Unveiling the Proton‐Feeding Effect in Sulfur‐Doped Fe−N−C Single‐Atom Catalyst for Enhanced CO2 Electroreduction

Heteroatom‐doping in metal‐nitrogen‐carbon single‐atom catalysts (SACs) is considered a powerful strategy to promote the electrocatalytic CO2 reduction reaction (CO2RR), but the origin of enhanced catalytic activity is still elusive. Here, we disclose that sulfur doping induces an obvious proton‐fee...

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Published in:Angewandte Chemie International Edition Vol. 61; no. 32; pp. e202206233 - n/a
Main Authors: Chen, Shanyong, Li, Xiaoqing, Kao, Cheng‐Wei, Luo, Tao, Chen, Kejun, Fu, Junwei, Ma, Chao, Li, Hongmei, Li, Ming, Chan, Ting‐Shan, Liu, Min
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 08.08.2022
Edition:International ed. in English
Subjects:
Absorption spectroscopy
Carbon dioxide
Catalysts
Catalytic activity
Chemical reduction
CO2 Electroreduction
Doping
Heteroatom Doping
Proton-Feeding Effect
Protons
Reaction Kinetics
Scanning transmission electron microscopy
Single atom catalysts
Sulfur
Transmission electron microscopy
CO2 electroreduction
single-atom catalyst
proton-feeding effect
Heteroatom doping
Reaction kinetics
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:Heteroatom‐doping in metal‐nitrogen‐carbon single‐atom catalysts (SACs) is considered a powerful strategy to promote the electrocatalytic CO2 reduction reaction (CO2RR), but the origin of enhanced catalytic activity is still elusive. Here, we disclose that sulfur doping induces an obvious proton‐feeding effect for CO2RR. The model SAC catalyst with sulfur doping in the second‐shell of FeN4 (Fe1−NSC) was verified by X‐ray absorption spectroscopy and aberration‐corrected scanning transmission electron microscopy. Fe1−NSC exhibits superior CO2RR performance compared to sulfur‐free FeN4 and most reported Fe‐based SACs, with a maximum CO Faradaic efficiency of 98.6 % and turnover frequency of 1197 h−1. Kinetic analysis and in situ characterizations confirm that sulfur doping accelerates H2O activation and feeds sufficient protons for promoting CO2 conversion to *COOH, which is also corroborated by the theoretical results. This work deepens the understanding of the CO2RR mechanism based on SAC catalysts. Sulfur‐doping in the second coordination shell of FeN4 induces the increased CO2 reduction reaction (CO2RR) performance relative to pristine FeN4. The proton‐feeding effect after sulfur doping is demonstrated to promote protonation of *CO2 to *COOH, and thus CO2RR performances, through kinetic analysis, in situ characterization and DFT calculations.
Bibliography:These authors contributed equally to this work.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202206233