N A N O S C A L E MAT E R I A L S

The past twenty years have brought incredible expansion of capabilities and
possibilities to all aspects of computing, and the computational catalysis field is no
exception. Electronic structure calculations are now readily used to provide
computational insight into the chemical and physical processes that determine the
properties of different types of catalysts.
Important advances in both physical simulation
algorithms and the development of massively par-
allel computers have greatly expanded the classes
of catalytic problems that can be treated with elec-
tronic structure-based approaches. Researchers
at Argonne National Laboratory (ANL) are devel-
oping efficient catalytic processes and are tackling
questions of energy production, usage, and secu-
rity. ANLs emphasis is on both the physical/chem-
ical nature of the problems, as well as the
computational software and hardware deployed.
As a field, catalysis spans a significant range of
length scalescatalysts can be composed of any-
thing from single metal atoms surrounded by
organic ligands (homogeneous catalysts), to clus-
ters of a few dozen metal, oxide, carbide, or nitride
atoms (subnanometer heterogeneous catalysts),
to metal particles of up to 10 nm or more in diam-
eter (nanoparticle heterogeneous catalysts). Sub-
nanometer and heterogeneous catalysts are
generally supported on other complex materials
(figure 1), and this adds complexity. Although the
support generally plays a secondary role in the cat-
alytic chemistry, the choice of this material, in
some cases, can affect the course of the reactions.
Each class of catalysts has unique properties that
are useful in different situations. Homogeneous
catalysts (which are not treated extensively herein)
can demonstrate a remarkable ability to tune
product distributions to favor desired reaction
products (they are very selective; sidebar General
Principles of Catalysis, p50). They may also show
a variety of other unique catalytic properties stem-
ming from the molecular-like nature of the cata-
lysts electronic orbitals. The drawback of this class
of catalysts is they cannot be easily immobilized,
and therefore they require sophisticated process-
ing technologies to function efficiently.
Heterogeneous catalysts, on the other hand,
have traditionally shown less selectivity, but they
are easy to synthesize and process, and are
extremely robust under a variety of reaction con-
ditions. Subnanometer heterogeneous catalysts
have only recently been reliably and reproducibly
synthesized. These catalysts, therefore, have not
yet received extensive attention but hold forth the
tantalizing prospect of combining the advantages
of homogeneous and heterogeneous catalysts.
Computational catalysis efforts have historically
focused on the study of both homogeneous cata-
lysts and single crystal catalysts (the latter structures
serve as simplified models for the surface geome-
tries of large nanoparticles). Both classes of systems
are readily treated with existing computational
approaches and are highly relevant to experimen-
tally studied catalysts. Less attention has been paid,
however, to the computational study of sub-
nanometer clusters on support materials (primarily
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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
Recent Trends in
Computational
CATALYSIS
Researchers at Argonne
National Laboratory are
developing efficient
catalytic processes and
are tackling questions of
energy production, usage,
and security.

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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
Figure 1. Methanol reacting on a subnanometer platinum cluster (light gray spheres) supported on an alumina substrate. Aluminum atoms are dark
gray, oxygen is red, carbon is yellow, and hydrogen is light blue.
because of the lack of suitable experimental data
to which to compare the computational results) or
to the explicit, electronic structure-based simula-
tion of large, heterogeneous catalytic nanoparti-
cles (due to the lack of suitable hardware and
software to perform the calculations).
Current Computational Resources
Computer codes are providing new opportuni-
ties for exploring and understanding the catalytic
properties of clusters and particles ranging from
a single atom to nanoparticles of 36 nm in size.
Most existing codes employ, in some form, the
KohnSham formulation of density functional
theory (DFT; sidebars Quantum Chemical Meth-
ods for Energy Predictions, p51, and Density
Functional Theory, p52). This approach provides
a reasonably reliable and computationally feasi-
ble methodology of calculating energies and bar-
riers for reactions occurring on a variety of
catalytic sites. In addition, DFT provides informa-
tion on the electronic structures, wave functions,
charge distributions, and spectroscopic charac-
teristics of catalysts.
A variety of DFT-based codes is employed,
including VASP, Dacapo, CASTEP, Car-Parrinello,
CRYSTAL, Gaussian, Jaguar, and others. Each code
employs different basis sets, boundary conditions,
and density functionals, and each finds a niche in
particular types of catalytic problems. In some
cases, molecular dynamics functionalities are also
incorporated into the codes, either through ab ini-
tio MD methods (for example, Car-Parrinello) or
through approximate, reactive forcefields.
New computer hardware is also advancing
computational catalysis. Numerous researchers
employ home-built Beowulf clusters, and high-
performance computing clusters at DOE facili-
tiessuch as Environmental Molecular Sciences
Laboratory (Pacific Northwest National Labora-
tory), National Energy Research Scientific Com-
puting Center (NERSC, at Lawrence Berkeley
National Laboratory), and Blue Gene (ANL; Oak
Ridge National Laboratory)provide the neces-
sary hardware to expand computational studies.
Indeed, the dramatic rise in computing power,
which will reach petaflop-scale in the next few
years and exascale beyond that, will provide
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Computer codes are
providing new
opportunities for exploring
and understanding the
catalytic properties of
clusters and particles.
New computer hardware
is also advancing
computational catalysis.

N A N O S C A L E MAT E R I A L S
researchers in the near future with the unprece-
dented capabilities to study the catalytic proper-
ties of clusters and nanoparticles.
Subnanometer Heterogeneous Catalysis
Metal clusters of less than one nanometer in
diameter have, until recently, been difficult to syn-
thesize in a reliable and reproducible manner.
Recent advances in synthetic techniques, how-
ever, have begun to overcome these problems,
and subnanometer clusters are emerging as
objects of intense interest in both the experimen-
tal and computational catalysis communities.
The clusters are known to possess reactivity
properties not observed in their bulk analogs,
which makes them attractive candidates for use
as novel catalytic materials. The distinct catalytic
properties of the clusters are often hypothesized
to result from their unique geometric and elec-
tronic characteristics, such as the presence of a
high density of highly under-coordinated surface
atoms. These under-coordinated atoms, in turn,
are expected to possess unique capabilities for
bond breaking and bond formation.
Given their relatively small size, subnanometer
clusters are readily treated with DFT-based com-
putational approaches. Such approaches can pro-
vide detailed information about the cluster
morphologies and the reactivity properties of
individual atomic features on the clusters. This
information would be extremely difficult to
obtain by purely experimental methods, and as
50
S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
Catalysis is the study of materials that can control
chemical transformations. The ideal catalyst for a given
chemical reaction satisfies two general criteria:
G
It converts the starting chemicals (reactants) to the
desired products with no production of undesired
byproducts (in other words, it is perfectly selective)
G
It enables the reaction to proceed at a very high rate (it
is very active)
In practice, real catalysts must compromise on one or
both of these criteria, and the challenge of catalyst design
is to find materials that will come as close to optimal
performance as possible.
Complex chemical reactions generally comprise many
interrelated elementary reaction steps. Catalysts function
by altering the kinetics and thermodynamics of the
various elementary steps. By lowering the activation
barrier for elementary steps that lead to desired products,
for example, the catalyst can increase the rate of
formation of those products (figure 2). Conversely, by
raising the activation barrier for steps leading to undesired
products, the catalyst can suppress the formation of
those unwanted chemicals. The catalyst is thus seen to
be a sort of master puppeteer, controlling the intricate
interactions between different chemical species and
elementary reactions to produce desired chemical
products with a high degree of activity and selectivity.
Catalysts can take many forms. Among the forms most
actively investigated are homogeneous catalysts, wherein
isolated metal atoms and associated ligands are
suspended in solution, and heterogeneous catalysts,
wherein metal clusters or nanoparticles are immobilized
on support materials (figure 3). Both types of catalysts
find broad application in the fundamental sciences and
industry.
Gener al Pr i nci pl es of Cat al y s i s
E
n
e
r
g
y
Reaction Coordinate
Products
Reactants
Catalyzed
Reaction
Uncatalyzed Reaction
(Gas Phase)
E
g
E
s
E

Figure 2. Potential energy surface illustrating how

catalysts reduce the activation barriers of reactions.
Figure 3. A gold nanoparticle supported on an oxide
substrate. Hydroxyl, carbon monoxide, and carbon
dioxide molecules are reacting on the surface of the
nanoparticle.
The dramatic rise in
computing power, which
will reach petaflop-scale in
the next few years and
exascale beyond that, will
provide researchers in the
near future with the
unprecedented
capabilities to study the
catalytic properties of
clusters and nanoparticles.
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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
such, the calculations provide a powerful com-
plement to the experimental studies. For exam-
ple, bonds between carbon and hydrogen are
extremely stable and difficult to break in chemi-
cal reactions. However, recent computational
investigations of the reaction energies and bar-
riers of alkanes adsorbed on metal atom clusters
have found that certain very small clusters (con-
taining only four to eight metal atoms) have very
small barriers to breaking carbonhydrogen
bonds compared to much larger barriers for the
bulk metals. The computations indicate this is
because the under-coordinated atoms in the clus-
ters strongly attract electrons from the bond,
which thereby weakens the bonds. These results,
in turn, suggest subnanometer metal clusters may
be highly active for reactions involving small alka-
nes and alcohols (figure 1, p49). Indeed, these pre-
dictions are completely consistent with recent
experimental results that show a very high activ-
ity of Pt
810
clusters for carbonhydrogen bond
cleavage.
Electrocatalysis on Subnanometer Clusters
Nanometer- and subnanometer-sized clusters can
also show unique reactivity properties in
Can current electronic structure methods predict
reaction energies and barriers of catalytic reactions to
the chemical accuracy? The long term goal of modern
quantum chemistry has been the prediction of
thermochemical data to an accuracy of 1 kcal/mol,
which is key to the reliable prediction of structure,
stability, and reaction mechanisms.
HartreeFock calculations used in the early years of
quantum chemical computations are based on the
mean field assumption and are surprisingly accurate
for many properties. However, large errors (up to 100
kcal/mol) can be produced in bond energies where
electron pairs are being broken. Such methods proved
to be unsatisfactory for such predictions of reaction
energies and barriers. Accounting for interaction
between all electrons is very complicated, but tools
such as coupled cluster methods from many-body
theory has been very successful in accounting for
correlations between electrons and providing accurate
predictions of thermochemical data to chemical
accuracy. Methods such as Gaussian-4 theory are
able to predict reaction energies and barriers accurate
to 1 kcal/mol. These methods are being used to
validate the widely used density functional methods,
which scale better and can handle much larger
systems (figure 4).
Quant um Chemi cal Met hods f or Ener gy Pr edi ct i ons
Negative Region
Electrostatic Potential 0.02
Figure 4. An electron density plot for the reaction of propane with a four-atom platinum cluster. The carbon and
hydrogen atoms are gray and white, respectively, while the platinum atoms are darker.
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N A N O S C A L E MAT E R I A L S
electrocatalytic environments (sidebar Electro-
catalysis). For a critical reaction of interest in the
anodes of fuel cells, carbon monoxide (CO) elec-
tro-oxidation, these clusters can show substan-
tially higher intrinsic activity than either smooth
or stepped metal electrode surfaces. However, as
with the propane/platinum subnanometer clus-
ters described above, the experimental results
alone do not provide a molecular-level explana-
tion for the remarkable properties the electrocat-
alytic clusters display. To develop such an
explanation, computational catalytic studies can
be of great use.
DFT calculations were used to estimate the
energetics of the reactants and products associ-
ated with the key elementary steps in this reac-
tion network. Estimates of the relative rates of CO
electro-oxidation on various geometrical features
were obtained by performing these calculations
on subnanometer clusters supported by metal
substrates, single crystal models of electrode
steps, and perfect single crystal terraces. More sig-
nificantly, molecular-level explanations for the
differences in activity were derived.
CO functions as both a reactant and a poison
for this reaction. If the CO is bound too strongly
to the surface, it will impede the adsorption of
OH (the other key reactant) and will inhibit fur-
ther reaction. The calculations indicate multiple
CO molecules can adsorb on highly under-coor-
dinated atoms on the subnanometer clusters. This
high coverage of CO effectively repels neighbor-
ing CO molecules and makes them easier to
remove from the surface, thus reducing the poi-
soning effect. On the other hand, the calculations
also show hydroxyl (OH) groups, a key interme-
diate in the reaction, are significantly stabilized
on the highly under-coordinated adsorption sites
present on the subnanometer clusters, and the
geometry of the adsorbed OH is such that it can
interact naturally with surrounding water mole-
cules and be stabilized by the associated hydro-
gen bonding (figure 5). The net result of these two
effects is higher CO electro-oxidation activity on
the clusters than on steps, terraces, or other sur-
face features.
Heterogeneous Catalysis:
Single Crystals and Large Nanoparticles
Although the scientific possibilities associated
with subnanometer heterogeneous catalysis are
very promising, heterogeneous catalysts employ-
ing larger nanoparticles remain a crucial and
indispensable component of this field. Recent
computational efforts in this area have been very
fruitful and have added an important new dimen-
sion to the understanding of heterogeneous catal-
ysis on nanoparticles.
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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
Figure 5. Reaction of carbon monoxide and hydroxyl groups on Pt(111)-supported
platinum adatoms. The adatom is shaded dark gray, and the other platinum atoms are
light gray. Oxygen is red, carbon is black, and hydrogen is white.
Electrocatalysis is the study of catalysis in electrochemical environments. Such
environments are typically aqueous, can be extremely complex, and may involve a variety
of phenomena that play a lesser role in many other types of catalysis, including solid
liquid interfacial effects, solvated charges, charge transfer, and strong electric fields. The
activity and selectivity of electrocatalysts can be tuned by changing the catalyst potential;
this provides a degree of control over the catalytic properties that is not always available in
other types of catalysts. Electrocatalysts can, however, suffer from significant stability
problems due to enhanced metal dissolution and corrosion that occur in electrochemical
systems, thereby significantly restricting the types of materials that can serve as robust
electrocatalysts.
El ect r ocat al y s i s
The conventional approach to the calculation of the bonding of atoms has involved a
quantum mechanical solution for the electron wave function. An alternative approach
is a description based on the density of electrons at any point in space, which is
referred to as density functional theory (DFT). This simpler method is much less
expensive computationally than the wave function approach.
In principle, DFT provides an exact path to the determination of the electronic
energy of a system in a ground state. In practice, the functional form to do this is not
known, but in recent years great progress has been made in deriving functionals that
give a reasonably accurate description of molecular and solid systems. The dramatic
increase in computer resources currently available has made it possible to compute
reaction energies and barriers of many complex catalytic systems that can be used in
designing new catalysts. Functionals such as RPBE, B3LYP, and PW91 are among
the most popular for studies of catalytic reaction mechanisms.
Dens i t y F unct i onal Theor y
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In particular, periodic DFT codes have permit-
ted the accurate calculation of binding energies,
activation barriers, and other key catalytic
parameters on a large number of single crystal
metal and oxide surfaces. These approaches have
been instrumental in elucidating the atomic-
scale chemistry and physics that govern the
macroscopic properties of single crystal hetero-
geneous catalysts. Further, by supplementing
these calculations with thermodynamic tech-
niques and the Wulff construction (sidebar
Wulff Construction), it has been possible to
extrapolate the behavior of large nanoparticles
from the calculated behavior of single crystal
facets.
Once catalytic properties have been calculated
on various single crystal facets of a given metal or
alloy, the Wulff construction can be used to effec-
tively combine these results to build a picture of
the catalytic properties of more complex
nanoparticles, including the effect of catalyst sup-
ports on the reaction chemistry (sidebar Cata-
lyst Supports, p54). In addition, for smaller
particles, energy contributions of edges and even
corners become non-negligible and introduce a
dependence of particle shape on the particle size.
Therefore, such approaches can ultimately yield,
for example, ab initio predictions of the catalytic
properties of metal nanoparticles as a function of
the nanoparticles size. A recent example of such
a prediction, in this case for the oxygen reduction
reaction, is shown in figure 7 (p54).
Heterogeneous CatalysisElectrocatalysis
In addition to their longstanding applications to
traditional heterogeneous catalysis, highly paral-
lelized electronic structure calculations are being
increasingly applied to the study of complex elec-
trocatalytic phenomena. While traditional elec-
tronic structure/DFT calculations are not
naturally applicable to problems of constant elec-
trode potential, as is found in electrochemistry,
various techniques have been recently developed
to straightforwardly extrapolate electrochemical
environments from standard electronic structure
calculations. One particularly simple approach is
based on the concept of the theoretical standard
hydrogen electrode. This scheme is used to deter-
mine the potential dependence of the free ener-
gies of elementary reaction steps involving
transfer of protons and electrons. The potential
energy change of proton/electron transfer reac-
tions of the type
AB+H
+
+e
-
is evaluated by replacing the proton/electron pair
with half of an H
2
molecule; the energies are then
straightforwardly calculated with standard DFT
or other electronic structure techniques (to esti-
mate the effect of the aqueous environment on
these values, water molecules may be explicitly
added to the simulation cell). Simple entropy cor-
rections are then added to get the free energy
change of the reaction. The resulting free energy
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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
In the general case, the equilibrium shape of
crystals is anisotropic. It can be found from the
requirement, going back to Gibbs, that the total
surface free energy of a crystal with fixed
volume V has to be at minimum:

dA= min
where is the surface energy and A is the
surface area. The shape can be determined with
help of the Wulff theorem, formulated in 1901,
which states that the minimum surface energy
condition is equivalent to
i
/h
i
=constant, where

i
is a surface free energy of a crystal face i and
h
i
is the distance from the center to the face i.
Here, the surface free energy is defined as half
the energy per unit area required to separate
the crystal parallel to the plane i. The Wulff
construction gives the crystal shape as the inner
polyhedron formed by planes orthogonal to
lines drawn from the origin and intersecting
these lines at distances proportional to the
surface energy of the respective faces. Thus,
knowledge of surface energies for crystal faces
with Miller indices (hkl) provides knowledge of
crystal shape. First-principles calculations with
periodic boundary conditions are capable of
producing accurate surface and interfacial
energies. The surface energy also depends on
the composition and coverage of adsorbed
species, and first-principles studies provide
their binding energies. Thermodynamic
treatments and the Wulff theorem permit us to
use these energies to predict equilibrium
particle shapes and surface chemistries in
different environments. An example of such
prediction of shape of a platinum particle
annealed in argon and argon/oxygen mixture is
shown in figure 6.
Wul f f Cons t r uct i on
Figure 6. Shape of a catalytic platinum
nanoparticle, as determined with a combination
of first-principles calculations and classical
thermodynamic optimizations (Wulff
constructions).
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N A N O S C A L E MAT E R I A L S
change corresponds to the situation of zero
potential on the standard hydrogen electrode
scale. To determine how the free energy changes
with potential, the potential multiplied by the
number of transferred proton/electron pairs is
simply subtracted.
The strategy described above is quite power-
ful in its scope, as it rapidly deploys to electro-
chemical problems the theoretical and
computational approaches that have been devel-
oped for traditional heterogeneous catalysis over
the past 15 years. Computational approaches can,
thus, be used to provide molecular-level insight
into catalytic chemistry on metals and other
materials in electrochemical environments in
much the same way such insight has been
obtained in traditional catalytic systems.
For example, the oxygen reduction reaction, an
electrochemical reaction essential for the opera-
tion of low-temperature fuel cells, has recently
been studied using DFT calculations on single
crystal surfaces. By calculating the free energies
changes for all elementary steps associated with
this reaction on metal surfaces for a large num-
ber of different elements, a classic volcano plot
(sidebar Volcano Plots) was developed for the
reaction. The predictions of the relative catalytic
activities of different platinum alloys determined
from this volcano plot were subsequently shown
to match extremely well with careful experimen-
tal measurements. This close match between pre-
dicted rates from computational electrocatalytic
theory and experimental results suggests, in turn,
that computational techniques might be well-
suited to screening and design of new alloys for
applications in catalysis.
Screening Techniques
Electronic structure-based computational tech-
niques are being increasingly applied to the pre-
diction of novel catalyst properties. The ultimate
goal of these predictive efforts is to screen for and
design new catalysts for desired reactions of inter-
est. These types of computationally based eval-
uations can generally be done at a fraction of the
cost of analogous experimental screening.
Computational catalyst screening is completely
dependent upon modern, high-performance
computers. For a screening effort to be successful,
it is typically necessary to evaluate the catalytic
properties of hundreds of transition metal alloys,
oxides, or other catalytic materials. Such evalua-
tions can only be performed if reliable access to
high-performance computing systems, such as
the new 100 TF Blue Gene/P at the Argonne Lead-
ership Computer Facility, are available.
The basic computational screening procedure
is straightforward. First, simple descriptors
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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
2.0
1.5
1.0
0.5
0.0
0 5 10 15 20
Particle Diameter (nm)
7
5
2
0
0 5 10 15 20
Particle Diameter (nm)
6
4
3
1
T
O
F
/
T
O
F
P
t
(
1
1
1
)
T
O
F
/
T
O
F
P
t
(
1
1
1
)

1
0

4
Figure 7. Calculated reaction rate (TOF) of the Oxygen Reduction Reaction (ORR) on
platinum and gold nanoparticles as a function of particle size. The rates are normalized
to the calculated rate on a Pt(111) single crystal surface.
Supports provide a platform from which heterogeneous catalysts, such as a
nanoparticle, can act to change the rate of a reaction without being consumed
during the reaction. The support material may or may not take part in the catalytic
reaction. The support is usually a surface such as a metal oxide or carbon material.
The support and catalyst may bond together in such a way to enhance the reactivity
of the catalyst; in other cases, the support may be inactive and provide a high
surface area substrate to increase the collisions of the reactants with the catalysts.
For example, in catalytic converters, a ceramic honeycomb acts as a high surface
area support for the catalyst such as platinum, rhodium, or palladium for changing
pollution gases from the engine to environmentally friendly products. In fuel cells,
platinum catalysts are located on a carbon support, which provides a means for
conduction of the electrons for the electrocatalytic reactions.
Cat al y s t Suppor t s
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S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
(catalytic parameters that can be straightfor-
wardly determined with DFT or other electronic-
structure methods) are identified for the reactions
or processes of interest. These descriptors should,
with the aid of simple thermodynamic or kinetic
analyses, including the famous volcano plot (side-
bar Volcano Plots), be able to predict trends in
the activity and selectivity of catalysts with a rea-
sonable degree of accuracy.
The value of these descriptors is then deter-
mined on a large search space of possible materi-
als. DFT simulations and correlations between
variables in pre-existing computational databases
are used to calculate these descriptor values. The
most interesting materials for the reaction or
process of interest (that is, the materials with
descriptor values that lead to optimal properties)
are then identified. The stability and durability of
these materials in practical reactive environments
toward surface segregation, islanding, and disso-
lution are then assessed. Finally, the most prom-
ising catalysts are tested experimentally. This
approach can be thought of as a catalyst filter-
ing process (sidebar Materials Filtering, p56),
and the end result is the identification of a limited
pool of candidate catalysts that are predicted to
have excellent properties.
This approach has been used successfully to iden-
tify improved catalysts for a limited number of reac-
tions in heterogeneous catalysis and electrocatalysis.
Recently, more than 700 bimetallic alloys were eval-
uated with a computational catalytic screening pro-
cedure as candidates for hydrogen evolution
catalysts (a reaction of interest in the production of
hydrogen from acids and in reversible, low-temper-
ature fuel cells). From this large pool of candidate
alloys, a few were identified as suitable for experi-
mental testing, and one such alloy was subsequently
shown to have superior experimental performance
to pure platinum, the canonical catalyst used in this
reaction (figure 10, p57).
Although computational catalytic design
efforts have already been proven to be successful,
these efforts could be enhanced by generating and
Many heterogeneously catalyzed reactions are highly
sensitive to the particular metal, oxide, or other material
that is employed as a catalyst. These reactions show
pronounced changes in both activity and selectivity from
one catalyst to the next, and to select the most useful
catalysts for the reaction of interest, it is essential to
understand these changes.
Trends in activity from one catalyst to the next often
take the form of volcano plots (figure 8). In these plots, a
particular descriptor of the catalytic activity for the reaction
of interest (for example, the activation energy of a
kinetically important elementary step) is determined for
each catalyst and forms one axis of the plot; the other axis
is typically the catalytic activity at a fixed set of conditions.
As the name suggests, these plots often take the form of a
volcano with a clearly identifiable maximum in the activity.
The location of the maximum often signifies a change in
the most kinetically important (rate limiting) step of the
reaction and is also related to the well-known Sabatier
Principle, which states that optimal catalysts will interact
neither too strongly nor too weakly with the reactant and
product molecules.
Vol cano Pl ot s
0.5
1.0
1.5
2.0
2.5
0
3 2 1 0 1 2 3 4
E
0
(eV)
A
c
t
i
v
i
t
y
Co
Ru Ni
Fe
Mo
W
Rh
Cu
Ir
Pd
Pt
Ag
Au
Figure 8. Calculated volcano plot for the ORR. The y-axis shows the calculated activity for each metal (the natural
logarithm of the reaction rate) while the x-axis shows the calculated binding energy of atomic oxygen on the same
metals.
The ultimate goal of these
predictive efforts is to
screen for and design new
catalysts for desired
reactions of interest.
These types of
computationally based
evaluations can generally
be done at a fraction of
the cost of analogous
experimental screening.
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N A N O S C A L E MAT E R I A L S
organizing large databases of physical and chem-
ical property data. A materials design work-
bench could be created based on a repository of
data generated from accurate electronic structure
calculations. Using a mix of artificial intelligence
and computer science methods, the workbench
would guide users to identify candidate materi-
alsand perhaps, by extrapolation, aid in the
proposal of novel candidates that may not have
been computationally analyzed.
The application of the concept of computational
design to new subnanometer catalytic materials
will also be very fruitful. The clusters and nanopar-
ticles have a wide range of compositions but are of
small enough size so that current and near-future
computer capabilities should be adequate for mak-
ing significant progress in materials by design.
Scaling to Larger Systems
Todays electronic structure methodologies are
well-suited to treating systems with a limited num-
ber of atoms and electrons. However, the compu-
tational cost of electronic structure calculations
increases rapidly with system size, which then
requires prohibitively long run times. One solution
to this problem is, in principle, quite straightfor-
ward: simply run the calculations on more proces-
sors. However, most electronic structure codes
generally do not parallelize well beyond O(100)
processors, and fundamentally new codes and
algorithms are needed to take full advantage of the
processing power of petaflop-scale machines.
Efforts are currently under way to develop DFT-
based electronic structure codes capable of par-
allelizing efficiently out to thousands of
56
S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
The goal of virtual catalyst design requires that a variety of
design criteria be taken into account, including the activity
of the catalyst for the reaction of interest, the selectivity,
and the stability; each of these general criteria, in turn, may
involve the evaluation of a variety of descriptors or the
assessment of multiple processes that could destabilize the
catalyst. For conceptual purposes, each of these processes
or criteria could be thought of in terms of a filter, and the
design work as a series of filtrations (figure 9). The work
begins with a large pool of potential catalyst candidates.
This initial group is passed through successive
computational filters, which eliminate the catalysts that are
not predicted to be active for the reaction of interest. Next
to be eliminated are those catalysts that produce too much
of one or more byproducts. Finally, catalysts susceptible to
various types of destabilization events are eliminated, until
a much smaller pool of catalystsones likely to be active,
stable, and selectivehas been identified.
Mat er i al s Fi l t er i ng
Activity Screening Filter
Selectivity Filters
Stability Filters
Hundreds of Alloys
Figure 9. Schematic of the computatational catalyst filtering process. An initial pool of catalytic candidates is
sequentially tested for activity, selectivity, and stability properties, and unsuitable catalysts are filtered out.
Using a mix of artificial
intelligence and computer
science methods, the
workbench would guide
users to identify candidate
materialsand perhaps,
by extrapolation, aid in
the proposal of novel
candidates that may not
have been computationally
analyzed.
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processors. Such codes could perform realistic
catalytic simulations on nanoparticles with at
least 1,000 metal atoms. Entirely new possibili-
ties may then be revealed for both the computa-
tional understanding of heterogeneous catalysis
and the design of novel catalytic nanoparticles.
Gpaw is a new real-space, projector augmented
wave-based DFT code being developed to over-
come the limitations described above. Initially
developed in Professor Jens Nrskovs group at
the Technical University of Denmark, the code
represents a very efficient implementation of
DFT. The codes projector augmented wave for-
malism represents one of the most efficient extant
approaches for treating systems with large num-
bers of core electrons. In addition, the real-space
algorithm at the heart of the code is inherently
more parallelizable than DFT codes that employ
basis functions, and encouraging preliminary
results about Gpaws scalability to large numbers
of processors have already been obtained. A col-
laboration between the Technical University and
several Argonne divisions has further optimized
the code to make it suitable for use on systems of
Blue Gene scale. Successful completion of this
work should yield a code that can efficiently and
accurately treat catalytic particles up to 34 nm
in diameter and will represent a breakthrough in
computational catalytic science.
Summary
The tremendous progress in recent years on com-
putational catalysis results from the advanced
computational hardware at numerous supercom-
puting centers around the world. This research
provides important insights into the physical and
chemical phenomena that underlie homoge-
neous and heterogeneous catalysis. This progress
continues, and new efforts to extend traditional
single crystal catalytic modeling to subnanome-
ter metal clusters, electrochemical systems, and
very largeO(1,000) atomsmetal nanoparti-
cles, together with new initiatives in computa-
tional catalytic screening and design, are under
way. The combination of such diverse areas of
inquiry within a single field should ensure its
growth and relevance for many years to come. G
Contributors: Jeff Greeley, Peter Zapol, and Larry Curtiss,
Argonne National Laboratory
57
S C I D A C R E V I E W W I N T E R 2 0 0 8 W W W . S C I D A C R E V I E W . O R G
Fe Co Ni Cu As Ru Rh Pd Ag Cd Sb Re Ir Pt Au Bi
Fe
Co
Ni
Cu
As
Ru
Rh
Pd
Ag
Cd
Sb
Re
Ir
Pt
Au
Bi
>0.5
0.4 G0.5
0.3 G0.4
0.2 G0.3
0.1 G0.2
0 G0.1
|G
H
|
F r e e E n e r g i e s
o f
H A d s o r p t i o n
Figure 10. Computational combinatorial screening results for the Hydrogen Evolution Reaction (HER). Each circle represents a binary surface alloy.
The color of the circle denotes the free energy of hydrogen adsorption on the alloy, G
H
, as calculated by DFT. Lighter colors indicate higher
predicted catalytic activity for the HER.
The tremendous progress
in recent years on
computational catalysis
results from the
advanced computational
hardware at numerous
supercomputing centers
around the world.
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