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

Highlights Cu species with tunable loading supported on N-doped TiO 2 /C were successfully fabricated utilizing MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy. Cu species with tunable loading supported on N-doped TiO 2 /C were successfully fabricated utilizing MOFs@CuPc precurso...

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Published in:Nano-micro letters 2023-12, Vol.15 (1), p.110-110, Article 110
Main Authors: Ji, Xue-Yang, Sun, Ke, Liu, Zhi-Kun, Liu, Xinghui, Dong, Weikang, Zuo, Xintao, Shao, Ruiwen, Tao, Jun
Format: Article
Language:English
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Summary:Highlights Cu species with tunable loading supported on N-doped TiO 2 /C were successfully fabricated utilizing MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy. Cu species with tunable loading supported on N-doped TiO 2 /C were successfully fabricated utilizing MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy. Restructured CuN 4 &Cu 4 performed the highest NH 3 yield (88.2 mmol h −1 g cata −1 ) and FE (~94.3%) at − 0.75 V due to optimal adsorption of NO 3 − and rapid conversion of the key intermediates. 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 TiO 2 /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 CuN 4 &Cu 4 deliver the high NH 3 yield of 88.2 mmol h −1 g cata −1 and FE (~ 94.3%) at − 0.75 V, resulting from the optimal adsorption of NO 3 − as well as the rapid conversion of *NH 2 OH to *NH 2 intermediates originated from the modulation of charge distribution and d -band center for Cu site. This work not only uncovers CuN 4 &Cu 4 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.
ISSN:2311-6706
2150-5551
DOI:10.1007/s40820-023-01091-9