to describe reaction kinetics based on binding
energies and lateral interaction terms determined from
DFT calculations. Indeed, today’s research groups are
beginning to combine quantum mechanics and molecular
dynamics calculations to describe a variety of surface
processes. Who knows what new computational methods
are on the horizon?
The sequential use of the aforementioned methods to
describe reaction kinetics in greater detail is depicted
in Fig. 8, as the digging of an ‘‘elucidation well’’. As
we dig deeper by using more sophisticated methods, we
learn more about the details of the surface chemistry.
Indeed, we are driven to dig deeper by our desire to learn
as much as possible about the fundamental principles
that control catalyst performance. However, this desire
to know as much as possible must be balanced by our
need to discover new catalysts and new catalytic processes.
Clearly, as we learn more about the fundamentals of the
catalytic process (i.e., as we dig deeper), we should have
better insight to guide our search for better catalysts.
Luckily, we need not dig to the deepest levels to begin the
search for better catalysts. As noted at the beginning
of this chapter, our industrialized society is facing
increasingly complex environmental and energy issues
for sustained growth. Thus, while our scientific curiosity
for fundamental knowledge drives us to dig deeper toward
detailed elucidation of catalytic phenomena, we must also
continue to look horizontally as we use our newfound
insight to develop new catalysts and catalytic processes
for the benefit of society.
List of Abbreviations
DFT density functional theory
EXAFS extended X-ray absorption fine structure
FTIR Fourier transform infrared
STY site time yield
TEM transmission electron microscopy
TOF turnover frequency
TOR turnover rate
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
References
1. J. M. Thomas, W. J. Thomas, Principles and Practice of Hetero-
geneous Catalysis, VCH, Weinheim, 1997, 669 pp.
2. J. N. Armor, Appl. Catal., A 2001, 222, 407.
3. I. Chorkendorff, J. W. Niemantsverdriet, Concepts of Mod-
ern Catalysis and Kinetics, Wiley-VCH, Weinheim, 2003,
452 pp.
4. R. J. Farrauto, C. H. Bartholomew, Fundamentals of Indus-
trial Catalytic Processes, Chapman & Hall, London, 1997,
754 pp.
5. R. A. van Santen, P. W. N. M. v. Leeuwen, J. A. Mooulijn,
B. A. Averill, Catalysis: An Integrated Approach, Elsevier
Science B.V., Amsterdam, 1999, 574 pp.
6. National Research Council Panel on New Directions in
Catalytic Sciences and Technology, Catalysis Looks to the Future,
National Academy Press, Washington D.C., 1992, p. 1.
7. W. Vielstich, A. Lamm, H. Gasteiger, Handbook of Fuel Cells:
Fundamentals, Technology, Applications, Wiley, Chichester,
2003, 2690 pp.
8. S. Park, J. M. Vohs, R. J. Gorte, Nature 2000, 404, 265.
9. S. Ha, R. Larsen, R. I. Masel, J. Power Sources 2005, 144, 28.
10. A. Corma, H. Garcia, Chem. Rev. 2003, 103, 4307.
11. G. Centi, Catal. Today 2003, 77, 287.
12. R. A. Sheldon, Green Chem. 2005, 7, 267.
13. A. Borgna, L. Balzano, J. E. Herrera, W. E. Alvarez, D. E.
Resasco, J. Catal. 2001, 204, 131.
14. H. van Bekkum, P. Gallezot, Top. Catal. 2004, 27, 1.
15. G. W. Huber, J. W. Shabaker, J. A. Dumesic, Science 2003,
300, 2075.
16. G. W. Huber, J. N. Chheda, C. J. Barrett, J. A. Dumesic, Sci-
ence 2005, 308, 1446.
17. I. K. Mbaraka, B. H. Shanks, J. Catal. 2005, 229, 365.
18. S. Varadarajan, D. J. Miller, Biotechnol. Progr. 1999, 15, 845.
19. E. K. Rideal, H. S. Taylor, Catalysis in Theory and Practice,
Macmillan, London, 1919, Chapter 2.
20. M. Boudart, in Perspectives in Catalysis, J. M. Thomas,
K. I. Zamaraev (Eds.), Blackwell, Oxford, 1992, p. 183.
21. G. A. Somorjai, Introduction to Surface Chemistry and Catalysis,
John Wiley, New York, 1994, 667 pp.
22. H. S. Taylor, Proc. Roy. Soc. (London) 1925, A108, 105.
23. J. B. Anderson, Kagaku Kogaku (Chem. Eng. Jpn.) 1962, 147,
191.
24. J. J. Carberry, AICHE 1961, 7, 350.
25. G. F. Froment, K. B. Bischoff, Chemical Reactor Analysis and
Design, Wiley, New York, 1990, 664 pp.
26. C. N. Satterfield, Mass Transfer in Heterogeneous Catalysis, MIT
Press, Cambridge, MA, 1970, 267 pp.
27. D. E. Mears, Ind. Eng. Chem. Proc. Des. Dev. 1971, 10, 541.
28. D. E. Mears, J. Catal. 1971, 20, 127.
29. J. M. Smith, J. Chem. Eng. Japan 1973, 6, 191.
30. P. B. Weisz, Z. Phys. Chem. 1954, 11, 1.
31. P. B. Weisz, C. D. Prater, Adv. Catal. 1957, 6, 143.
ch1.1
32. R. Aris, in Catalyst Design: Progress and Perspectives,
L. L. Hegedus (Ed.), Wiley Interscience, New York, 1987,
Chapter 7.
33. P. A. Jacobs, J. A. Martens, J. Weitkamp, H. K. Beyer, Faraday
Discuss. Chem. Soc. 1981, 72, 353.
34. W. O. Haag, R. M. Lego, P. B. Weisz, Faraday Discuss. Chem.
Soc. 1981, 72, 317.
35. E. G. Derouane, P. Dejaifve, Z. Gabelica, Faraday Discuss.
Chem. Soc. 1981, 72, 331.
36. J. M. Thomas, G. R. Millward, S. Ramdas, L. A. Busil,
M. Audier, Faraday Discuss. Chem. Soc. 1981, 72, 345.
37. P. Sabatier, La catalyse en chimie organique, Bérange, Paris,
1920, 388 pp.
38. M. Boudart, Kinetics of Chemical Processes, Blackwell, Oxford,
Stoneham, MA, 1991, 246 pp.
39. J. V. Lauritsen, M. Nyberg, J. K. Norskøv, J. Catal. 2004, 224,
94.
40. B. Hinnemann, J. K. Norskøv, H. Topsøe, J. Phys. Chem. B
2005, 109, 2245.
41. H. H. Hwu, J. G. Chen, Chem. Rev. 2005, 105, 185.
42. R. B. Levy, M. Boudart, Science 1973, 181, 547.
43. M. K. Neylon, S. Choi, H. Kwon, K. E. Curry, L. T. Thompson,
Appl. Catal., A 1999, 183, 253.
44. S. T. Oyama, Catal. Today 1992, 15, 179.
45. S. G. Podkolzin, J. Shen, J. J. D. Pablo, J. A. Dumesic, J. Phys.
Chem. B 2000, 104, 4169.
46. R. M. Watwe, B. E. Spiewak, R. D. Cortright, J. A. Dumesic,
Catal. Lett. 1998, 51, 139.
47. C. G. M. Hermse, A. P. van Bave, A. P. J. Jansen, L. A. M. M.
Barbosa, P. Sautet, R. A. van Santen, J. Phys. Chem. B 2004,
108, 11035.
48. M. Neurock, S. A. Wasileski, D. Mei, Chem. Eng. Sci. 2004, 59,
4703.
49. S. Raimondeau, P. Aghalayam, A. B. Mhadeshwar, D. G.
Vlachos, Ind. Eng. Chem. Res. 2003, 42, 1174.
50. F. J. Garcia, E. E. Wolf, Chem. Eng. Sci. 2004, 59, 4723.
51. J. M. Thomas, C. R. A. Catlow, G. Sankar, Chem. Commun.
2002, 2921.
52. A. A. Gokhale, Water–Gas Shift Reaction and Fischer–Tropsch
Synthesis on Transition Metal Surfaces, Phd thesis, University
of Wisconsin, 2005.
53. P. S. Cremer, X. Su, Y. R. Shen, G. A. Somorjai, J. Am. Chem.
Soc. 1996, 118, 2942.
54. H. Topsøe, J. Catal. 2003, 216, 155.
55. I. E. Wachs, Catal. Today 1996, 27, 437.
56. J. A. Dumesic, J. Catal. 1999, 185, 496.
57. O. Beeck, Disc. Faraday Soc. 1950, 8, 118.
58. W. J. M. Rootsaert, W. M. H. Sachtler, Z. Physik. Chem. 1960,
26, 16.
59. J. H. Sinfelt, Bimetallic Catalysts, Wiley, New York, 1983 p. 14.
60. M. Boudart, J. Am. Chem. Soc. 1950, 72, 1050.
61. T. Bligaard, J. K. Norskøv, S. Dahl, J. Matthiesen, C. H.
Christensen, J. Sehested, J. Catal. 2004, 224, 206.
62. J. K. Norskøv, T. Bligaard, A. Logadottir, S. Bahn, L. B. Hansen,
M. Bollinger, H. Bengaard, B. Hammer, Z. Sljivancanin, M.
Mavrikakis, Y. Xu, S. Dahl, C. J. H. Jacobsen, J. Catal. 2002,
209, 275.
63. V. Pallassana, M. Neurock, J. Catal. 2000, 191, 301.
64. Z. P. Liu, P. J. Hu, J. Chem. Phys. 2001, 114, 8244.
65. R. A. van Santen, J. W. Niemantsverdriet, Chemical Kinetics
and Catalysis, Plenum Press, New York, 1995, p. 233.
66. C. H. Bartholomew, Appl. Catal., A 2001, 212, 17.
67. G. A. Somorjai, Annu. Rev. Phys. Chem. 1994, 45, 721.
References 15
68. H. Topsøe, J. A. Dumesic, N. Topsøe, H. Bohlbro, in
Proceedings of the Seventh International Congress in Catalysis,
T. Seiyama, K. Tanabe (Eds.), Elsevier, Amsterdam, 1981,
p. 247.
69. H. Knözinger, Adv. Catal. 1976, 25, 183.
70. J. G. Goodwin Jr., S. Kim, W. D. Rhodes, Catal. 2004, 17, 320.
71. D. W. Goodman, J. Catal. 2003, 216, 213.
72. G. A. Somorjai, K. R. McCrea, J. Zhu, Top. Catal. 2002, 18,
157.
73. H.-J. Freund, M. Baumer, J. Libuda, T. Risse, G. Rupprechter,
S. Shaikhutdinov, J. Catal. 2003, 216, 223.
74. G. Ertl, J. Mol. Catal. A: Chem. 2002, 182–183, 5.
75. J. V. Lauritsen, M. Nyberg, J. K. Norskov, B. S. Clausen,
H. Topsoe, E. Laegsgaard, F. Besenbacher, J. Catal. 2004,
224, 94.
76. M. S. Chen, D. W. Goodman, Science 2004, 306, 252.
77. J. Greeley, J. K. Norskøv, M. Mavrikakis, Annu. Rev. Phys.
Chem. 2002, 53, 319.
78. M. Neurock, J. Catal. 2003, 216, 73.
79. B. Hammer, J. K. Norskøv, Adv. Catal. 2000, 45, 71.
80. S. Linic, H. Piao, K. Adib, M. A. Barteau, Angew. Chem. Int.
Ed. 2004, 43, 2918.
81. M. T. M. Koper, R. A. van Santen, M. Neurock, in Catalysis
and Electrocatalysis at Nanoparticle Surfaces, A. Wieckowski,
E. R. Savinova, C. G. Vayenas (Eds.), Marcel Dekker, Inc., New
York, 2003, p. 1.
82. A. Hagemeyer, P. Strasser, J. Anthony, F. Volpe, High-
Throughput Screening in Chemical Catalysis: Technologies,
Strategies and Applications, Wiley-VCH Verlag, Weinheim,
Germany, 2004, 339 pp.
83. A. Hagemeyer, R. Borade, P. Desrosiers, S. Guan, D. M. Lowe,
D. M. Poojary, H. Turner, H. Weinberg, X. Zhou, R. Armbrust,
G. Fengler, U. Notheis, Appl. Catal., A 2002, 227, 43.
84. R. J. Hendershot, C. M. Snively, J. Lauterbach, Chem. Eur. J.
2005, 11, 806.
85. J. M. Serra, E. Guillon, A. Corma, J. Catal. 2005, 232, 342.
86. S. Senkan, Angew. Chem. Int. Ed. 2001, 40, 312.
87. J. W. Saalfrank, W. F. Maier, Angew. Chem. Int. Ed. 2004, 43,
2028.
88. B. Timm, Proceedings of the 8 th International Congress on
Catalysis Berlin 1984, Verlag Chemie, Frankfurt, 1984, Vol. I,
p. 7.
89. P. L. J. Gunter, J. W. Niemantsverdriet, F. H. Ribeiro, G. A.
Somorjai, Cat. Rev. - Sci. Eng. 1997, 39, 77.
90. J. W. Niemantsverdriet, Spectroscopy in Catalysis, Wiley, Wein-
heim, Germany, 1993, 288 pp.
91. P. L. Hansen, J. B. Wagner, S. Helveg, J. R. Rostrup-Nielsen,
B. S. Clausen, H. Topsøe, Science 2002, 295, 2053.
92. D. Teschner, A. Pestryakov, E. Kleimenov, M. Haevecker,
H. Bluhm, H. Sauer, A. Knop-Gericke, R. Schloegl, J. Catal.
2005, 230, 186.
93. A. Corma, F. Rey, J. Rius, M. J. Sabater, S. Valencia, Nature
2004, 431, 287.
94. Y. Yin, R. M. Rioux, C. K. Erdonmez, S. Hughes, G. A.
Somorjai, A. P. Alivisatos, Science 2004, 304, 711.
95. M. J. Pellin, P. C. Stair, G. Xiong, J. W. Elam, J. Birrell,
L. Curtiss, S. M. George, C. Y. Han, L. Iton, H. Kung, M.
Kung, H. H. Wang, Catal. Lett. 2005, 102, 127.
96. A. Gervasini, P. Carniti, J. Keranen, L. Niinisto, A. Auroux,
Catal. Today 2004, 96, 187.
97. F. Besenbacher, E. Laegsgaard, I. Stensgaard, Mater. Today
2005, 8, 26.