Issue 14, 2024

Regulating the coordination microenvironment of zinc single-atom catalysts to enhance intramolecular hydroamination performance

Abstract

Precise tuning of the coordination microenvironment is essential to enhance the intrinsic catalytic performance and reaction kinetics of metal single-atom catalysts (SACs). This study proposes a novel strategy to optimize the electronic properties of zinc (Zn) SACs by manipulating the s-band center of the Zn atom within the zinc–nitrogen moieties (Zn–Nx, x = 2, 3, and 4) through adjusting the number of coordination atoms (N) and introducing heteroatoms (P, B, and S) with varying electronegativity. The results demonstrate that the Zn–N2P site, characterized by optimal electron density, exhibits superior performance (conversion ≥ 99.9%, chemoselectivity = 100%), and accelerated reaction kinetics (Ea as low as 94.7 kJ mol−1) in the intramolecular hydroamination of 2-(2-phenylethynyl)aniline, surpassing state-of-the-art transition metal catalysts. In contrast, both experimental and theoretical results indicate that Zn–N2B and Zn–N2S catalysts exhibit significantly lower activities than Zn–N2P and Zn–N3. The superior performance of Zn–N2P originates from an electronic effect, where the electron-donating P heteroatom redistributes the electron cloud, adjusts the polarization of the Zn–N2P moiety, and thereby markedly enhances the adsorption and activation capabilities of 2-(2-phenylethynyl)aniline. This study provides a promising approach for the efficient regulation of the coordination microenvironment of SACs in heterogeneous catalysis.

Graphical abstract: Regulating the coordination microenvironment of zinc single-atom catalysts to enhance intramolecular hydroamination performance

Supplementary files

Article information

Article type
Research Article
Submitted
18 Mai 2024
Accepted
22 Jun 2024
First published
24 Jun 2024

Inorg. Chem. Front., 2024,11, 4207-4218

Regulating the coordination microenvironment of zinc single-atom catalysts to enhance intramolecular hydroamination performance

L. Wang, C. Lv, K. Dou, D. Xie, Y. Fu, F. Zhang, D. Chen and W. Zhu, Inorg. Chem. Front., 2024, 11, 4207 DOI: 10.1039/D4QI01244E

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