Viewpoint
Cite This: ACS Catal. 2018, 8, 1520−1527 pubs.acs.org/acscatalysis
Direct Synthesis of H2O2 from H2 and O2 on Pd Catalysts: Current
Understanding, Outstanding Questions, and Research Needs
David W. Flaherty*
Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana−Champaign, Urbana, Illinois 61801, United
States
1. MOTIVATION AND CHALLENGES FOR DIRECT
SYNTHESIS OF H2O2
Catalytic reactions that utilize H2O2 as a terminal oxidant
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possess high selectivities for industrially relevant oxidations that
rival Cl2 mediated chemistry and reactions with organic
peroxides. H2O2 does not present, however, the same risks to
environmental and human health as those more commonly
used oxidants.1 The direct synthesis of hydrogen peroxide
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(reaction 1) over transition metal nanoparticles offers an
environmentally attractive method to enable a wide array of
impactful selective oxidation reactions including epoxidations of
alkenes, oxidations of thiols, thiophenes, and sulfides, and
conversion of alkanes to alcohols.
H 2 + O2 → H 2O2
The appeal of the direct synthesis reaction stems from the
potential of direct synthesis to create inexpensive H2O2 at
midscale, geographically distributed facilities, because direct
synthesis facilities have much lower capital and operating costs
than comparably sized Riedl−Pfleiderer plants (the auto-
oxidation of anthraquinones, the incumbent technology).1,2
Direct synthesis has not emerged as a practical technology
due to several technological and scientific barriers. Process
designs reveal a few barriers, such as process safety. For
example, direct synthesis requires that both H2 and O2 gas are
present in a single reactor at pressures sufficiently high to
achieve acceptable rates. Yet these conditions require also the
use of significant amounts of diluent gases (e.g., N2, CO2) to
prevent the formation of explosive mixtures.1,3 The use of
diluted reactant streams decreases the H2O2 productivity per
unit volume of reactor for a given total pressure and also
introduces the need for a sizable recycle stream to recover the
diluent gas and minimize compression costs.3 Perhaps more
importantly, scientific challenges and questions remain that
relate to the design of stable catalytic systems that convert H2
to H2O2 selectively. Specifically, how and why H2O2 formation
rates and selectivities on Pd nanoparticle catalysts depend on
reactant pressures and the solvents (water, alcohols) and
promoters (halide salts and acids) used are not understood.
Further, the solvents and promoters used to achieve significant
selectivities on Pd catalysts reduce their stability and useful
lifetime, which presents one of the greatest challenges for direct
synthesis. This Viewpoint introduces and describes current
understanding of this deceptively complex chemistry as well as
concepts important for developing selective, productive, and
stable Pd catalysts. Outstanding questions related to this
promising catalytic reaction and needs for future investigations
are described.
© 2018 American Chemical Society
2. SELECTIVITY IN THE DIRECT SYNTHESIS REACTION
The direct synthesis reaction involves reactions among
intermediates derived from H2 and O2 on transition metal
nanoparticles in a liquid solvent at low temperatures (273−313
K). A series of elementary steps appear to add H atoms
sequentially to O2 to form H2O2 while avoiding the production
of H2O by irreversible O−O bond rupture in any intermediate
which is followed by further reduction. Success requires
kinetically trapping unstable surface intermediates such as
OO* and OOH* as well as H2O2 to prevent formation of
thermodynamically preferred intermediates (O*, OH*) that
lead to H2O. The primary challenge, therefore, is suppressing
O−O bond rupture on metal nanoparticles that must activate
H2 under conditions where O2 dissociation seems facile (∼300
(1) K, 0.5−10 MPa H2, 0.5−10 MPa O2).
Data from nearly five decades of academic research show that
H2O2 rates and selectivities on Pd depend strongly on a
number of factors. The fact that H2 and O2 pressures affect
reaction rates4−6 is not unexpected. Figure 1 portrays several
Figure 1. Direct synthesis of H2O2 on Pd proceeds in complex
mixtures of aqueous solvents that contain mineral acids, halide salts,
alcohols, and their reaction byproducts. The reasons why these
additives affect H2O2 formation are not well understood.
other attributes of the catalytic system that are, perhaps,
surprising to researchers not familiar with this chemistry. These
include the choice of solvent (e.g., water, methanol, or ethanol),
the presence of trace amounts of halide salts (e.g., ∼ 5 ppm
NaBr), the addition of mineral acids (e.g., HCl, H2SO4), and
the identity of the diluent gas (e.g., N2 or CO2).1,4 These
complex combinations of halide salts, acids, and alcohol
solvents are required to achieve even modest H2O2 selectivities
(>60%) on supported Pd nanoparticles (the most selective and
Received: November 30, 2017
Published: January 24, 2018
1520 DOI: 10.1021/acscatal.7b04107
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ACS Catalysis
frequently studied monometallic catalyst). Slight differences in
these attributes of the catalytic systems significantly change
H2O2 production rates and selectivities (several comparisons
are provided in Table 2 of ref 1), and in some cases, these
changes suggest that these species participate directly in the
reaction.
Efforts to increase H2O2 selectivities fall largely into two
categories; catalyst design and reaction engineering. One
challenge is that the stability of O2* and OOH* surface
species that may be reduced to H2O2 are strongly correlated
with those of reactive intermediates that ultimately form H2O
(O*, OH*) on extended metal surfaces.7−11 Therefore, a
common principle of catalyst design for direct synthesis focuses
on the formation of bimetallic catalysts (e.g., PdAu,12,13 PdSn,14
PdZn15) or the use of promoters and additives (e.g., Cl−,
Br−)16−18 that may change or break scaling relationships among
O-containing intermediates. Both bimetallics and promoted Pd
catalysts give greater H2O2 selectivities perhaps by preventing
the formation of binding configurations thermodynamically
preferred on uniform metal surfaces (η2-O2 on Pd(111)) in
favor of those that involve less electron exchange (η1-O2 on
PdxAu(111)).19−21 Reaction engineering approaches attempt to
capitalize on differences between mechanisms and coreactants
for the kinetically relevant steps and transition states that form
H2O2 (e.g., OOH* + H* → H2O2* + *) and those that form
H2O (e.g., OOH* + * → OH* + O*). Among other factors,
changes in H2 pressure, the identity of the solvent, and the
addition of mineral acids to the liquid phase affect H2O2
selectivities. Several plausible explanations have been proposed
for these effects within individual studies, but direct evidence to
support or disprove many hypotheses is difficult to obtain.
Aside from the potential technological impact of selective
and stable catalysts for the direct synthesis of H2O2, this
chemistry is an appealing probe reaction to develop greater
understanding (and quantitative descriptions) of the manner by
which distinct aspects of catalytic systems (e.g., solvent, surface
promoters, catalyst composition, etc.) dictate chemistry at the
liquid−solid interface. Many opportunities exist for exper-
imental and particularly computational investigations of this
reaction, because, we understand much less about the direct
synthesis of H2O2 than many other reactions of small
molecules. Future studies need to embrace the complexity of
this system and include the critical “additives” that permit H2O2
to form in order to account for the complete set of species and
interactions required for this chemistry. Such work would help
to build a conceptual framework that describes this fascinating
chemistry. To build such a framework, we need first to
understand the mechanism for H2O2 formation.
3. PROPOSED MECHANISMS FOR H2O2 FORMATION
ON PD
Detailed discussions of the mechanism for direct synthesis of
H2O2 date to seminal publications by Lunsford and co-workers
who reported several key observations for H2O2 production
over Pd-SiO2 catalysts from reactions in semibatch reac-
tors.6,22−24 Analysis of the oxygen isotope labels in H2O2
produced from reactant mixtures of 18O2, 16O2, and H2
demonstrated that O−O bonds cleave irreversibly and always
lead to H2O formation.22 Consequently, achieving high
selectivities to H2O2 requires catalysts and active sites that
bind O2* but lack e− of sufficient energy to populate the 2π*
orbitals and cleave the O−O bond in O2*, OOH*, or other
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intermediates. Perhaps surprisingly, the way in which O2
reduces to form H2O2 is still unclear.
3.1. H2O2 Formation in Water. Within purely aqueous
solvents (i.e., in the absence of alcohols), most studies measure
H2O2 formation in acidic solutions of either HCl or H2SO4 that
also contain NaBr or NaCl, because H2O2 will not form in
measurable quantities otherwise.5,6,25,26 Under these conditions,
Lunsford reported that H2O2 formation increase in proportion
to both H2 and O2 pressures at lower pressures and become
independent of reactant pressures at greater values (water
formation rates were not reported).22 Complementary experi-
ments demonstrated rates did not differ between perhydro-
genated and perdeuterated combinations of aqueous solvents,
acids, and hydrogen.6 These data were interpreted as evidence
that the reaction rates were transport limited or that O2 binding
was rate determining,6 although these explanations seem
inconsistent with the measured rate dependencies. The
addition of HCl or H2SO4 to aqueous solvents (or neat
ethanol) increases rates significantly but the manner by which
these proton donors promoted H2O2 formation was not clear in
initial reports.6,22,27 Contemporaneous work by Stahl et al.
illustrated that H2O2 forms upon reduction of bathocuproine
Pd−O2 complexes28,29 and inspired Lunsford to propose that a
similar catalytic cycle may form H2O2 during direct syn-
thesis.6,30
Figure 2 shows steps that corrosively oxidize Pd to form
soluble Pd-peroxo complexes that are protonated by HCl and
Figure 2. Proposed catalytic cycle for H2O2 formation by Pd within
acidified water. O2 binds to soluble PdII complexes and reduces by
proton electron transfer as described by Lunsford et al.6
subsequently reduced by H2 gas to reform metallic Pd and HCl.
Importantly, this work hypothesized that proton−electron
transfer pathways were responsible for H2O2 formation on Pd
sites under nominally thermocatalytic conditions.6,30 Kinetic
dependencies on reactant pressures similar to these early
studies (rH2O2 ∼ [H2]0−1[O2]0−1) were recently reported from
experiments in continuous flow microreactors that also used
water as a solvent (5−10 ppm NaBr, 0.05−0.5 M H2SO4).5,26,31
However, these data were interpreted as evidence for a two-site
surface reaction in which H*-atoms and O2* adsorb non-
competitively and react on the surface to reduce O2 to H2O2.5
Neither of these mechanisms contains quantitative descrip-
tions that show protons or acids are coreactants or cocatalysts
for H2O2 formation, rather, the given interpretations state that
these species participate indirectly. Protons are frequently
described as modifying the electronic structure of Pd.32
Similarly, halides are denoted as site blockers, despite the fact
that even trace quantities of H2O2 do not form in aqueous
solvents in their absence.32 These conclusions seem speculative
and specific to aqueous systems. As described next, rate
dependencies and kinetic behavior for H2O2 formation differ
significantly within alcohol solvents and also in aprotic solvents.
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These differences suggest that the solvent participates directly
within the catalytic cycle as either a coreactant or a cocatalyst.
Moreover, H2O2 can form even without halide “site blockers.”
3.2. H2O2 Formation in Non-Aqueous Solvents. Direct
synthesis may become an economical method to produce H2O2
for epoxidation or oxidation catalysis over transition metal
oxides.1 Water can significantly decrease rates in these systems,
and therefore, H2O2 may be produced in alcohol solvents that
are compatible with these chemistries.33 The significant
differences in H2O2 formation rates and selectivities between
aqueous and alcohol solvents are frequently attributed to
greater solubility of H2 in alcohols compared to water (vide
inf ra).34−36 A few specific observations suggest, however, that
the mechanism for H2O2 in methanol and ethanol may differ
fundamentally from the mechanism within water.
Lunsford first reported that H2O2 formation rates increase in
proportion to H2 pressure and do not depend on O2 pressure
(rH2O2 ∼ [H2]1[O2]0) within ethanol (0.12 M H2SO4),23 but
the report did not propose a molecular mechanism to explain
these results. These results were quickly followed by reports for
the effects of H2SO4, Cl−, and CH3COOH on H2O2 rates
within ethanol that were interpreted as evidence for high
coverages of acetate (formed by ethanol oxidation) and Cl− on
Pd surfaces that block Pd ensembles needed to dissociate O−O
bonds (vide inf ra).32 Again, halides and protons derived from
mineral salts and acids were described as critical promoters for
H2O2 that modify the reactivity of the Pd surface but are not
involved directly.
Our group recently reported mechanistic analysis of steady
state H2O2 and H2O formation rates measured as functions of
reactant pressures along with complementary experiments
probing the influence of the solvent properties.4 In pure
methanol (i.e., without water, NaBr or H2 SO 4 ), H 2 O 2
formation rates increase with H2 pressure but do not depend
on O2 pressure (rH2O2 ∼ [H2]1/2−1[O2]0; similar to reports in
ethanol23).4 H2O formation rates depend more weakly on H2
and are also independent of O2 (rH2O ∼ [H2]0−1/2[O2]0).4
These observations are inconsistent with competitive adsorp-
tion of H2 and O2 on a single active site. Independent
experiments demonstrated that H2O2 forms only in the
presence of protic solvents (methanol, water) and was
undetectable in aprotic solvents (acetonitrile, dimethyl
sulfoxide, and propylene carbonate).4 Together these observa-
tions provide strong evidence that protic solvents cocatalyze
H2O2 formation.
Figure 3 depicts one method by which water or methanol
may participate directly in H2O2 formation by introducing low
barrier pathways for O2* reduction. Protons form by heterolytic
Figure 3. Catalytically coupled heterolytic hydrogen oxidation and two
electron oxygen reduction reactions may form H2O2 on Pd
nanoparticles. Adapted with permission from ref 4. Copyright 2016
American Chemical Society.
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oxidation of H2 (i.e., H2 → 2H+ + 2e−) and shuttle via oxonium
species during consecutive proton−electron transfer steps that
reduce O2 to H2O2. This mechanism accounts for the need for
H2 as a reductant (i.e., H2O2 did not form at detectable rates in
methanol without external H2) and provides a means to
maintain the solvent pH and the electronic charge on Pd
nanoparticles.4 Pd-based bimetallic nanoparticles also appear to
directly involve alcohol molecules in the formation of H2O2.
Bimetallic AuPd nanoparticle catalysts exhibit similar depend-
encies of rates on H2 and O2 pressures and on the protic nature
of the solvent, even though H2O2 selectivities are nearly 6-fold
greater on the most Au-rich nanoparticles.37 These differences
reflect changes in the electronic structure of the Pd active sites
that increase activation enthalpies for O−O bond dissociation
and the formation of H2O, consistent with theoretical
predictions for close-packed surfaces.19,38−40 Kinetic data and
solvent requirements for H2O2 formation on intermetallic β-
PdZn nanoparticles15 also match the mechanism shown in
Figure 3.
Despite these recent findings, the molecular mechanism
responsible for H2O2 formation is by no means resolved. The
results reviewed here for both aqueous and nonaqueous
solvents (Sections 3.1and 3.2) are all consistent with proton−
electron transfer mechanisms. Based upon current findings,
such heterolytic reaction mechanisms seem most likely to be
responsible for the direct synthesis of H2O2. However, the
identity of the kinetically relevant step, the most abundant
surface intermediate, and the details of how the protic solvent
(or the derived surface fragments) shuttle protons and
electrons to O2 may differ. Additional experimental and
computational investigations are needed to develop detailed
understanding of the steps that combine H atoms with O2 and
the ways in which halides, acids, and solvent molecules
participate. In situ spectroscopy and increasingly complex
molecular simulations should be integrated into future studies
to probe other ways in which solvent molecules may be
involved.
4. SOLVENTS HAVE MULTIPLE ROLES FOR H2O2
FORMATION
The solvent used for the direct synthesis of H2O2 has a
significant effect on the rate of the reaction and the selectivity
to H2O2. Solvents such as water, methanol, and ethanol may
influence H2O2 yields by facilitating transport of the reactants
to the active sites and by chemically binding to and modifying
exposed metal atoms. These effects are shown by comparisons
of catalytic rates performance to the solubility of O2 and H2 in
pure solvents and multiple component solutions.29,34,35 Several
reports suggest that the adsorption of organic molecules (e.g.,
CH3COO−) to catalyst surfaces increases H2O2 selectivities in
several reports.23,32,41 Solvent molecules seem likely to
influence H2O2 formation and decomposition pathways by
less frequently discussed methods as well. H2O2 only forms
within protic solvents,4,15,37 which strongly suggests that
solvents participate directly in proton or hydride transfer
processes. In addition, solvent molecules may stabilize critical
intermediates via intermolecular interactions such as hydrogen-
bonding.
Undoubtedly, the use of appropriate solvents to facilitate
mass transport is important for implementing direct synthesis
chemistry, particularly in industrial reactors that would operate
near the limit of mass transfer rates. Yet, carefully designed
laboratory experiments can eliminate interphase and inter- and
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intraparticle concentration gradients such that measured H2O2
and H2O formation rates reflect only the kinetics of the
catalytic reaction.42,43 Under these conditions, solvents still
change formation rates of H2O2 and H2O, which shows that the
solvent influences this catalytic reaction in ways that are not
related to transport processes or reactant solubility alone.
The potential ability to use solvent molecules or other
species (e.g., halides, acids) to chemically modify the surface of
nanoparticle catalysts or to stabilize transition states directly are
intriguing. Lunsford and co-workers suggested that ethanol and
acetic acid (added directly or produced in situ) may be
responsible for greater H2O2 selectivities in ethanol in
comparison to water.23,32 The formation of chelating acetate
species32 may inhibit O−O bond rupture by disrupting
ensembles of Pd atoms required to bind η2-O2, η1-OOH, and
the transition states for their reduction or dissociation, similar
to proposals for bimetallic catalysts with improved H2O2
selectivities.38,44−46 Similarly, Nijhuis et al. demonstrated that
H2O2 selectivities increase by a factor of two on Pd and AuPd
nanoparticles with the addition of small amounts (≥2 vol %) of
acetonitrile to an aqueous solvent (containing 0.05 M H2SO4, 9
ppm NaBr), which was attributed to acetonitrile reducing the
coverage of O2 at Pd ensembles responsible for O−O bond
rupture.34 This concept could explain also one role of alcohol
solvents (methanol), surface ligands (e.g., long-chain ammo-
nium dihydrogen phosphates depicted in Figure 4),47,48 and
Figure 4. Long-chain alkyl ammonium phosphates coadsorbed on Pd
increase H2O2 selectivities and are predicted to increase barriers for
O−O bond rupture during the direct synthesis of H2O2. In general,
dense adlayers of solvent molecules or intentional ligands can modify
binding modes of reactive intermediates and electron exchange with
surfaces and can subsequently influence H2O2 selectivities. Repro-
duced with permission from ref 47. Copyright 2017 Wiley-VCH.
perhaps diluent CO2,13,14 which forms carbonic acid in situ.4 All
of these species can form adlayers of chelating species that
reduce the number of accessible metal sites and hinder
adsorption modes of reactive species such that O−O bonds
are more difficult to cleave. In situ vibrational spectroscopy
would be useful to determine if the proposed carboxylate and
ligand adlayers exist during catalysis and to correlate the
coverage of these species to rates and activation energies for
H2O2 and H2O formation. These comparisons would directly
test how these adlayers influence the two reaction pathways.
Apparent activation energies, selectivities, and rates for H2O2
and H2O formation depend on the solvent likely because
solvent molecules participate directly in the catalytic cycle and
assist by solvating reactive intermediates or transition states
through intermolecular interactions. Methanol, water, and their
protonated forms cocatalyze proton−electron transfer steps by
providing low barrier pathways to shuttle protons, which can
explain the need for protic solvents to form detectable
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quantities of H2O2.4,15,49 Further, alcohols may provide greater
rates and selectivities than water by acting as coreagents for
catalytic transfer hydrogenation of O2 by hydride-proton
transfer steps akin to the Meerwein-Ponndorf-Verley mecha-
nism for reduction of carbonyl groups.33 Fluid-phase solvent
(or adsorbed fragments) molecules can also influence catalysis
by stabilizing kinetically relevant transition states via
intermolecular interactions such as hydrogen-bonding or by
solvating highly charged structures (e.g., those involved in
proton−electron transfer processes).50,51 Classical models for
these effects in catalysis are described in texts51,52 and can be
quantified in the framework of thermodynamic activity
coefficients for solvent-species pairs, which can include
transition states.
5. HALIDES AND ACIDS AFFECT H2O2 RATES AND
SELECTIVITIES
The vast majority of publications that report the direct
synthesis of H2O2 in water or in alcohol solvents also include
catalytically significant quantities of halide salts (e.g., NaBr) or
inorganic acids (e.g., HCl, H2SO4). These additives are often
used with little discussion of their role in catalysis, which
suggests that their use is based on phenomenological
observations that they increase H2O2 selectivities. Pospelova
et al. first demonstrated that H2O2 formed in immeasurable
quantities on pure supported Pd catalysts in water, but the
addition of millimolar quantities of acids and halides increased
H2O2 yields to nearly 60%.53 More recently, H2O2 selectivities
above 90% and nearing 100% were achieved through more
complex combinations of H2SO4, HCl, and Br− promoters.
Several publications have probed how these species influence
H2O2 formation and decomposition pathways, but few
investigations probe the intrinsic way in which these species
influence surface catalysis.
The additions of halides, and more specifically Cl− and Br−,
to solvents or to catalyst supports increase H2O2 selectivities
significantly. Adsorption and activation of O2, H2, and other
surface intermediates are undoubtedly influenced by the
presence of halide coadsorbates, and these species are
frequently described as blocking specific sites responsible for
cleaving O−O bonds.6,16−18,24,53 However, halides are likely to
influence the density of states of greater numbers of metal
atoms in their vicinity and may confer greater selectivity for
H2O2 formation to multiple sites by limiting the extent of e−
back-donation to 2π* orbitals of O2 via through-surface
interactions.54 This explanation is consistent with greater
work functions for Pd(111)55 and weaker O*-atoms binding
energies on Pt(111)56 and Au(111)57 in the presence of Cl*-
adatoms. However, increasing concentrations of halides oxidize
Pd to form soluble Pd2+-complexes (e.g., PdCl42−),49 which
leads to greater rates of metal dissolution from the support and
reduces the longevity (and utility) of the catalyst. More
commonly, Br− is used to promote H2O2 formation on Pd,
because Br− leads to comparably high H2O2 selectivities yet
does not leach Pd from the catalyst as rapidly.27 The changes in
selectivities, H2O2 formation rates, and Pd leaching rates do not
depend significantly on the precursor used to add Br− to the
solvent for the reaction58 but are sensitive to the concentration
of acids used as copromoters.59
The role of acids in H2O2 formation is more difficult to
understand, because their dissociation leads to two inter-
mediates that may each modify surface reactivity. The anions
derived from acids commonly used (e.g., HBr, HCl, and
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H2SO4) may influence catalysis by their adsorption and
interaction with nanoparticle surfaces. For example, halide
anions may coordinate to the surface of Pd nanoparticles and
either inhibit reaction at Pd ensembles or electronically modify
Pd sites by withdrawing charge (vide supra).54−56 In addition,
acids have been proposed to inhibit the decomposition of H2O2
by preventing its deprotonation to more reactive forms (e.g.,
OOH−) that bind strongly to metal surfaces and decompose.27
Thus, the addition of acids may shift the position of equilibria
related to these deprotonated and more reactive forms. Finally,
the changes in the concentrations of acids (and also halide
salts) in a solvent will influence the ionic strength of the
solution and affect the thermodynamic activity of charged
intermediates and transition states within the catalytic cycle.51
Such changes may preferentially stabilize pathways for H2O2
formation over those for H2O. These potential effects have not
been deconvoluted in previous experimental investigations, but
these points may be addressed with computational studies.
6. THE STATE OF THE ACTIVE PD CATALYST IS
UNKNOWN
Despite ongoing work to determine the mechanism(s) by
which H2O2 forms, it is clear that molecular O2 binds to the
active site and reduces to form H2O2 without O−O bond
rupture.22 Pristine Pd surfaces and nanoparticles readily
dissociate O2 at cryogenic temperatures, which suggests that
active sites for direct synthesis differ significantly from these
more reactive surfaces. Pd nanoparticles can form PdO and
PdH phases when exposed to O2 and H2 respectively, which
coexist at significant pressures during H2O2 formation. These
observations and the effects of ligand and halide additives
indicate that the active state(s) of Pd responsible for selective
formation of H2O2 is not a clean, metallic surface. Rather, H2O2
likely forms either on surfaces of metallic Pd nanoparticles
covered by halides or reactive intermediates (e.g., O*, OH*),
surfaces of PdO or PdH nanoparticles, or on soluble Pd-
complexes formed by dissolution of nanoparticles.
Lunsford first showed that rates of H2O2 formation in
semibatch reactors did not correlate to the amount of Pd
supported on SiO2 supports in the presence of HCl.49 The Pd
nanoparticles dissolved into vividly colored Pd2+ complexes
(e.g., PdCl42−, observed in many batch reactor experiments)
and redistributed as nanometer sized Pd colloids throughout
the solvent and across the walls of the reactor (steps shown in
Figure 2).24,49 These Pd colloids were proposed to be the active
catalysts responsible for the majority (>97%) of H2O 2
produced, because, significant mass transfer limitations limited
the productivity of the Pd-SiO2 catalyst particles (i.e.,
effectiveness factors (η) ≪ 1).24,49 While this work suggests
that Pd colloids form H2O2, it is not clear if the experiments
performed could rule out the possibility that soluble Pd-
complexes are also active sites for H2O2 formation. We are not
aware of further studies that have provided evidence for or
against the idea that liquid-phase Pd2+ species contribute to
measured H2O2 formation rates during direct synthesis.
However, barriers for O2 dissociation on these and other
mononuclear Pd complexes28,60 are greater than on pristine Pd
surfaces,19,21 and the populations of such complexes increase
significantly with the addition of halide and acid promoters.
The surfaces of metal nanoparticles are most commonly
considered to expose the active sites for H2O2 formation. Yet
knowledge of the chemical state and structure of these
nanoparticles during direct synthesis is often obtained
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indirectly. PdO nanoparticles supported on silica do not form
measurable amounts of H2O2 in semibatch reactors (5 kPa H2,
75 kPa O2, 283 K, ethanol, 2 h).61 However, H2O2 forms
readily within the same system after sparging with 20 kPa H2
(in N2, 1 h) and reintroducing the H2 and O2 coreactants.61
Han et al. proposed that Pd-PdO sites located at the interface
with a TiO2 support were active sites for H2O2 formation based
upon comparisons of measured H2O2 selectivities to ex situ
XAS and XPS assessments of Pd oxidation states.62 Our group
has observed that PdO nanoparticles exhibit significant
induction times (∼0.5 h) prior to forming H2O2, whereas, Pd
nanoparticles form H2O2 immediately (9 kPa H2, 5 kPa O2, 298
K, methanol).63 Cumulatively, these observations indicate that
at least a fraction of the nanoparticles must exist as reduced Pd
in order to form H2O2, but it is not clear if the active sites that
bind and selectively reduce O2 to H2O2 are reduced, partially,
or fully oxidized Pd atoms.62
A few publication have applied in situ X-ray absorption
spectroscopy (XAS) to probe the state of Pd during
catalysis.41,64 Results from Centomo et al. suggested that Pd
nanoparticles on a resin support contained a significant fraction
of Pd0 (60%) in pure methanol, which increased slightly upon
adding the reactant stream (H2 and O2 in CO2).41 On the other
hand, more recent results reported by Hensen and Schouten
indicated that Pd nanoparticles existed largely as PdH during
catalysis in water.64 These differences likely reflect differences
in reactant pressures and solvents used. Systematic comparisons
of H2O2 formation rates and selectivities to the state of the Pd
nanoparticles (determined by in situ XAS or Raman) across a
wide-range of O2 and H2 pressures would be useful, because
such data may shed some light on the state of Pd responsible
for selective H2O2 formation.
7. RECOMMENDATIONS FOR FUTURE RESEARCH
Many fundamental aspects of the direct synthesis of H2O2
remain uncertain, but the great potential of this chemistry to
enable selective and environmentally benign oxidations
provides considerable motivation to continue investigating
this complex reaction. The comparisons of the mechanistic
studies highlight several questions that should be addressed in
future studies, and which will need contributions from both
theoretical and experimental methods to unravel the more
intricate aspects of H2O2 formation. Specific points for further
investigation include: the mechanism for O2 reduction to H2O2
and the potentially direct participation of solvent molecules in
this process; the interaction between coadsorbates (i.e., halides,
solvent molecules, and reactive intermediates) that influence
the reactions of dioxygen intermediates; and chemical or
electronic characterization of the active sites that produce
H2O2.
7.1. Need for Computational Work with Complete
Models. Computational studies of H2O2 formation have the
potential to provide atomistic insight that eludes even the most
carefully designed experiments. To date, density functional
theory (DFT) calculations have been used to probe the
elementary steps that determine selectivity and differences
between Pd, PdH and more selective Pd-based bimetallic
catalysts (e.g., PdAu).8,38−40,47,65 Investigations of AuPd
bimetallic surfaces demonstrated that intrinsic activation
energies for O−O bonds in O 2 * or OOH* surface
intermediates increase systematically with the number of Au
atoms within the close-packed (111) surfaces,19,38,39 whereas,
the activation energies for hydrogenation pathways (e.g., O2* +
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ACS Catalysis
H* → OOH* + H*) increase to a somewhat smaller
extent.38,39 These trends reproduce the greater selectivities
toward H2O2 on AuPd materials.12,13,49,66 Analysis of the
densities of states upon Pd atoms within these bimetallic
surfaces shows that the addition of Au leads to systematic shifts
of the d-band to lower energies (presumably due to
rehybridization of Pd atomic orbitals as a result of changes in
strain)38,39 and a concurrent reduction in the extent of electron
back-donation to 2π* orbitals of O2*.
Notably, most computational investigations into direct
synthesis of H2O2 utilize periodic boundary conditions for
two-dimensional unit cells (e.g., 3 × 3) and treat low coverages
of reactants (<0.25 monolayers) but do not incorporate solvent
molecules (explicitly or implicitly) or interactions between
coadsorbates, such as halide promotors or other reactive
intermediates. As described above, H2O2 rates are immeasur-
able on most catalysts (and particularly on Pd) in the absence
of alcohol solvents or halide and acid promoters. Therefore, we
must carefully consider the meaning of predictions derived
from models that do not contain these species. These aspects
are regularly treated in quantum chemical studies of the
electrocatalytic oxygen reduction reaction (ORR) by two
electron (2e−) and four electron (4e−) pathways,44−46,67,68
which may have more similarities to direct synthesis of H2O2
than initially expected.4,15,49 The computational expense to
implement models that include all the species crucial for H2O2
formation will be greater, but the understanding gained from
these studies would be valuable. Such work will need to be
performed in close cooperation with experiments that provide
kinetic parameters (e.g., activation enthalpies) and measure
physical attributes of the catalyst surface (e.g., adsorbate
coverages, oxidation states) that can be used to develop and
validate these models.
7.2. Areas for Further Experimental Study. Many
previous investigations of the direct synthesis of H2O 2
compared H2O2 formation rates, yields and selectivities across
different reaction conditions or between different forms of Pd
catalysts to learn a great deal. However, further progress will
require application of experimental methods less commonly
used in this topic (e.g., in situ spectroscopy) and more
quantitative analysis of intrinsically meaningful kinetic variables.
In situ vibrational spectroscopy could provide vital
information regarding the identity and relative coverages of
reactive species present on nanoparticles during catalysis. Such
measurements will, however, challenge researchers, because
liquid solvents and high gas pressures require combinations of
specialized spectroscopy methods (e.g., attenuated total
reflectance, Raman, sum-frequency generation)69 and exper-
imental protocols (e.g., modulation excitation)70 to differentiate
reactive surface intermediates from spectating surface species
and the solvent. These experiments could directly test multiple
hypotheses related to this chemistry. First, the proposal that
active sites are saturated with O2* and OOH* species during
direct synthesis in alcohol solvents (suggested by rH2O2 ∼
[O2]0)4,23,37 should be tested with vibrational spectroscopy,
because this suggestion conflicts with the facile dissociation of
O2 on pristine Pd nanoparticles and Pd(111).19−21 Use of
infrared or Raman spectroscopy may detect vibrational features
related to O2*-species (e.g., peroxides or superoxides) that
would provide evidence for these intermediates. Second, Pd
catalysts that form H2O2 selectively may support dense adlayers
of halides6,18 or solvent molecules (and their decomposition
products, such as acetate)32,34 that impede O−O bond rupture.
1525
Viewpoint
Vibrational spectroscopy and kinetic measurements can be
combined to determine if coverages of such coadsorbates
correlate with activation enthalpies or selectivities for H2O2
selectivities, the identity of these coadsorbates, and to inform
computational studies that probe adsorbate−adsorbate inter-
actions.
In situ XAS or Raman can be used to determine the
electronic and structural states of Pd nanoparticles (and
particularly their surfaces) under relevant reaction conditions.
Pd nanoparticles may become oxidized by reaction with O2 and
form regions of PdO62 or mixed Pd oxides14 that increase H2O2
selectivities by possessing greater barriers for O−O dissocia-
tion.71,72 Particularly, comparisons of how Pd−Pd coordination
and mean oxidation states of Pd change between conditions
that give low to undetectable H2O2 selectivities (e.g., modest
H2 pressures and aqueous solvents)6 to those that give high
selectivities (e.g., high H2 pressures, alcohols solvents, and
halides or acid promoters)18 would provide valuable insight.
Such measurements would help identify subtle changes in the
electronic state of surface Pd atoms or more dramatic phase
changes (e.g., formations of hydrides or oxides) that depend on
the concentrations of fluid phase species known to influence
H2O2 formation rates and selectivities.
We can still learn a significant amount about mechanistic
aspects of the direct synthesis reaction and the roles of the
many additives with accessible experimental methods (e.g., rate
measurements), but the measurements will need to strictly
reflect chemical kinetics (and not mass transfer)42 and the data
analysis must be quantitative and model-based.4,5,31,37 More-
over, researchers need to report fundamental and transferable
kinetic quantities (e.g., turnover rates, activation enthalpies)
that provide direct comparison to model calculations.73
Within such studies, it would be useful to probe how the
apparent dependence of rates on H2 and O2 pressures change
with the identity of the solvents, such as aqueous and alcohol
solvents, and the presence of halides. Disparities between
observed rate dependencies in water,5,6,31 methanol,4,37 and
ethanol,23 suggest that certain aspects of the mechanism for
H 2 O 2 formation may change along with the solvent.
Comparisons between data and rate expressions need to be
built upon derivations from systems of elementary steps.
Measurements of both isotope scrambling and kinetic isotope
effects were useful in early mechanistic studies of H2O2
formation in water.6,22 Yet, isotope methods have been
underutilized recently despite their ability to directly probe
the kinetic relevance and reversibility of specific steps and to
implicate particular reactive species. For example, unpublished
data from our lab show that H2O2 formation rates differ
between H2 and D2 reactants but also between labeled alcohol
solvents (e.g., CH3OH, CH3OD, and CD3OH), which suggests
that solvent molecules may participate in O2 reduction
directly.63
7.3. Need for Benchmark Catalytic Measurements.
Experimental studies should provide benchmark measurements
of H2O2 formation rates and selectivities at common conditions
(and upon a standard catalyst).73 A survey of the literature on
direct synthesis shows the difficulty in making direct
comparisons between publications and transferring knowledge
from one study to the next. These difficulties are caused by the
variability in methods for catalytic evaluation among different
groups and catalytically significant (yet quantitatively small)
differences between composition and concentrations of the
additives and solvents used. Researchers in direct synthesis of
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ACS Catalysis
H2O2 should agree upon the use of a standard catalyst and
solvent composition for benchmark measurements to be
included in new investigations. Control experiments in our
own laboratory demonstrate that intraparticle diffusion of
reactant gases and product H2O2 influence catalytic measure-
ments obtained on Pd nanoparticle catalysts with loadings
greater than 0.05% wt on silica particles (0.25−0.5 mm in
diameter). Inadvertently, we have learned that exposure of
stainless steel reactors to halide salts or mineral acid promoters
irreversibly corrupts all catalytic measurements obtained within
the same reactor for a period of months, presumably due to
corrosion of metal from the reactor walls. These same
phenomena may affect also catalytic data from other groups.
Within our laboratory, we now measure H2O2 formation
rates (0.02 (mol H2O2) (mol PdS s)−1), selectivities (20%), and
activation enthalpies (−8 ± 3 kJ mol−1) on Pd-SiO2 catalysts
(<1 nm Pd nanoparticles; 0.05% wt Pd on Davisil 646, 60 kPa
H2, 60 kPa O2, 277 K) within pure methanol to validate new
reactors, benchmark catalysts, and train researchers (see
citation for details of catalyst synthesis and testing).4,37 High
purity methanol, without halides or acids promoters, appears to
be the most suitable solvent for these benchmark measure-
ments, because it does not introduce possible contamination
and H2O2−methanol solutions are industrially relevant for
applications such as alkene epoxidation (e.g., in the hydrogen
peroxide−propylene oxide process).24
8. SUMMARY
Successful implementation of the direct synthesis of H2O2 (and
the resultant inexpensive H2O2) would decrease the environ-
mental impact of industrial oxidation reactions and could
enable a number of ground-breaking processes (e.g., selective
oxidations of alkanes to alcohols). The greatest barriers that
stand in the way of implementation stem from outstanding
scientific challenges. Namely, the combinations of solvents and
promoters that provide high selectivities to H2O2 on Pd
catalysts (and Pd-based bimetallic catalysts) also decrease the
stability of those catalysts by increasing rates of Pd dissolution
and leaching. Current understanding of this presumably simple
reaction between small molecules (H2 and O2) on nanoparticle
surfaces is surprisingly limited. Consequently, the pathway to
develop new combinations of solvents and promoters that may
provide both selective and stable catalysts is uncertain. Further
progress in understanding this deceptively intricate chemistry
will require rigorous studies that combine kinetic, spectro-
scopic, and computational methods and which develop
quantitative descriptions of how the many components of the
system influence intrinsic kinetic parameters and reaction
mechanisms. To do so, researchers will need to embrace the
complexity of this reaction and consider that Pd nanoparticles
are only one part of the complete catalytic system that produces
H2O2 selectively.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: (217) 244-2816. E-mail: dwflhrty@illinois.edu.
ORCID
David W. Flaherty: 0000-0002-0567-8481
Notes
The author declares no competing financial interest.
1526
Viewpoint
■ ACKNOWLEDGMENTS
DWF acknowledges helpful discussions with Neil M. Wilson,
Pranjali Priyadarshini, Jason S. Adams, and Matthew Neurock.
Financial support for this work was provided by a research
grant from the National Science Foundation (CBET-
15531377) and the Energy Biosciences Institute funded by
Royal Dutch Shell.
■
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