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Vol. 12 (2020)

A Universal Principle to Accurately Synthesize Atomically Dispersed Metal–N4 Sites for CO2 Electroreduction

https://doi.org/10.1007/s40820-020-00443-z
Wanzhen Zheng
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Feng Chen
College of Geography and Environmental Science, Zhejiang Normal University, Jinhua 321004, People’s Republic of China
Qi Zeng
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Zhongjian Li
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Bin Yang
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Lecheng Lei
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Qinghua Zhang
Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Feng He
College of Environment, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
Xilin Wu
College of Geography and Environmental Science, Zhejiang Normal University, Jinhua 321004, People’s Republic of China
Yang Hou
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China

Corresponding Author: Yang Hou

yhou@zju.edu.cn

Nano-Micro Letters, Vol. 12 (2020), Article Number: 108

Abstract

Atomically dispersed metal–nitrogen sites-anchored carbon materials have been developed as effective catalysts for CO2 electroreduction (CO2ER), but they still suffer from the imprecisely control of type and coordination number of N atoms bonded with central metal. Herein, we develop a family of single metal atom bonded by N atoms anchored on carbons (SAs–M–N–C, M = Fe, Co, Ni, Cu) for CO2ER, which composed of accurate pyrrole-type M–N4 structures with isolated metal atom coordinated by four pyrrolic N atoms. Benefitting from atomically coordinated environment and specific selectivity of M–N4 centers, SAs–Ni–N–C exhibits superior CO2ER performance with onset potential of − 0.3 V, CO Faradaic efficiency (F.E.) of 98.5% at − 0.7 V, along with low Tafel slope of 115 mV dec−1 and superior stability of 50 h, exceeding all the previously reported M–N–C electrocatalysts for CO2-to-CO conversion. Experimental results manifest that the different intrinsic activities of M–N4 structures in SAs–M–N–C result in the corresponding sequence of Ni > Fe > Cu > Co for CO2ER performance. An integrated Zn–CO2 battery with Zn foil and SAs–Ni–N–C is constructed to simultaneously achieve CO2-to-CO conversion and electric energy output, which delivers a peak power density of 1.4 mW cm−2 and maximum CO F.E. of 93.3%.


Highlights:


1 A family of SAs–M–N–C consisted of carbon nanosheets supported atomic sites of isolated metal atom coordinated with four pyrrolic N atoms was fabricated.
2 The SAs–Ni–N–C exhibited superior electrochemical CO2 electroreduction (CO2ER) activity and selectivity.

Keywords

Atomic dispersion Pyrrole-type metal–N4 structure Catalytic site CO2 electroreduction Zn–CO2 battery
Zheng, Wanzhen, Feng Chen, Qi Zeng, Zhongjian Li, Bin Yang, Lecheng Lei, Qinghua Zhang, Feng He, Xilin Wu, and Yang Hou. 2020. “A Universal Principle to Accurately Synthesize Atomically Dispersed Metal–N4 Sites for CO2 Electroreduction”. Nano-Micro Letters 12 (May):108. https://doi.org/10.1007/s40820-020-00443-z.
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