Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single-Atom Nickel Catalyst

Song Liu; Hong Bin Yang; Sung-Fu Hung; Jie Ding; Weizheng Cai; Linghui Liu; Jiajian Gao; Xuning Li; Xinyi Ren; Zhichong Kuang; Yanqiang Huang; Tao Zhang; Bin Liu

doi:10.1002/anie.201911995

Elucidating the Electrocatalytic CO₂ Reduction Reaction over a Model Single-Atom Nickel Catalyst

Angew Chem Int Ed Engl. 2020 Jan 7;59(2):798-803. doi: 10.1002/anie.201911995. Epub 2019 Dec 10.

Authors

Song Liu^{1

2

3}, Hong Bin Yang³, Sung-Fu Hung⁴, Jie Ding¹, Weizheng Cai³, Linghui Liu^{1

5}, Jiajian Gao³, Xuning Li³, Xinyi Ren^{1

2}, Zhichong Kuang^{1

2}, Yanqiang Huang^{1

6}, Tao Zhang¹, Bin Liu³

Affiliations

¹ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459, Singapore.
⁴ Department of Chemistry, National (Taiwan) University, No. 1, Sec. 4, Roosevelt Rd, Taipei, 10617, Taiwan.
⁵ School of Chemistry and Chemical Engineering, Chongqing University, Shapingba 174, Chongqing, 400044, P. R. China.
⁶ Dalian National Laboratory for Clean Energy, Dalian, 116023, China.

PMID: 31657106
DOI: 10.1002/anie.201911995

Abstract

Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO₂ RR) is an appealing approach to tackling the challenges posed by rising CO₂ levels and realizing a closed carbon cycle. However, fundamental understanding of the complicated CO₂ RR mechanism in CO₂ electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single-atom catalyst (Ni SAC) with a uniform structure and well-defined Ni-N₄ moiety on a conductive carbon support with which to explore the electrochemical CO₂ RR. Operando X-ray absorption near-edge structure spectroscopy, Raman spectroscopy, and near-ambient X-ray photoelectron spectroscopy, revealed that Ni⁺ in the Ni SAC was highly active for CO₂ activation, and functioned as an authentic catalytically active site for the CO₂ RR. Furthermore, through combination with a kinetics study, the rate-determining step of the CO₂ RR was determined to be *CO₂ ^- +H⁺ →*COOH. This study tackles the four challenges faced by the CO₂ RR; namely, activity, selectivity, stability, and dynamics.

Keywords: Active site; Electrochemistry; In situ reactions; Reaction mechanisms; Single-atom catalysts.

Abstract

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