Unveiling the In Situ Generation of a Monovalent Fe(I) Site in the Single-Fe-Atom Catalyst for Electrochemical CO2 Reduction

Li, Xuning1,2; Zeng, Yaqiong2; Tung, Ching-Wei3; Lu, Ying-Rui4; Baskaran, Sambath5; Hung, Sung-Fu3; Wang, Shifu2; Xu, Cong-Qao5; Wang, Junhu6; Chan, Ting-Shan4; Chen, Hao Ming3; Jiang, Jianchao7; Yu, Qi7; Huang, Yanqiang2; Li, Jun5,8,9; Zhang, Tao2,10; Liu, Bin1

2021-06-18

10.1021/acscatal.1c01621

ACS Catalysis   影响因子和分区

2155-5435

Atomically dispersed single-atom catalysts are among the most attractive electrocatalysts for the CO2 reduction reaction (CRR). To elucidate the origin of the exceptional activity of atomically dispersed Fe-N-C catalyst in CRR, we have performed operando Fe-57 Mossbauer spectroscopic studies on a model single-Fe-atom catalyst with a well-defined N coordination environment. Combining with operando X-ray absorption spectroscopy, the in situ-generated four pyrrolic nitrogen atom-coordinated low-spin Fe(I) (LS FeIN4) featuring monovalent iron is identified as the reactive center for the conversion of CO2 to CO. Furthermore, density functional theory calculations reveal that the optimal binding strength of CO2 to the LS (FeN4)-N-I site, with strong orbital interactions between the singly occupied d(z)(2) orbital of the Fe(I) site and the singly occupied pi* orbital of [COOH] fragment, is the key factor for the excellent CRR performance.

electrochemistry single-atom catalyst operando Mossbauer spectroscopy reaction mechanism

SCI ; EI

英语

通讯

National Key Projects for Fundamental Research and Development of China[2016YFA0202804] ; Strategic Priority Research Program of the Chinese Academy of Sciences[XDB36030200] ; National Natural Science Foundation of China[21925803,22033005,22038002] ; Ministry of Education of Singapore["RG4/20","RG115/18","T2EP10120-0009"] ; Agency for Science, Technol-ogy, and Research (A*Star AME IRG)[IRG A20E5c0080] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Physical

WOS:000664333800050

AMER CHEMICAL SOC

20212610563129

Atoms ; Carbon dioxide ; Density functional theory ; Electrocatalysts ; Iron metallography ; Spectroscopic analysis ; X ray absorption spectroscopy

Metallography:531.2 ; Chemistry:801 ; Chemical Agents and Basic Industrial Chemicals:803 ; Inorganic Compounds:804.2 ; Atomic and Molecular Physics:931.3

Web of Science

1.Nanyang Technol Univ, Sch Chem & Biomed Engn, Singapore 637459, Singapore
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
3.Natl Taiwan Univ, Dept Chem, Taipei 106, Taiwan
4.Natl Synchrotron Radiat Res Ctr, Hsinchu 300, Taiwan
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
6.Chinese Acad Sci, Mossbauer Effect Data Ctr, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
7.Shaanxi Univ Technol, Shaanxi Key Lab Catalysis, Hanzhong 723000, Peoples R China
8.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
9.Tsinghua Univ, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China
10.Univ Chinese Acad Sci, Beijing 100049, Peoples R China

Li, Xuning,Zeng, Yaqiong,Tung, Ching-Wei,et al. Unveiling the In Situ Generation of a Monovalent Fe(I) Site in the Single-Fe-Atom Catalyst for Electrochemical CO2 Reduction[J]. ACS Catalysis,2021,11(12):7292-7301.

Li, Xuning.,Zeng, Yaqiong.,Tung, Ching-Wei.,Lu, Ying-Rui.,Baskaran, Sambath.,...&Liu, Bin.(2021).Unveiling the In Situ Generation of a Monovalent Fe(I) Site in the Single-Fe-Atom Catalyst for Electrochemical CO2 Reduction.ACS Catalysis,11(12),7292-7301.

Li, Xuning,et al."Unveiling the In Situ Generation of a Monovalent Fe(I) Site in the Single-Fe-Atom Catalyst for Electrochemical CO2 Reduction".ACS Catalysis 11.12(2021):7292-7301.