Atomically dispersed metal-nitrogen-carbon catalysts with d-orbital electronic configuration-dependent selectivity for electrochemical CO2-to-CO reduction

doi:10.1021/acscatal.2c05249

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題名:	Atomically dispersed metal-nitrogen-carbon catalysts with d-orbital electronic configuration-dependent selectivity for electrochemical CO2-to-CO reduction
作者:	Jialin Wang, Yu-Cheng Huang, Yiqing Wang, Hao Deng, Yuchuan Shi, Daixing Wei, Mingtao Li, Chung-Li Dong, Hui Jin, Samuel S. Mao, Shaohua Shen
關鍵詞:	CO2 Reduction Reaction;Single-Atom Catalysts;Crystal-Field Theory;Electronic Configurations;CO Production
日期:	2023-02
上傳時間:	2024-07-31 12:10:55 (UTC+8)
出版者:	American Chemical Society
摘要:	A variety of atomically dispersed transition-metal-anchored nitrogen-doped carbon (M–N–C) electrocatalysts have shown encouraging electrochemical CO2 reduction reaction (CO2RR) performance, with the underlying fundamentals of central transition-metal atom determined CO2RR activity and selectivity yet remaining unclear. Herein, a universal impregnation-acid leaching method was exploited to synthesize various M–N–C (M: Fe, Co, Ni, and Cu) single-atom catalysts (SACs), which revealed d-orbital electronic configuration-dependent activity and selectivity toward CO2RR for CO production. Notably, Ni–N–C exhibits a very high CO Faradaic efficiency (FE) of 97% at −0.65 V versus RHE and above 90% CO selectivity in the potential range from −0.5 to −0.9 V versus RHE, much superior to other M–N–C (M: Fe, Co, and Cu). With the d-orbital electronic configurations of central metals in M–N–C SACs well elucidated by crystal-field theory, Dewar–Chatt–Duncanson (DCD) and differential charge density analysis reveal that the vacant outermost d-orbital of Ni2+ in a Ni–N–C SAC would benefit the electron transfer from the C atoms in CO2 molecules to the Ni atoms and thus effectively activate the surface-adsorbed CO2 molecules. However, the outermost d-orbital of Fe3+, Co2+, and Cu2+ occupied by unpaired electrons would weaken the electron-transfer process and then impede CO2 activation. In situ spectral investigations demonstrate that the generation of *COOH intermediates is favored over Ni–N–C SAC at relatively low applied potentials, supporting its high CO2-to-CO conversion performance. Gibbs free energy difference analysis in the rate-limiting step in CO2RR and hydrogen evolution reaction (HER) reveals that CO2RR is thermodynamically favored for Ni–N–C SAC, explaining its superior CO2RR performance as compared to other SACs. This work presents a facile and general strategy to effectively modulate the CO2-to-CO selectivity from the perspective of electronic configuration of central metals in M–N–C SACs.
關聯:	ACS Catalysis 13(4), p.2374-2385
DOI:	10.1021/acscatal.2c05249
顯示於類別:	[電機工程學系暨研究所] 期刊論文

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