Dataset Information

DFT Study of the BH₄ ^- Hydrolysis on Au(111) Surface.

ABSTRACT: The mechanism of the catalytic hydrolysis of BH₄ ^- on Au(111) as studied by DFT is reported. The results are compared to the analogous process on Ag(111) that was recently reported. It is found that the borohydride species are adsorbed stronger on the Au⁰ -NP surface than on the Ag⁰ -NP surface. The electron affinity of the Au is larger than that of Ag. The results indicate that only two steps of hydrolysis are happening on the Au(111) surface and the reaction mechanism differs significantly from that on the Ag(111) surface. These remarkable results were experimentally verified. Upon hydrolysis, only three hydrogens of BH₄ ^- are transferred to the Au surface, not all four, and H₂ generation is enhanced in the presence of surface H atoms. Thus, it is proposed that the BH₄ ^- hydrolysis and reduction mechanisms catalyzed by M⁰ -NPs depend considerably on the nature of the metal.

SUBMITTER: Raju Karimadom B

PROVIDER: S-EPMC9400865 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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DFT Study of the BH4 - Hydrolysis on Au(111) Surface.

Raju Karimadom Basil B Varshney Shalaka S Zidki Tomer T Meyerstein Dan D Kornweitz Haya H

Chemphyschem : a European journal of chemical physics and physical chemistry 20220517 13

The mechanism of the catalytic hydrolysis of BH4 - on Au(111) as studied by DFT is reported. The results are compared to the analogous process on Ag(111) that was recently reported. It is found that the borohydride species are adsorbed stronger on the Au0 -NP surface than on the Ag0 -NP surface. The electron affinity of the Au is larger than that of Ag. The results indicate that only two steps of hydrolysis are happening on the Au(111) surface and the ...[more]

PMID: 35403783

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Project description: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 (H2) + Cu(111), deuterium (D2) + Ag(111), H2 + Au(111), and D2 + 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 D2 + Ag(111) and D2 + 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 H2 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 H2 (D2) interacting with late transition metals.

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DFT Study of the BH₄ ^- Hydrolysis on Au(111) Surface.

Publications

DFT Study of the BH<sub>4</sub> <sup>-</sup> Hydrolysis on Au(111) Surface.

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