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Vol. 15 (2023)

Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis

https://doi.org/10.1007/s40820-023-01127-0
Yuhang Gao
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Jingnan Wang
Molecular Plus and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin 300072, People’s Republic of China
Yijun Yang
Department of Physics, School of Physical Science and Engineering, Beijing Jiaotong University, Beijing 100044, People’s Republic of China
Jian Wang
Research Center for Magnetic and Spintronic Materials National Institute for Materials Science, Tsukuba 305‑0047, Japan
Chuang Zhang
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Xi Wang
Department of Physics, School of Physical Science and Engineering, Beijing Jiaotong University, Beijing 100044, People’s Republic of China
Jiannian Yao
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China

Corresponding Author: Xi Wang

xiwang@bjtu.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 158

Abstract

The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: CuIII-HHTP and CuII-HHTP. CuIII-HHTP exhibits an improved urea production rate of 7.78 mmol h−1 g−1 and an enhanced Faradaic efficiency of 23.09% at − 0.6 V vs. reversible hydrogen electrode, in sharp contrast to CuII-HHTP. Isolated CuIII species with S = 0 spin ground state are demonstrated as the active center in CuIII-HHTP, different from CuII with S = 1/2 in CuII-HHTP. We further demonstrate that isolated CuIII with an empty d0x2-y2 orbital in CuIII-HHTP experiences a single-electron migration path with a lower energy barrier in the C–N coupling process, while CuII with a single-spin state (d1x2-y2) in CuII-HHTP undergoes a two-electron migration pathway.


Highlights:


1 The single-atom Cu species with S = 0 spin ground state in CuIII-HHTP have been fabricated.
2 The CuIII-HHTP exhibits remarkable performance with a high urea yield of 7.780 mmol h−1 g−1 with the corresponding Faradaic efficiency of 23.09% at − 0.6 V (vs. RHE).
3 Low spin state and empty (d0x2-y2) orbitals are favorable to enhance the production urea of C–N coupling process.

Keywords

Electrocatalysis Urea synthesis Metal–organic framework Spin catalysis C–N coupling
Gao, Yuhang, Jingnan Wang, Yijun Yang, Jian Wang, Chuang Zhang, Xi Wang, and Jiannian Yao. 2023. “Engineering Spin States of Isolated Copper Species in a Metal–Organic Framework Improves Urea Electrosynthesis”. Nano-Micro Letters 15 (June):158. https://doi.org/10.1007/s40820-023-01127-0.
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