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Vol. 15 (2023)

Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia

https://doi.org/10.1007/s40820-023-01091-9
Xue‑Yang Ji
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, People’s Republic of China
Ke Sun
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, People’s Republic of China
Zhi‑Kun Liu
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, People’s Republic of China
Xinghui Liu
Department of Chemistry, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea
Weikang Dong
Beijing Advanced Innovation Center for Intelligent Robots and Systems and Institute of Engineering Medicine, Beijing Institute of Technology, Beijing 100081, People’s Republic of China
Xintao Zuo
Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, People’s Republic of China
Ruiwen Shao
Beijing Advanced Innovation Center for Intelligent Robots and Systems and Institute of Engineering Medicine, Beijing Institute of Technology, Beijing 100081, People’s Republic of China
Jun Tao
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, People’s Republic of China

Corresponding Author: Jun Tao

taojun@bit.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 110

Abstract

Direct electrochemical nitrate reduction reaction (NITRR) is a promising strategy to alleviate the unbalanced nitrogen cycle while achieving the electrosynthesis of ammonia. However, the restructuration of the high-activity Cu-based electrocatalysts in the NITRR process has hindered the identification of dynamical active sites and in-depth investigation of the catalytic mechanism. Herein, Cu species (single-atom, clusters, and nanoparticles) with tunable loading supported on N-doped TiO2/C are successfully manufactured with MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy. Restructuration behavior among Cu species is co-dependent on the Cu loading and reaction potential, as evidenced by the advanced operando X-ray absorption spectroscopy, and there exists an incompletely reversible transformation of the restructured structure to the initial state. Notably, restructured CuN4&Cu4 deliver the high NH3 yield of 88.2 mmol h−1 gcata−1 and FE (~ 94.3%) at − 0.75 V, resulting from the optimal adsorption of NO3− as well as the rapid conversion of *NH2OH to *NH2 intermediates originated from the modulation of charge distribution and d-band center for Cu site. This work not only uncovers CuN4&Cu4 have the promising NITRR but also identifies the dynamic Cu species active sites that play a critical role in the efficient electrocatalytic reduction in nitrate to ammonia.


Highlights:


1 Cu species with tunable loading supported on N-doped TiO2/C were successfully fabricated utilizing MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy.
2 Cu species with tunable loading supported on N-doped TiO2/C were successfully fabricated utilizing MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy.
3 Restructured CuN4&Cu4 performed the highest NH3 yield (88.2 mmol h−1 gcata−1) and FE (~94.3%) at − 0.75 V due to optimal adsorption of NO3− and rapid conversion of the key intermediates.

Keywords

Metal–organic frameworks Copper phthalocyanine Electrocatalytic nitrate reduction reaction
Ji, Xue‑Yang, Ke Sun, Zhi‑Kun Liu, Xinghui Liu, Weikang Dong, Xintao Zuo, Ruiwen Shao, and Jun Tao. 2023. “Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia”. Nano-Micro Letters 15 (April):110. https://doi.org/10.1007/s40820-023-01091-9.
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