Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO2 Electroreduction

Zhi-Zheng Wu; Xiao-Long Zhang; Zhuang-Zhuang Niu; Fei-Yue Gao; Peng-Peng Yang; Li-Ping Chi; Lei Shi; Wen-Sen Wei; Ren Liu; Zhi Chen; Shaojin Hu; Xiao Zheng; Min-Rui Gao

doi:10.1021/jacs.1c09508

Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO₂ Electroreduction

J Am Chem Soc. 2022 Jan 12;144(1):259-269. doi: 10.1021/jacs.1c09508. Epub 2021 Dec 28.

Authors

Affiliations

¹ Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China.
² Anhui Key Laboratory of Condensed Matter Physics at Extreme Conditions, High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China.
³ Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China.
⁴ Division of Theoretical and Computational Sciences, Hefei National Laboratory for Physical Sciences at Microscale, CAS Centre for Excellence and Synergetic Innovation Centre in Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei 230026, China.

PMID: 34962375
DOI: 10.1021/jacs.1c09508

Abstract

The electrosynthesis of valuable multicarbon chemicals using carbon dioxide (CO₂) as a feedstock has substantially progressed recently but still faces considerable challenges. A major difficulty lines in the sluggish kinetics of forming carbon-carbon (C-C) bonds, especially in neutral media. We report here that oxide-derived copper crystals enclosed by six {100} and eight {111} facets can reduce CO₂ to multicarbon products with a high Faradaic efficiency of 74.9 ± 1.7% at a commercially relevant current density of 300 mA cm^-2 in 1 M KHCO₃ (pH ∼ 8.4). By combining the experimental and computational studies, we uncovered that Cu(100)/Cu(111) interfaces offer a favorable local electronic structure that enhances *CO adsorption and lowers C-C coupling activation energy barriers, performing superior to Cu(100) and Cu(111) surfaces, respectively. On this catalyst, no obvious degradation was observed at 300 mA cm^-2 over 50 h of continuous operation.