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Vol. 14 (2022)

MOF-Transformed In2O3-x@C Nanocorn Electrocatalyst for Efficient CO2 Reduction to HCOOH

https://doi.org/10.1007/s40820-022-00913-6
Chen Qiu
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Kun Qian
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Jun Yu
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Mingzi Sun
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, People’s Republic of China
Shoufu Cao
School of Materials Science and Engineering, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
Jinqiang Gao
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Rongxing Yu
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Lingzhe Fang
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Youwei Yao
Shenzhen International Graduate School, Tsinghua University, Shenzhen, People’s Republic of China
Xiaoqing Lu
School of Materials Science and Engineering, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
Tao Li
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Bolong Huang
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, People’s Republic of China
Shihe Yang
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China

Corresponding Author: Shihe Yang

chsyang@pku.edu.cn

Nano-Micro Letters, Vol. 14 (2022), Article Number: 167

Abstract

For electrochemical CO2 reduction to HCOOH, an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density (JHCOOH) at a low overpotential. Indium oxide is good HCOOH production catalyst but with low conductivity. In this work, we report a unique corn design of In2O3-x@C nanocatalyst, wherein In2O3-x nanocube as the fine grains dispersed uniformly on the carbon nanorod cob, resulting in the enhanced conductivity. Excellent performance is achieved with 84% Faradaic efficiency (FE) and 11 mA cm−2 JHCOOH at a low potential of − 0.4 V versus RHE. At the current density of 100 mA cm−2, the applied potential remained stable for more than 120 h with the FE above 90%. Density functional theory calculations reveal that the abundant oxygen vacancy in In2O3-x has exposed more In3+ sites with activated electroactivity, which facilitates the formation of HCOO* intermediate. Operando X-ray absorption spectroscopy also confirms In3+ as the active site and the key intermediate of HCOO* during the process of CO2 reduction to HCOOH.


Highlights:


1 The nanocorn design enables In2O3-x@C a high Faradaic efficiency of 98% and a high formate current density of 320 mA cm−2 at a low potential of -1.2 V versus hydrogen electrode without iR correction.
2 The rich O vacancy activates In3+ sites on the nanocube shell of In2O3-x@C and the carbon cob enhances conductivity.
3 Operando X-ray absorption spectroscopy unveils the active site of In3+ for formate production although reduction of In3+ to In is conceivable at the applied negative potentials during CO2 reduction reaction.

Keywords

CO2 reduction Indium oxide Formate Corn design Active sites
Qiu, Chen, Kun Qian, Jun Yu, Mingzi Sun, Shoufu Cao, Jinqiang Gao, Rongxing Yu, Lingzhe Fang, Youwei Yao, Xiaoqing Lu, Tao Li, Bolong Huang, and Shihe Yang. 2022. “MOF-Transformed In2O3-x@C Nanocorn Electrocatalyst for Efficient CO2 Reduction to HCOOH”. Nano-Micro Letters 14 (August):167. https://doi.org/10.1007/s40820-022-00913-6.
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