Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity

Huishan Shang; Xiangyi Zhou; Juncai Dong; Ang Li; Xu Zhao; Qinghua Liu; Yue Lin; Jiajing Pei; Zhi Li; Zhuoli Jiang; Danni Zhou; Lirong Zheng; Yu Wang; Jing Zhou; Zhengkun Yang; Rui Cao; Ritimukta Sarangi; Tingting Sun; Xin Yang; Xusheng Zheng; Wensheng Yan; Zhongbin Zhuang; Jia Li; Wenxing Chen; Dingsheng Wang; Jiatao Zhang; Yadong Li

doi:10.1038/s41467-020-16848-8

Engineering unsymmetrically coordinated Cu-S₁N₃ single atom sites with enhanced oxygen reduction activity

Nat Commun. 2020 Jun 16;11(1):3049. doi: 10.1038/s41467-020-16848-8.

Authors

Huishan Shang^#¹, Xiangyi Zhou^#², Juncai Dong^#³, Ang Li⁴, Xu Zhao⁵, Qinghua Liu⁵, Yue Lin⁶, Jiajing Pei⁷, Zhi Li⁸, Zhuoli Jiang¹, Danni Zhou¹, Lirong Zheng³, Yu Wang⁹, Jing Zhou⁹, Zhengkun Yang¹⁰, Rui Cao¹¹, Ritimukta Sarangi¹¹, Tingting Sun¹², Xin Yang², Xusheng Zheng⁵, Wensheng Yan⁵, Zhongbin Zhuang⁷, Jia Li¹³, Wenxing Chen¹⁴, Dingsheng Wang¹⁵, Jiatao Zhang¹⁶, Yadong Li⁸

Affiliations

¹ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China.
² Laboratory for Computational Materials Engineering, Division of Energy and Environment, Graduate School at Shenzhen, Tsinghua University, Shenzhen, 518055, China.
³ Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China.
⁴ Beijing Key Laboratory of Microstructure and Property of Advanced Materials, Beijing University of Technology, Beijing, 100029, China.
⁵ National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei, 230029, China.
⁶ Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
⁷ State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China.
⁸ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
⁹ Shanghai Synchrotron Radiation Facilities (SSRF), Shanghai Institute of Applied Physics, Chinese Academy of Science, Shanghai, 201204, China.
¹⁰ Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
¹¹ Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA.
¹² Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing, 100083, China.
¹³ Laboratory for Computational Materials Engineering, Division of Energy and Environment, Graduate School at Shenzhen, Tsinghua University, Shenzhen, 518055, China. lijia@phys.tsinghua.edu.cn.
¹⁴ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China. wxchen@bit.edu.cn.
¹⁵ Department of Chemistry, Tsinghua University, Beijing, 100084, China. wangdingsheng@mail.tsinghua.edu.cn.
¹⁶ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China. zhangjt@bit.edu.cn.

^# Contributed equally.

Abstract

Atomic interface regulation is thought to be an efficient method to adjust the performance of single atom catalysts. Herein, a practical strategy was reported to rationally design single copper atoms coordinated with both sulfur and nitrogen atoms in metal-organic framework derived hierarchically porous carbon (S-Cu-ISA/SNC). The atomic interface configuration of the copper site in S-Cu-ISA/SNC is detected to be an unsymmetrically arranged Cu-S₁N₃ moiety. The catalyst exhibits excellent oxygen reduction reaction activity with a half-wave potential of 0.918 V vs. RHE. Additionally, through in situ X-ray absorption fine structure tests, we discover that the low-valent Cuprous-S₁N₃ moiety acts as an active center during the oxygen reduction process. Our discovery provides a universal scheme for the controllable synthesis and performance regulation of single metal atom catalysts toward energy applications.

Abstract

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