Atomic Tuning of Single-Atom Fe-N-C Catalysts with Phosphorus for Robust Electrochemical CO2 Reduction

Ke Li; Shengbo Zhang; Xiuli Zhang; Shuang Liu; Haosong Jiang; Taoli Jiang; Chunyue Shen; Yi Yu; Wei Chen

doi:10.1021/acs.nanolett.1c04382

Atomic Tuning of Single-Atom Fe-N-C Catalysts with Phosphorus for Robust Electrochemical CO₂ Reduction

Nano Lett. 2022 Feb 23;22(4):1557-1565. doi: 10.1021/acs.nanolett.1c04382. Epub 2022 Feb 1.

Authors

Ke Li¹, Shengbo Zhang², Xiuli Zhang³, Shuang Liu¹, Haosong Jiang¹, Taoli Jiang¹, Chunyue Shen¹, Yi Yu³, Wei Chen¹

Affiliations

¹ Department of Applied Chemistry, School of Chemistry and Materials Science, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.
² Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, China.
³ School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.

PMID: 35104146
DOI: 10.1021/acs.nanolett.1c04382

Abstract

The electrochemical reduction of CO₂ to produce carbon-based fuels and chemicals possesses huge potentials to alleviate current environmental problems. However, it is confronted by great challenges in the design of active electrocatalysts with low overpotentials and high product selectivity. Here we report the atomic tuning of a single-Fe-atom catalyst with phosphorus (Fe-N/P-C) on commercial carbon black as a robust electrocatalyst for CO₂ reduction. The Fe-N/P-C catalyst exhibits impressive performance in the electrochemical reduction of CO₂ to CO, with a high Faradaic efficiency of 98% and a high mass-normalized turnover frequency of 508.8 h^-1 at a low overpotential of 0.34 V. On the basis of ex-situ X-ray absorption spectroscopy measurements and DFT calculations, we reveal that the tuning of P in single-Fe-atom catalysts reduces the oxidation state of the Fe center and decreases the free-energy barrier of *CO intermediate formation, consequently maintaining the electrocatalytic activity and stability of single-Fe-atom catalysts.

Keywords: CO2RR; DFT calculations; Fe−N/P−C; ex-situ XAS; single-atom catalyst.