Precisely doping the surface of tin-based electrocatalysts for improved CO2 conversion to liquid chemicals

Nguyen-Phan, Thuy-Duong; Ellis, James E.; Nagarajan, Anantha Venkataraman; Howard, Bret H.; Mpourmpakis, Giannis; Kauffman, Douglas R.

doi:10.1016/j.apcatb.2023.123250

Title: Precisely doping the surface of tin-based electrocatalysts for improved CO₂ conversion to liquid chemicals

Journal Article · 01 September 2023 · Applied Catalysis. B, Environmental

DOI: https://doi.org/10.1016/j.apcatb.2023.123250 · OSTI ID:1997990

^[1]; Ellis, James E. ^[1]; Nagarajan, Anantha Venkataraman ^[2]; Howard, Bret H. ^[1]; Mpourmpakis, Giannis ^[2]; Kauffman, Douglas R. ^[1]

National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); Univ. of Pittsburgh, PA (United States)

Doping tin catalysts with sulfur can improve the electrochemical CO₂ conversion into formate/formic acid, but the lack of composition-dependent activity trends hinders further catalyst development. Here, we precisely controlled the composition of sulfur-doped Sn catalysts to show that sulfur doping only improves CO₂ conversion over a very narrow composition range, achieving maximum activity at 1.4 at% S. In situ Raman spectroscopy indicted working catalysts were in a primarily metallic state (e.g. S-Sn), and we achieved some of the highest reported partial current densities in both H-cell and full-cell electrolyzer configurations. Density Functional Theory calculations predicted S atoms preferentially occupied the catalyst surface and improved CO₂ reduction by localizing charge density at the catalyst/intermediate interface, which stabilized the *OCOH intermediate and lowered the CO₂ conversion thermodynamic barrier. Our work quantifies the composition-dependent influence of S dopants on Sn-based CO₂ reduction catalysts and provides a pathway for maximizing their CO₂ conversion activity.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy and Carbon Management (FECM)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1997990

Journal Information:: Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Journal Issue: 2024 Vol. 340; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Precisely doping the surface of tin-based electrocatalysts for improved CO2 conversion to liquid chemicals

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Title: Precisely doping the surface of tin-based electrocatalysts for improved CO₂ conversion to liquid chemicals