Commentary

pubs.acs.org/accounts

Heterogeneous Catalysis: A Central Science for a Sustainable Future

Published as part of the Accounts of Chemical Research special issue “Holy Grails in Chemistry”.
Cynthia M. Friend*,† and Bingjun Xu*,§
†
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
§
Department of Chemical and Biological Engineering, University of Delaware, Newark, Delaware 19716, United States

ABSTRACT: Developing active, selective, and energy efficient

heterogeneous catalytic processes is key to a sustainable future
because heterogeneous catalysis is at the center of the
chemicals and energy industries. The design, testing, and
implementation of robust and selective heterogeneous catalytic
processes based on insights from fundamental studies could
have a tremendous positive impact on the world.

H eterogeneous catalysis is one of the pillars of the

chemicals and energy industries and will be a central
science in driving the transition to their eventual carbon neutral
operation. The design of active and robust catalytic processes to
improve the world is the ultimate goal. Ideally, materials with
self-regenerating active sites under functioning conditions can
be designed at the atomic level for critical catalytic processes.
The pursuit of rational design in catalysis was one of the “holy
grails” in the 1995 ACR articles by Breslow1 and by Bard and
Fox;2 the quest continues but with a greater urgency. The
increased urgency of catalyst development for key processes, for
example, biomass upgrading, CO2 reduction, water splitting,
and light alkanes activation, is due to the soaring demand for
energy, chemical products, and food and the rise in
anthropogenic CO2 emissions worldwide (Figure 1a).
Catalytic processes are central to the production of
chemicals, which accounts for approximately 25% of industrial
energy use,3 and the most energy-intensive processes rely on
heterogeneous catalysis. Hence, there is a major opportunity to
decrease energy consumption and reduce environmental impact
by increasing the efficiency of catalytic processes. Among them
are development of CO2-neutral processes, efficient and
sustainable production of H2 (one of the most energy intensive
processes now), selective oxidation of methane, and electro-
chemical production of ammonia.
In this Commentary, we use two examples related to the
sustainable production of chemicals that illustrate the value of
fundamental studies. We specifically show the importance of
using advanced spectroscopy and imaging to interrogate
catalytic systems under functioning conditions. Sustainable
production of chemicals by converting renewable biomass to
major chemicals is an area where new catalytic processes are of
paramount importance. The oxygen-rich and multifunctional
nature of biomass feedstocks suggest that more direct and cost-
effective routes could be developed to produce oxygenates than
the oxygen-lean hydrocarbon feedstocks (Figure 1b). Rational
design of catalysts with high activity and selectivity relies on the
fundamental understanding of key parameters (descriptors) of
catalysts that determine the surface mediated bond activation
and formation of reactants and intermediates. In this regard, it
is key to establish structure−activity relations using model and
platform chemicals, for example, alcohols, based on which
sustainable production of a wide spectrum of chemicals and
fuels can be developed.
Historically, heterogeneous catalysts have been developed by
trial and error. The development of the ammonia synthesis
process in the early 1900s illustrates how empirical screening
can yield a robust catalytic process.4,5 This example also
illustrates the huge potential impact of heterogeneous catalysis
on the world; in this case, the dramatic increase in agricultural
production enabled by synthetic fertilizers was estimated to
support almost half of the world population in 2008.6
Fundamental understanding of catalytic processes has
subsequently been used to further optimize catalysts and
process conditions. For example, the development of the
catalytic converter for automobiles benefitted from fundamen-
tal understanding of reaction kinetics for CO oxidation and
reduction of NOx on Pt single crystals.7 Likewise, improve-
ments in hydrodesulfurization catalysts were made using
guiding principles from fundamental studies and from in situ
studies of structure and mechanism.8,9
Major advances in experimental10−12 and theoretical13,14
methodology and a strong foundation of principles for
understanding surface reactions are now driving forward the
design of new catalytic processes. At the same time, major
advances in synthesis of new materials (well-defined nano-
particles, enabling control of shape and size, to hierarchical and
hybrid materials) provide a library of potential catalysts. There
Received: October 12, 2016
Published: March 21, 2017

© 2017 American Chemical Society 517 DOI: 10.1021/acs.accounts.6b00510

Acc. Chem. Res. 2017, 50, 517−521
Accounts of Chemical Research Commentary

Figure 1. (a) US energy consumption by sectors (data from eia.gov). (b) The differences in the composition and structure of fossil carbon sources
and biomass dictate that the strategy for and economics of their processing be fundamentally different. Oxygen-lean fossil carbon sources are ideal for
fuels and require selective oxidation to produce key chemicals.

Figure 2. (a) Selective dehydration of methylate requires the protection of the carboxyl group and removal of in situ generated H+. (b) Cooperative
metal−Lewis acid catalysis is needed to achieve high selectivity in converting furfural to 2-methylfuran.18 (c) Schematic of the ATR flow cell for
probing adsorbed species at solid−liquid interfaces. (d) Vibrational spectra of pyridine adsorbed on dehydrated NaY under vacuum (bottom
spectrum) and NaY in the presence of liquid water (top spectrum).

have also been major advances in the use of theoretical

modeling to design effective catalysts,15,16 as reviewed
previously.
Experimental design of catalytic processes can be achieved by
first establishing detailed reaction mechanisms on well-defined
model systems that apply to functioning catalytic conditions.
This approach enables generalization to predict new reactions
through the development of simple chemical paradigms. The
key to this approach is to select conditions such that the
dominant pathways in the model studies are the same as those
under operative catalytic conditions. Specifically, the concen-
trations and nature of surface species in the model studies must
mirror those under catalytic conditions. The predominance of
similar atomic scale structures of the model system and the
functioning catalyst is also an important factor. An exhaustive
survey of rational catalyst design is outside the scope of this
Commentary, and we will illustrate the successes and challenges
of “catalysis by design” with two specific examples from our
laboratories.
518
■ EXAMPLE 1. SELECTIVE BIOMASS CONVERSION:
MULTIFUNCTIONAL SUBSTRATES AND
CATALYSTS
The interrogation of catalytic processes under functional
conditions is extremely challenging for biomass conversion
processes, which often are conducted in liquid or multiphase
media. As the only substantial source of renewable carbon,
biomass is the preferred feedstock for producing renewable
liquid fuels and chemicals compatible with the existing
infrastructure.17 The “holy grail” of biomass upgrade is breaking
down a wide range of biomass feedstocks into a manageable
number of platform compounds before upgrading them to
desired products. Gasification of biomass to syngas by cleaving
all C−C and C−H bonds fails to take advantage of structures
and functional groups, for example, aromatic rings, shared
between the biomass and desired products. Depolymerizing
biomass into molecular building blocks and reassembling them
to valuable products should be more efficient.
In the complex environment of biomass upgrading reactions,
one-to-one correlations between model systems and function-
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Accounts of Chemical Research Commentary

Figure 3. Illustration of multiscale approach to understanding catalyst function for oxidative coupling of dissimilar alcohols. Model systems (right)
provide an atomic scale understanding of bonding and reaction mechanism. Atomic scale imaging of adsorbed O on Au(110), the active site, is
combined with density function functional theory (DFT) calculations to model bonding. The reaction mechanism is also established by model
studies. Nanoporous Au catalysts with 3% Ag are used to test the model under steady-state flow conditions. The dependence of selectivity for
formation of the methyl ester from oxidative coupling of allyl alcohol and methanol are nearly identical for the single crystal and under catalytic
conditions as shown on the bottom two panels.26−28

ing catalysts are far from established. Nevertheless, concepts
derived from fundamental studies can provide clues to effective
catalytic biomass conversion. The well-defined structure of
zeolite catalyst is an excellent platform for understanding
biomass conversion. The multifunctional nature of biomass
feedstocks and platform chemicals necessitates tailored catalysts
to selectively activate specific bonds while preserving others; for
example, the α-hydroxy group needs to be removed without
impacting the adjacent carboxyl group in the dehydration of
lactic acid to produce acrylic acid. Our recent work
demonstrates that the dissociative adsorption of methyl lactate
and the formation of sodium lactate on Na-exchanged FAU
zeolite (NaY) is key to selectivity control by protecting the
carboxylate group from decarbonylation (Figure 2a).19,20
In situ transmission FTIR spectroscopy investigations show
that Brønsted acid sites are formed during the during the
dissociative adsorption of methyl lactate on NaY in the
presence of water, which are known to catalyze the decarbon-
ylation reaction of methyl lactate to acetaldehyde. This led to
the hypothesis and validation that the removal of in situ
generated protons by a base in the feed, for example, pyridine,
could suppress the Brønsted acid catalyzed decarbonylation
reaction and enhance the selectivity for desired dehydration
products (Figure 2a).19,20 Although the introduction of
pyridine to the methyl lactate feed is unlikely to be industrially
feasible due to the downstream separation cost, these results set
the stage for the rational design of catalysts with intrinsic base
functionalities to quench the unwanted sites generated in the
reaction.
Multiple bond cleavages and formation are frequently needed
to reach the desired product, necessitating catalysts that enable
519
tandem reactions. Detailed isotopic labeling studies demon-
strated that the coexistence of Lewis acidic and metal sites on
Ru/RuOx/C was required to enable the tandem hydrogenation
and hydrogenolysis of furfural to 2-methylfuran.18 In this case,
the cooperativity between the metallic Ru and Lewis acidic
RuOx is achieved through the mixing of these sites on the
atomic level (Figure 2b): the hydrogenation of the carbonyl
group in furfural proceeds through a Lewis acid mediated
Mervin−Ponndorf−Verley (MPV) mechanism while the
hydrogenolysis of the resulting C−OH group occurs on the
metal site. Moreover, the crucial roles of oxygen vacancy on the
RuOx phase and the solvent were proposed via complementary
density functional theory and microkinetic calculations, leading
to a more comprehensive mechanistic picture of this complex
system.21,22 Such molecular level understanding will be the
basis for the rational design of hydrodeoxygenation catalysts for
biomass-derived furanic compounds.
The presence of solvent in many biomass upgrading
processes makes the understanding of surface mediated
reaction mechanisms in the liquid phase even more
challenging.23 It is critical to characterize catalytic sites in the
presence of solvents to establish structure−activity relations
because interactions with solvents could drastically change the
properties or even the structure of active sites, as well as the
interaction between the substrate and the catalytic site. To this
end, attenuated total reflection (ATR) based techniques have
been shown to be effective in selectively probing the adsorbed
species at the liquid−solid interface.24 With the customized
flow ATR cell (Figure 2c), we recently showed that the nature
of acid sites on NaY, a purely Lewis acidic material, were
modified in the presence of liquid water.25 Only vibrational
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Acc. Chem. Res. 2017, 50, 517−521
Accounts of Chemical Research
bands corresponding to pyridine adsorbed on Lewis acid sites
were observed on dehydrated NaY under vacuum; however, a
vibrational band for protonated pyridine, that is, pyridinium, at
1545 cm−1 was observed in the presence of liquid water (Figure
2d). These observations clearly highlight the importance of
molecular level understanding of solvent effects under func-
tional conditions on a model system in establishing the
structure−activity relations in heterogeneous catalytic reactions
carried out in the condensed phase.
■
EXAMPLE 2: BRIDGING THE PRESSURE AND
MATERIALS GAPS IN SELECTIVE OXIDATION
CATALYSIS
Once platform chemicals produced from biomass are available,
their selective transformation to an array of chemicals is
required. Selective partial oxidation of molecules such as
alcohols is a critical class of catalytic reactions for which high
selectivity is essential. An example of model studies that provide
the foundation for predicting how to achieve high selectivity
under functioning catalytic conditions is our study of ester
synthesis from selective oxidative coupling of dissimilar alcohols
on Au (Figure 3). A detailed model of the oxidative coupling of
alcohols was developed, first from foundational studies of
methyl formate production from methanol, followed by
generalization to longer-chain alcohols. Control of the
selectivity for coupling of dissimilar alcohols has the added
complexity that reaction selectivity depends strongly on the
competition of the key alkoxide intermediates for active sites
created by Oads. Hence, the selectivity for production of the
desired methyl ester depends on the mole fraction of the two
different alcohols in the gas phase.26,27,29 The selectivity was
highest for an excess of methanol. Theoretical studies
demonstrated that van der Waal’s interactions are critical in
determining the relative stability of these alkoxides on Au.30
The selectivity trends were essentially the same for Au single
crystals with low concentrations of Oads and for a functioning
nanoporous Au (npAu) catalyst operating under flow
conditions at atmospheric pressure (Figure 3).26−28
This case also illustrates the need for investigation of catalytic
materials under functioning catalytic conditions in order to
probe the nature of the active material and the robustness of
the catalyst; the application of advanced imaging and
spectroscopy methods to catalytic processes has been recently
reviewed demonstrating the state-of-the-art in this area.31 The
catalytic function of npAu has been illuminated through a
combination of in situ imaging with transmission electron
microscopy (TEM) and determination of compositional
changes under reaction conditions using ambient pressure X-
ray photoelectron spectroscopy (AP XPS).32 npAu is a dilute
alloy of ∼3% Ag in Au that is highly crystalline. The in situ work
demonstrates that the surface of the active catalyst is enriched
in Ag and that the composition changes depending on whether
the gas phase is net oxidizing or reducing. The Ag−Au
nanostructures are critical for the initial dissociation of O2 to
form Oads, the active site for reaction. Theoretical studies show
that Ag structures below the surface reduce the barrier for O2
dissociation to a value similar to that measured experimen-
tally.33,34 Although silver is essential for creation of Oads, the
ensuing reactions are characteristic of the majority gold
component yielding highly selective oxidative processes.
Advances in spectroscopic and imaging methods that can be
used under functioning catalytic conditions in the vapor phase
have already increased our understanding of heterogeneous
520
Commentary
processes. In the future, further advances are necessary that can
determine composition and structure at higher resolution, but
also to measure functionality locally under operating con-
ditions.
■ SUMMARY
The design, testing, and implementation of new catalytic
processes is a tremendous opportunity for positive impact on
the world. We have used two examples here to illustrate the
need for development of appropriate models that can be
translated into realistic conditions and to probe catalysis under
functional conditions, but there are many challenges in catalysis
that need to be addressed in the future.
From a chemist’s viewpoint, the goal of catalysis by design is
to map out catalytic steps at the molecular level and to develop
simple paradigms for classes of reactions. However, catalytic
processes are multiscale in their nature. Specific chemical
transformations occur on the molecular scale; whereas,
materials transport is at larger scales. As we look ahead,
investigation of catalyst structure and mechanism over multiple
length scales and time scales simultaneously using multiple
techniques will be essential. Theory also has an important role
to play in multiscale modeling that includes more accurate
electronic structure calculations, multiscale modeling of
reaction kinetics, including kinetic Monte Carlo and micro-
kinetic modeling, and grafting to larger scale macroscopic
engineering models.
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: friend@fas.harvard.edu.
*E-mail: bxu@udel.edu.
ORCID
Cynthia M. Friend: 0000-0002-8673-9046
Bingjun Xu: 0000-0002-2303-257X
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
C.M.F. and B.X. acknowledge the helpful discussion with Dr.
Robert J. Madix. C.M.F. also acknowledges the support
provided through the Integrated Mesoscale Architectures for
Sustainable Catalysis (IMASC), an Energy Frontier Research
Center funded by the U.S. Department of Energy (DOE),
Office of Science, Basic Energy Sciences (BES), under Award
Number DE-SC0012573. B.X. acknowledges the support from
the Catalysis Center for Energy Innovation, an Energy Frontier
Research Center funded by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, under Award
No. DE-SC0001004, and the National Science Foundation,
CBET, under Grant Number CBET-1437129.
■
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521 DOI: 10.1021/acs.accounts.6b00510

Acc. Chem. Res. 2017, 50, 517−521