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Contributed by James A. Dumesic, February 24, 2016 (sent for review August 18, 2015; reviewed by Alexis T. Bell and Jens K. Nørskov)
A combination of periodic, self-consistent density functional theory are also thermodynamically favorable reactions. The optimal
(DFT-GGA-PW91) calculations, reaction kinetics experiments on a DSHP catalyst must therefore selectively produce H2O2 at high
SiO2-supported Pd catalyst, and mean-field microkinetic modeling rates and preserve H2O2 from decomposition.
are used to probe key aspects of H2O2 decomposition on Pd in the Pd is widely recognized as the most effective transition metal
absence of cofeeding H2. We conclude that both Pd(111) and for the DSHP; however, Pd generally exhibits poor selectivity in
OH-partially covered Pd(100) surfaces represent the nature of the the absence of promoters and is highly active for the H2O2 de-
active site for H2O2 decomposition on the supported Pd catalyst composition reactions. Experimental strategies to improve se-
reasonably well. Furthermore, all reaction flux in the closed catalytic lectivity of Pd-based catalysts include the following (8, 9): adding
cycle is predicted to flow through an O–O bond scission step in either strongly coordinating anions (e.g., CN−, Cl−, Br−) and acids to
H2O2 or OOH, followed by rapid H-transfer steps to produce the the solvent; alloying Pd with other noble metals, namely Au or
H2O and O2 products. The barrier for O–O bond scission is sensitive Pt; and controlling the nature of the catalyst support material.
to Pd surface structure and is concluded to be the central param- The performance of Pd-based catalysts has also been shown to
eter governing H2O2 decomposition activity.
strongly depend on the oxidation state of Pd (i.e., catalyst pre-
CHEMISTRY
treatment conditions, O2:H2 feed ratio, etc.) (8).
|
catalysis density functional theory | hydrogen peroxide | palladium | A common goal in many of these modifications is the minimi-
microkinetic analysis
zation of the H2O2 decomposition reactions (reactions 3 and 4)
(10). Importantly, H2O2 has been identified as the primary
H ydrogen peroxide (H2O2) is a desirable oxidant because the
only by-product from its reduction is water (1). The largest
demand for H2O2 is in the pulp and paper industry (2). In addition,
product on Au-Pd catalysts at low H2 conversion (11, 12), whereas
the subsequent H2O2 decomposition reactions decrease overall
yield as the reaction progresses. Experiments also suggest that the
there are applications for H2O2 in catalytic oxidations (3) such as the active sites for H2O2 synthesis (reaction 1) and decomposition on
epoxidation of propene to propylene oxide (4). However, the current Pd-based catalysts may be different (12, 13). In particular, Hutchings
production process for H2O2, the anthraquinone process, is complex,
and coworkers (14) demonstrated that the H2O2 decomposition
energy intensive, and only economic for large-scale productions (5).
reactions on a Au-Pd/C catalyst could be suppressed by pretreating
The direct synthesis of hydrogen peroxide (DSHP) from H2
the carbon support with HNO3, and this resulted in a stable catalyst
and O2 is an appealing alternative that has the potential to enable
with >95% selectivity for H2O2 during the DSHP reaction. A de-
small-scale integrated production of H2O2 (5). A commercial tailed understanding of the active site(s) and elementary reaction
DSHP process has not yet been implemented, although Degussa/ mechanisms for these undesired reactions would benefit the identi-
Headwaters announced the successful integration of a pilot plant fication of improved catalysts. Nonetheless, there is still much work
for the DSHP and a pilot plant for the manufacture of propylene to be performed to elucidate the optimal structure and composition
oxide in 2005 (6). García-Serna et al. (7) have discussed the
economic viability of a DSHP process in comparison with the Significance
existing industrial-scale anthraquinone process.
The primary catalytic challenge for the DSHP is identifying cat- The use of hydrogen peroxide (H2O2) for catalytic oxidations is
alysts that can maintain high selectivity for H2O2 at industrially rel- limited by the energy-intensive and wasteful process by which
evant H2O2 concentrations. The complete reduction of O2 to H2O is H2O2 is currently produced—the anthraquinone process. The
more thermodynamically favorable than the partial reduction of O2 direct synthesis of H2O2 (DSHP) is a promising alternative pro-
to H2O2: cess, yet catalysts active for this reaction (Pd being the most
widely studied) are generally hindered by subsequent H2O2 de-
H2 ðgÞ + O2 ðgÞ → H2 O2 ð1Þ ΔG°298K = −120.4 kJ=mol, composition. Through a combined theoretical and experimental
[Reaction 1; approach, our work (i) provides an understanding of the nature
of Pd active sites responsible for H2O2 decomposition and (ii)
H2 ðgÞ + O2 ðgÞ → H2 Oð1Þ + 1/ 2O2 ðgÞ ΔG°298K = −237.1 kJ=mol, identifies a single type of elementary step that controls the rate.
These structural and mechanistic insights are important for de-
[Reaction 2: signing improved DSHP catalysts and for developing transition-
metal–catalyzed oxidations that efficiently use H2O2.
Consequently, H2O2 decomposition,
Author contributions: A.P., E.E.S., J.A.D., and M.M. designed research; A.P. performed
H2 O2 ð1Þ → H2 Oð1Þ + 1/ 2O2 ðgÞ ΔG°298K = −116.7 kJ=mol, research; A.P., J.A.D., and M.M. analyzed data; and A.P., E.E.S., J.A.D., and M.M. wrote
the paper.
[Reaction 3; Reviewers: A.T.B., University of California, Berkeley; and J.K.N., Stanford University.
The authors declare no conflict of interest.
and H2O2 hydrogenation by H2, 1
To whom correspondence may be addressed. Email: jdumesic@wisc.edu or emavrikakis@
wisc.edu.
H2 O2 ð1Þ + H2 ðgÞ → 2H2 Oð1Þ ΔG°298K = −353.8 kJ=mol,
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.
[Reaction 4; 1073/pnas.1602172113/-/DCSupplemental.
CHEMISTRY
The binding energies of H2O* and H2O2* are weak (<0.4 eV)
on both Pd(111) and Pd(100). H2O* preferentially binds to top
Thermochemistry and Binding Configurations of Reaction Intermediates
sites on both Pd(111) and Pd(100) with the O–H bonds parallel
on Clean Pd Surfaces. Table 1 summarizes the most stable adsorption
to the Pd surface. The binding energy of H2O* on Pd(100) is
sites and binding energies for all surface species on Pd(111) and
−0.30 eV. H2O2* also preferentially binds to top sites and adopts
Pd(100). Images of the individual adsorbates in their preferred
the trans configuration on both Pd facets; one oxygen atom is
binding geometry on Pd(100) can be viewed in Fig. 1; refer to ref. 33
bound to a top site with its hydrogen atom pointing slightly away
for the corresponding images on Pd(111). The Pd(100) facet is more
from the surface plane, and the other oxygen atom is positioned
open than the Pd(111) one and binds all intermediates more strongly.
over an adjacent (fcc or hollow) site with its hydrogen atom
The BE of atomic hydrogen (H*) on Pd(100) is −2.74 eV, only
pointing toward the surface.
0.04 eV stronger than its BE on Pd(111). H* preferentially binds Other potential intermediates include aquoxyl (OOHH*, an
to the fcc site on Pd(111) and the hollow site on Pd(100). Fur- isomer of H2O2* with both hydrogen atoms on the same oxygen
thermore, H* is expected to be mobile on Pd(100), as the BE of atom) and trihydrogen peroxide (HOOHH*). Similar to our
H* on a bridge site of Pd(100) is only 0.14 eV less stable than findings on Pd(111) (33), neither of these species is stable on
that on the hollow site. Similarly, on Pd(111), the BE of H* con- Pd(100), i.e., adsorption of aquoxyl and trihydrogen peroxide
strained to a bridge site is 0.14 eV less stable than that on the fcc site. structures on Pd(100) results in spontaneous decomposition to
Atomic oxygen (O*) has the same site preferences as H* on (O* + H2O*) and (OH* + H2O*), respectively.
both Pd(111) and Pd(100). The binding strength of O* on Pd(100) Table 1 provides the calculated O–O bond lengths for the
is −3.90 eV, which is 0.26 eV stronger than that on Pd(111). adsorbed dioxygen species (O2*, OOH*, and H2O2*) and the
Moreover, O* has a strong preference for the hollow site on corresponding values calculated in the gas phase. There is sig-
Pd(100), with the next best adsorption site (bridge) being less nificant expansion of the O–O bond in both O2* and OOH*
stable by 0.48 eV. On Pd(111), the next best adsorption site for upon adsorption, whereas the O–O bond length in H2O2* re-
O* is the hcp site, which is 0.15 eV less stable than O* binding to mains within 2% of its calculated gas-phase value. The larger
the fcc site. O–O bond expansion on Pd(100) compared with Pd(111) suggests
Hydroxyl (OH*) is often proposed to be the initial interme- a weaker O–O bond strength on the more open surface for all of
diate generated during H2O2 decomposition, resulting from the dioxygen species.
homolytic O–O bond cleavage in H2O2 (55). OH* binds most
stably to the bridge site on both Pd(111) and Pd(100) with the Activation Energy Barriers of Elementary Steps. The calculated ac-
O–H bond tilted away from the plane perpendicular to the sur- tivation energy barriers (Ea) and reaction energies (ΔE) are
face. The BE of OH* on Pd(100) is −2.43 eV, which is 0.40 eV reported with respect to reactant and product states at infinite
stronger than the BE on Pd(111). OH* binding at the hollow site
of Pd(100) is only 0.05 eV weaker than on the bridge site, which is
similar to the difference in energy between OH* binding at the fcc
site and bridge site on Pd(111) (0.08 eV).
Hydroperoxyl (OOH*) is considered an important intermediate
in the DSHP and was identified spectroscopically during the gas-
phase reaction of H2 and O2 on Au/TiO2 using inelastic neutron
scattering (56). OOH* binds through its nonhydrogenated oxy-
gen atom to a top site on Pd(111) with the hydroxyl group po-
sitioned over an adjacent bridge site and the O–H bond pointing
away from the surface, whereas OOH* binds through its non-
hydrogenated oxygen atom to a bridge site on Pd(100) with the Fig. 1. (A–G) Side and top-down views of the preferred binding sites for all
hydroxyl group positioned over an adjacent hollow site and the adsorbates on Pd(100). Blue spheres are hydrogen, red spheres are oxygen,
O–H bond pointing away from the surface. The binding energy and gray spheres are Pd atoms.
Energetics are reported with respect to either reactants/products at infinite separation (steps 1–11) or
coadsorbed for H-transfer reactions (steps 12–17) because these reactants/products are generally stabilized
through hydrogen bonding. Elementary steps are classified as follows: adsorption/desorption (steps 1–4);
O–O scission (steps 5–7); dehydrogenation (steps 8–11); and H transfer (steps 12–17). Ea and ΔE represent
the calculated activation energy and reaction energy in the forward direction. —, no activation barriers
are calculated for adsorption/desorption steps.
†
Data for steps 1–12 on Pd(111) are based on ref. 33.
‡
Activation energy corresponds to breaking Pd–O bonds to lift O* from its preferred binding site (fcc or
fourfold hollow).
CHEMISTRY
Pd–O bonds to lift O* from its preferred binding site, followed by spontaneous H transfer from H2O2* to O*.
and has a barrier of 1.03 eV on Pd(100), and the reaction is slightly tential pathways for formation of both the H2O (H transfers to
endothermic. The transition state for O–H cleavage in both H2O* O*/OH*) and O2 (H transfers from H2O2*/OOH*, retaining the
and OH* occurs over a hollow site on Pd(100). O–O bond) products of H2O2 decomposition.
Hydrogen transfer. Formation and cleavage of O–H bonds in which H transfer to O. H2O2*, OOH*, and H2O* can all directly transfer
the Pd surface is directly involved have significant activation a H atom to O*; the activation energy barriers for these steps are
barriers (>0.4 eV). Alternatively, the Pd surface can mediate H 0.04, 0.00, and 0.33 eV on Pd(111), with reaction energies of
transfer between oxygenated intermediates—without involving −0.44, −0.27, and 0.33 eV. The corresponding activation energy
an explicit H* species. These elementary steps involve nearly barriers on Pd(100) are 0.14, 0.02, and 0.00 eV with significantly
spontaneous H transfer in the exothermic direction on both more exothermic reaction energies of −0.87, −0.81, and −0.51 eV.
Pd(111) and Pd(100) (Table 2). The activation energy barriers H transfer to OH. H2O2* and OOH* can also directly transfer a
and reaction energies in this section are reported with respect to H atom to OH*. We calculate that these steps proceed with
coadsorbed reactant and product states, because these states are nearly zero activation energy barrier on Pd(111) and Pd(100).
generally stabilized through hydrogen bonding (∼0.1–0.4 eV per The reaction energy for H transfer from H2O2* to OH* is weakly
hydrogen bond) with respect to the infinitely separated reactants exothermic [−0.16 eV on Pd(111) and −0.17 eV on Pd(100)].
and products. The reaction energy for H transfer from OOH* to OH* is more
The hydrogen atom is always transferred between O atoms exothermic on Pd(111) (−0.38 eV) than that on Pd(100) (−0.13 eV).
involved in hydrogen bonding in the most stable coadsorbed An additional H-transfer step that was explored is H transfer
configuration. Importantly, the H-transfer steps represent po- from H2O2* to O2*. This reaction is nearly thermoneutral on
Fig. 3. Schematic representation of reaction pathways for H2O2 decomposition on clean surfaces. The numbers by the black arrows correspond to the el-
ementary steps from Table 2. The overall reaction for each of the three complete mechanisms described in this figure is as follows: 2 H2O2 → 2 H2O + O2.
Pd(111), with a reaction energy of −0.02 eV and an activation studies of H2O2 decomposition on Pd under similar conditions of
energy barrier of 0.20 eV. On Pd(100), the reaction is thermo- temperature and H2O2 concentration (13, 65). We also observed
neutral with negligible barrier. that the addition of O2 to the gas phase did not significantly
affect the decomposition rate of H2O2 up to O2 partial pressures
Catalytic Cycles and Potential Energy Surfaces. Based on the ele- of at least 37 psi, indicating negligible product inhibition over the
mentary steps above, several mechanisms are available to com- conditions studied. This finding is in agreement with the result of
plete the catalytic cycle on clean Pd facets, as summarized in Fig. Choudhary and Samanta (66), who observed only a minor dif-
3: “O*-assisted,” “OH*-assisted,” “O*+O*-recombination,” and ference in the reaction rate for H 2 O 2 decomposition over
“direct dehydrogenation.” A complete mechanism for direct Pd/Al2O3 (in the absence of H2) in a semibatch reactor when
dehydrogenation is not shown for simplicity, as both the DFT flowing either O2 or N2 through the liquid phase.
calculations and microkinetic modeling results suggest that direct Initial estimates for microkinetic model rate parameters are de-
dehydrogenation steps are characterized by much higher barriers rived from the DFT-calculated energetics. The reactor is simulated
and therefore not relevant under the reaction conditions explored as a continuous stirred tank reactor. The turnover frequencies for
in this study. The first step in all other pathways is H2O2 ad- H2O2 decomposition obtained from this model (i.e., the rate of
sorption followed by homolytic O–O bond cleavage to form two H2O2 converted per surface site) are used to calculate reaction
OH* species. The second H2O2* species can also adsorb and orders and apparent activation barrier for comparison with the
directly decompose to two OH*; these OH* species can then experimental data.
disproportionate to form H 2O* and O*—necessitating the The rates, reaction orders, and apparent activation barriers
recombination of two O* to form O2* (O*+O*-recombination predicted by the microkinetic model were initially in poor agree-
mechanism). Alternatively, two channels exist that bypass the ment with the experimental data when using purely DFT-derived
thermodynamically unfavorable and highly activated O* recom- parameters from Pd(111) or Pd(100). We subsequently used
bination step; both involve consecutive H-transfer steps from sensitivity analysis to identify the sensitive DFT-derived BEs of
the second H2O2 molecule to the O*/OH* fragments with re- surface species and transition-state energies. We then fit model-
tention of the original O–O bond in H 2O 2 (O*-assisted and predicted reaction rates to experimental rates (such that the re-
OH*-assisted mechanisms). sidual error is less than 20%) by modifying sensitive parameters,
The potential energy surfaces for all pathways are displayed in
Fig. 4 for both Pd(111) and Pd(100). Based on the DFT calcu-
lations alone, the O*-assisted and OH*-assisted pathways not Table 3. Reaction rates obtained from the kinetics experiments
only provide the most energetically efficient route to form the on Pd/spSiO2
products, but are also mutually competitive on both Pd(111)
Experimental rate,
and Pd(100). However, the deep potential wells associated
Run† Temperature, K y(O2) x(H2O2) mol·molPds−1·s−1
with the strongly bound O*/OH* fragments indicate that there
is a strong thermodynamic driving force to populate the surfaces 1 307 0.00 0.60 71.8
with O*/OH*—especially Pd(100). Therefore, the active surface 2 307 0.00 0.30 31.5
under reaction conditions may be partially covered by O*/OH*. 3 307 0.00 0.15 17.1
Note that on O*/OH*-modified surfaces, there is an increased 4 307 0.00 0.08 10.5
probability of H transfer from H2O2* before O–O bond scission; 5 297 0.00 0.15 7.9
the required O–O bond scission step may then occur in OOH* 6 285 0.00 0.15 3.4
rather than in H2O2*, slightly altering the succession of ele- 7 307 0.25 0.15 16.7
mentary steps proposed in Fig. 3. 8 307 0.13 0.15 16.2
9 307 0.06 0.15 16.9
Kinetics Experiments and Microkinetic Modeling. The results from †
our kinetics experiments are shown in Tables 3 and 4. The ex- y denotes mole fraction in the gas phase (balance Ar), and x denotes molarity
(moles per liter) in the liquid phase at the start of reaction. Pds denotes surface
perimentally determined activation energy barrier of 53.3 ± Pd atoms determined by CO uptake. Total pressure was 150 psi, and the stir rate
3.0 kJ/mol indicates that there is a significant variation in H2O2 was 1,200 rpm for all experiments. Reaction rates reported here correspond to
decomposition rate with reaction temperature under conditions the initial rates measured from conversion versus time data at <15% conversion,
relevant to the DSHP. The nearly first-order dependence on which was approximately linear in this regime. Each reported rate represents
concentration of H2O2 is in agreement with other experimental the average from at least two repeated sets of conversion versus time data.
where ki and Ki,eq are the rate constant and equilibrium constant
for step i, and r is the overall reaction rate. O–O bond scission in
Fig. 5. (A and C ) Parity plots of experimental and model-predicted re-
H2O2* (step 5 of Table 2) carries the highest degree of rate
action rates for H2O2 decomposition. Refer to Table 3 for reaction condi-
control over the reaction conditions examined, shown in Table
CHEMISTRY
tions at each of the points in A and C. Pds denotes surface Pd atoms
determined by CO uptake. Red points are varying temperature; blue points 5; the remaining rate control is distributed between the subse-
are varying O2 partial pressure; black points are varying feed concentra- quent H-transfer reactions.
tion of H2O2. (B and D) Microkinetic model-predicted surface coverages of OH*-coverage solution. Using the DFT calculations on clean Pd(100)
the most abundant surface intermediates (0.15 M H2O2 in H2O feed with to derive initial estimates of parameters, a second solution was
150 psi Ar in gas phase). Plots on the Left refer to the O*-coverage solu- identified that also gave agreement with the experimental data set
tion, and plots on the Right refer to the OH*-coverage solution obtained (Fig. 5C and Table 4). In this case, the model-predicted surface
from the microkinetic model. Insets in B and D provide graphical repre- coverage is ∼0.5 ML of OH* (Fig. 5D) and is therefore not self-
sentations of the nature of the active sites as concluded through this study
consistent with the clean Pd(111) and Pd(100) surface models used
[nearly clean Pd(111) and OH*-modified Pd(100)]. Blue spheres are hy-
drogen, red spheres are oxygen, and gray spheres are Pd atoms.
in the DFT calculations. To ensure a solution self-consistent in
coverage, we recalculated the binding energies of surface inter-
mediates and the activation energy barriers for steps carrying sig-
constraining the adjustment of parameters such that (i) the de- nificant reaction flux (as predicted by the OH*-coverage solution)
viation between DFT-derived BEs and activation barriers on a in the presence of 0.5 ML of OH* spectators, i.e., two OH* were
given Pd facet and the corresponding values from the microkinetic added to the unit cell and allowed to relax in the DFT calculations.
model should be within the ∼0.1- to 0.2-eV error bars generally The DFT-derived parameter set for the OH*-modified
attributed to DFT calculations (67), and (ii) the adsorbate cov- Pd(100) surface is found to be in close agreement with the adjusted
erage used in the DFT calculations should be consistent with the parameter set from the OH*-coverage solution (BEs shown in
coverage predicted by the microkinetic model (that is, the solution Table 6, with further details in Supporting Information). The DFT
should be self-consistent with respect to coverage). calculations show that 0.5 ML of OH* destabilizes most inter-
Next, we present the results from two model solutions that mediates and transition states investigated on Pd(100) relative to
satisfy the above criteria, but differ in both the coverage and identity the clean Pd(100) calculations. The binding energies of O*,
of the most abundant surface intermediate, and are denoted as the OH*, O2*, and OOH* are weakened by >0.5 eV, whereas the
“O*-coverage solution” and the “OH*-coverage solution.” binding energies of H*, H2O*, and H2O2* are not significantly
O*-coverage solution. Fig. 5A shows a parity plot comparing the affected. In addition, the activation energy barriers for O–O
experimental H2O2 decomposition rates with the microkinetic bond breaking in OOH* and H2O2* increase by 0.39 and 0.56 eV,
model predictions for the O*-coverage solution [initial estimates respectively. Activation energy barriers for H transfer from
of parameters are derived from DFT calculations on clean H2O2* or OOH* to OH* or O* remain small (<0.2 eV). The
Pd(111), and Supporting Information provides details of the pa- maximum deviation in binding energy or activation barrier be-
rameter adjustments used to obtain this solution]. There is good tween the OH*-coverage solution and DFT calculations on
agreement between model-predicted and experimental reaction OH*-modified Pd(100) is a 0.18-eV decrease in the activation
rates, and the microkinetic model is able to accurately reproduce
the experimental activation barrier and reaction orders (Table 4).
The microkinetic model predictions for the surface coverage Table 4. Experimental and microkinetic model-predicted
for the most abundant intermediate, O*, range from 0.13 to reaction orders and apparent activation energy barriers (Eapp)
0.16 ML (Fig. 5B), with the remaining sites being vacant. Mar- O*-coverage OH*-coverage
ginal changes to the clean surface energetics are expected from Species Experiment† solution solution
adsorbate–adsorbate interactions at such low O* coverage (68),
and furthermore this adjusted parameter set compares well with H2O2 0.92 ± 0.08 1.00 0.97
the DFT-derived parameters on clean Pd(111); the maximum O2 −0.01 ± 0.03 −0.01 0.00
deviation in binding energy or activation barrier is a 0.24 eV Eapp, kJ/mol 53.3 ± 3.0 53.1 56.6
destabilization of the binding energy of O2* on Pd(111). Reported experimental error is the SE from linear regression.
Therefore, a partially O*-covered Pd(111) surface is a plausible †
Subsequent catalyst batches yielded reaction orders and an apparent bar-
representation of the active site for H2O2 decomposition. rier within ∼15% of the values reported here.
explanations addressing the role of H2 have been proposed, adjusted parameters are consistent with the DFT-derived pa-
such as maintaining the Pd surface in the reduced state (59) for rameters on a Pd(100) surface with OH* spectators. Therefore,
facile O–O bond breaking. Additionally, direct hydrogenation the microkinetic model suggests that both Pd(111) and Pd(100)
of H2O2 was shown to be a highly activated step using DFT cal- can contribute to H2O2 decomposition activity. Experimental
culations (86). The influence of subsurface hydrogen or even identification of dominant surface species during H2O2 de-
Pd-hydrides may also be relevant (87). The next stage of this work composition on Pd might be realized by in situ X-ray photo-
is to investigate the mechanistic role of H2 in accelerating H2O2 electron spectroscopy measurements in a similar manner to work
decomposition on Pd, in addition to probing the nature of the performed on Pt for the oxygen reduction reaction (88).
active site(s) in the presence of H2. Consistent with the insights from DFT calculations, the domi-
Conclusions nant reaction pathways involve O–O bond breaking in either
H2O2* or OOH* followed by H-transfer reactions between vari-
Both the close-packed (111) and more open (100) facets can
represent the active site for SiO2-supported Pd nanoparticles. The ous reaction intermediates. Breaking of the O–O bond is identi-
DFT results show that O–O bond scission is facile on both Pd fied as the key parameter governing H2O2 decomposition activity,
facets, such that O* and OH* intermediates are readily produced. because this step carries the highest degree of rate control.
Furthermore, H2O2* and OOH* can reduce O* and OH* to H2O
ACKNOWLEDGMENTS. A.P. thanks Assistant Professor Fuat E. Celik for his
CHEMISTRY
through thermodynamically driven H-transfer reactions, liberating initial guidance with the density functional theory calculations, as well as
O2. The alternative step to produce O2 (recombination of O*) is Yunhai Bai and Benjamin Chen for their comments on the article. This material
both thermodynamically and kinetically unfavorable. In addition, is based on work supported as part of a Dow Chemical Company University
steps involving dehydrogenation through direct O–H bond Partner Initiative with the University of Wisconsin–Madison, under Dow Agree-
ment 235744C. Computational time was used at supercomputing resources
cleavage over Pd are less favored than the H-transfer steps. located at Environmental Molecular Sciences Laboratory (EMSL), a national
Microkinetic models based on two parameter sets are able to scientific user facility at Pacific Northwest National Laboratory (PNNL); the
describe the experimental data for a SiO2-supported Pd catalyst: Center for Nanoscale Materials (CNM) at Argonne National Laboratory (ANL);
the first set corresponds to a Pd surface partially covered in <0.2 and the National Energy Research Scientific Computing Center (NERSC). EMSL is
sponsored by the Department of Energy’s Office of Biological and Environmental
ML of O*, and these adjusted parameters are consistent with the Research located at PNNL. CNM and NERSC are supported by the US Department
DFT-derived parameters on clean Pd(111); the second set cor- of Energy, Office of Science, under Contracts DE-AC02-06CH11357 and DE-AC02-
responds to a Pd surface covered in ∼0.5 ML of OH*, and these 05CH11231, respectively.
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