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Subsurface oxide plays a critical role in CO₂ activation by Cu(111) surfaces to form chemisorbed CO₂, the first step in reduction of CO₂.

ABSTRACT: A national priority is to convert CO₂ into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO₂ electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO₂ in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO₂ in the presence of water as the first step toward CO₂ reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

SUBMITTER: Favaro M

PROVIDER: S-EPMC5495248 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

Favaro Marco M Xiao Hai H Cheng Tao T Goddard William A WA Yano Junko J Crumlin Ethan J EJ

Proceedings of the National Academy of Sciences of the United States of America 20170612 26

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of ...[more]

PMID: 28607092

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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.

Dataset Information

Subsurface oxide plays a critical role in CO₂ activation by Cu(111) surfaces to form chemisorbed CO₂, the first step in reduction of CO₂.

Publications

Subsurface oxide plays a critical role in CO<sub>2</sub> activation by Cu(111) surfaces to form chemisorbed CO<sub>2</sub>, the first step in reduction of CO<sub>2</sub>.

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