The kinetics of elementary thermal reactions in heterogeneous catalysis

Park, G. Barratt; Kitsopoulos, Theofanis N.; Borodin, D.; Golibrzuch, Kai; Neugebohren, Jannis; Auerbach, Daniel J.; Campbell, Charles T.; Wodtke, Alec M.

doi:10.1038/s41570-019-0138-7

Cited by 40 publications

(30 citation statements)

References 51 publications

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“…To obtain information on the reaction rate, we used the recently developed velocity resolved kinetics technique [39,40,42]. Two differentially pumped molecular beams delivered short pulses of O 2 and H 2 to the surface of a Pt(111) crystal, which was cleaned by Ar + sputtering and annealed to recover surface order.…”

Section: Methodsmentioning

confidence: 99%

“…One reason is the lack of high temporal resolution kinetic data from which the influence of the individual reaction steps might be observed. In this paper, we provide such data using the newly developed velocity resolved kinetics technique [39,40]. The observable in our measurements is the time dependent flux of water, a quantity that is identical to the instantaneous rate of water production.…”

Section: Introductionmentioning

confidence: 99%

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The puzzle of rapid hydrogen oxidation on Pt(111)

et al. 2021

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We have known for over 200 years that hydrogen undergoes rapid oxidation to water on Pt catalysts; yet the reaction mechanism remains unclear. Here, we report high temporal resolution measurements of the production rate of H 2 O from hydrogen oxidation catalysed by a Pt (111) single crystal surface with a known concentration of adsorbed oxygen atoms and a step density of approximately 0.002 ML. We obtain two rate constants describing the rise, and fall of the reaction rate between 350 and 470 K and compare our observations to modern ab initio predictions of the reaction rates in surface chemistry. Remarkably, a mechanism based on a standard set of elementary reaction steps with energies and barrier heights obtained from Density Functional Theory (DFT), predicts a rate that is four orders of magnitude smaller than observed experimentally. Furthermore, the theoretically predicted reaction rate follows first-order kinetics, whereas the experimental observations clearly show a second-order reaction. The theoretical predictions are robust -six different exchange-correlation functionals lead to similar predictions. We suggest that the reason for these disagreements is that the active sites of the catalyst and the associated elementary reactions have, so far, not been properly identified.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The puzzle of rapid hydrogen oxidation on Pt(111)

et al. 2021

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“…There are several excellent recent reviews and perspective papers that are related to the broader field of scattering of molecules from metal surfaces at the gas solid interface. Topics addressed include DFT for surface chemistry and catalysis, 11 kinetics of chemical reactions at gas-surface interfaces 41 and in heterogeneous catalysis, with emphasis on a new powerful pump-probe technique, 256 surface catalysis modeling, 257 reactive and non-reactive scattering of H 2 from metal surfaces, 28 O 2 activation by metal surfaces, 258 dissociation dynamics of methane on TM surfaces, 259 energetics and dynamics of methane and water dissociation on transition metal surfaces, 260 quantum state-resolved studies of chemisorption reactions, 261,262 electronically non-adiabatic effects in surface chemistry and dynamics [263][264][265][266] and how to address these effects, 255,267 effects of surface atom motion on dissociation reactions, 30,266 mode-specificity and bond-selectivity in QD descriptions of reactions of polyatomic molecules on metals, 29 and how experiments can test central assumptions made in theory applied to the dynamics of molecular interactions and chemical reactions at metal surfaces. 268 A recent theoretical perspective on the dynamics of reactions on metal surfaces was published by Jiang and Guo.…”

Section: Introductionmentioning

confidence: 99%

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

Kroes

2021

Phys. Chem. Chem. Phys.

167

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“… 6 − 8 Calculating chemically accurate barrier heights 9 for rate-controlling reactions to obtain accurate rates of the overall reaction network 10 potentially has a large financial impact on the chemical industry since it allows theoretical screening for more efficient catalysts. 11 …”

Section: Introductionmentioning

confidence: 99%

Performance of Made Simple Meta-GGA Functionals with rVV10 Nonlocal Correlation for H₂ + Cu(111), D₂ + Ag(111), H₂ + Au(111), and D₂ + Pt(111)

Smeets

Kroes

2021

J. Phys. Chem. C

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Accurately modeling heterogeneous catalysis requires accurate descriptions of rate-controlling elementary reactions of molecules on metal surfaces, but standard density functionals (DFs) are not accurate enough for this. The problem can be solved with the specific reaction parameter approach to density functional theory (SRP-DFT), but the transferability of SRP DFs among chemically related systems is limited. We combine the MS-PBEl, MS-B86bl, and MS-RPBEl semilocal made simple (MS) meta-generalized gradient approximation (GGA) (mGGA) DFs with rVV10 nonlocal correlation, and we evaluate their performance for the hydrogen (H 2 ) + Cu(111), deuterium (D 2 ) + Ag(111), H 2 + Au(111), and D 2 + Pt(111) gas-surface systems. The three MS mGGA DFs that have been combined with rVV10 nonlocal correlation were not fitted to reproduce particular experiments, nor has the b parameter present in rVV10 been reoptimized. Of the three DFs obtained the MS-PBEl-rVV10 DF yields an excellent description of van der Waals well geometries. The three original MS mGGA DFs gave a highly accurate description of the metals, which was comparable in quality to that obtained with the PBEsol DF. Here, we find that combining the three original MS mGGA DFs with rVV10 nonlocal correlation comes at the cost of a slightly less accurate description of the metal. However, the description of the metal obtained in this way is still better than the descriptions obtained with SRP DFs specifically optimized for individual systems. Using the Born–Oppenheimer static surface (BOSS) model, simulations of molecular beam dissociative chemisorption experiments yield chemical accuracy for the D 2 + Ag(111) and D 2 + Pt(111) systems. A comparison between calculated and measured E 1/2 (ν, J ) parameters describing associative desorption suggests chemical accuracy for the associative desorption of H 2 from Au(111) as well. Our results suggest that ascending Jacob’s ladder to the mGGA rung yields increasingly more accurate results for gas-surface reactions of H 2 (D 2 ) interacting with late transition metals.

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The kinetics of elementary thermal reactions in heterogeneous catalysis

Cited by 40 publications

References 51 publications

The puzzle of rapid hydrogen oxidation on Pt(111)

The puzzle of rapid hydrogen oxidation on Pt(111)

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

Performance of Made Simple Meta-GGA Functionals with rVV10 Nonlocal Correlation for H₂ + Cu(111), D₂ + Ag(111), H₂ + Au(111), and D₂ + Pt(111)

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The kinetics of elementary thermal reactions in heterogeneous catalysis

Cited by 40 publications

References 51 publications

The puzzle of rapid hydrogen oxidation on Pt(111)

The puzzle of rapid hydrogen oxidation on Pt(111)

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

Performance of Made Simple Meta-GGA Functionals with rVV10 Nonlocal Correlation for H2 + Cu(111), D2 + Ag(111), H2 + Au(111), and D2 + Pt(111)

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Performance of Made Simple Meta-GGA Functionals with rVV10 Nonlocal Correlation for H₂ + Cu(111), D₂ + Ag(111), H₂ + Au(111), and D₂ + Pt(111)