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

被引：71

作者：

Li, Xuning ^{[1
,2
]}

Zeng, Yaqiong ^{[2
]}

Tung, Ching-Wei ^{[3
]}

Lu, Ying-Rui ^{[4
]}

Baskaran, Sambath ^{[5
]}

Hung, Sung-Fu ^{[3
]}

Wang, Shifu ^{[2
]}

Xu, Cong-Qao ^{[5
]}

Wang, Junhu ^{[6
]}

Chan, Ting-Shan ^{[4
]}

Chen, Hao Ming ^{[3
]}

Jiang, Jianchao ^{[7
]}

Yu, Qi ^{[7
]}

Huang, Yanqiang ^{[2
]}

Li, Jun ^{[5
,8
,9
]}

Zhang, Tao ^{[2
,10
]}

Liu, Bin ^{[1
]}

机构：

[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

来源：

ACS CATALYSIS | 2021年 / 11卷 / 12期

基金：

中国国家自然科学基金;

关键词：

electrochemistry; single-atom catalyst; operando; Mossbauer spectroscopy; reaction mechanism; OXYGEN REDUCTION; MOSSBAUER-SPECTROSCOPY; ELECTRO-REDUCTION; HIGHLY EFFICIENT; POROUS CARBON; FUEL-CELL; N-C; ELECTROREDUCTION; ELECTROCATALYSTS; METAL;

D O I：

10.1021/acscatal.1c01621

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：7292 / 7301

页数：10

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