Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO2 Reduction

Cavalca, Filippo; Ferragut, Rafael; Aghion, Stefano; Eilert, André; Diaz-Morales, Oscar; Liu, Chang; Koh, Ai Leen; Hansen, Thomas W.; Pettersson, Lars G. M.; Nilsson, Anders

doi:10.1021/acs.jpcc.7b08278

Title: Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO₂ Reduction

Journal Article · Tue Oct 10 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b08278· OSTI ID:1463314

^[1]; Ferragut, Rafael ^[2]; Aghion, Stefano ^[2]; Eilert, André ^[3];

^[4];

^[5]; Hansen, Thomas W. ^[6]; Pettersson, Lars G. M. ^[4];

^[4]

Stockholm Univ., Stockholm (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
LNESS Lab. and Dipartimento di Fisica, Como (Italy); Instituto Nazionale di Fisica Nucleare, Milano (Italy)
Stockholm Univ., Stockholm (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
Stockholm Univ., Stockholm (Sweden)
Stanford Univ., Stanford, CA (United States)
Technical Univ. of Denmark, Lyngby (Denmark)

Oxide-derived copper (OD-Cu) electrodes exhibit higher activity than pristine copper during the carbon dioxide reduction reaction (CO₂RR) and higher selectivity toward ethylene. The presence of residual subsurface oxygen in OD-Cu has been proposed to be responsible for such improvements, although its stability under the reductive CO₂RR conditions remains unclear. This work sheds light on the nature and stability of subsurface oxygen. Our spectroscopic results show that oxygen is primarily concentrated in an amorphous 1–2 nm thick layer within the Cu subsurface, confirming that subsurface oxygen is stable during CO₂RR for up to 1 h at –1.15 V vs RHE. Besides, it is associated with a high density of defects in the OD-Cu structure. In conclusion, we propose that both low coordination of the amorphous OD-Cu surface and the presence of subsurface oxygen that withdraws charge from the copper sp- and d-bands might selectively enhance the binding energy of CO.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1463314

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 45; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 82 works

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Title: Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO₂ Reduction