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

Wanzhen Zheng; Feng Chen; Qi Zeng; Zhongjian Li; Bin Yang; Lecheng Lei; Qinghua Zhang; Feng He; Xilin Wu; Yang Hou

doi:10.1007/s40820-020-00443-z

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

Nanomicro Lett. 2020 May 9;12(1):108. doi: 10.1007/s40820-020-00443-z.

Authors

Wanzhen Zheng^{1

2}, Feng Chen³, Qi Zeng¹, Zhongjian Li¹, Bin Yang^{1

4}, Lecheng Lei^{1

4}, Qinghua Zhang⁵, Feng He², Xilin Wu⁶, Yang Hou^{7

8

9}

Affiliations

¹ 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.
² College of Environment, Zhejiang University of Technology, Hangzhou, 310014, People's Republic of China.
³ College of Geography and Environmental Science, Zhejiang Normal University, Jinhua, 321004, People's Republic of China.
⁴ Institute of Zhejiang University - Quzhou, Quzhou, 324000, People's Republic of China.
⁵ 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.
⁶ College of Geography and Environmental Science, Zhejiang Normal University, Jinhua, 321004, People's Republic of China. dbwxl@zjnu.cn.
⁷ 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. yhou@zju.edu.cn.
⁸ Institute of Zhejiang University - Quzhou, Quzhou, 324000, People's Republic of China. yhou@zju.edu.cn.
⁹ Ningbo Research Institute, Zhejiang University, Ningbo, 315100, People's Republic of China. yhou@zju.edu.cn.

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%.

Keywords: Atomic dispersion; CO2 electroreduction; Catalytic site; Pyrrole-type metal–N4 structure; Zn–CO2 battery.