Two-Dimensional Metal Covalent Organic Polymers with Dirhodium(II) Photoreduction Centers for Efficient Nitrogen Fixation

IF 2.6 4区材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY

ChemNanoMat Pub Date : 2024-10-24 DOI:10.1002/cnma.202400462

Qian-Qian Qiu, Wang-Kang Han, Ruo-Meng Zhu, Yong Liu, Jia-Xing Fu, Zhi-Guo Gu

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Abstract

Photocatalytic nitrogen fixation is a green method for converting N₂ to NH₃, but it remains a challenging task due to the lack of effective photocatalysts. Herein, a series of porous metal covalent organic polymers (MCOPs) with the integration of dinuclear rhodium(II) catalytic centers were rationally constructed for photocatalytic N₂ fixation. Interestingly, the porous MCOPs had double-layers two-dimensional (2D) structures with the coordinated Rh(II) as the point of registry. The photocatalytic experiment showed that Rh-TAPA with significant donor-acceptor (D−A) features exhibited a high activity toward NH₃ production with a rate of 319.8 μmol g⁻¹ h⁻¹. The electron transfer process, N₂ adsorption and activation mechanism of RhCOPs were further investigated through comprehensive characterization, including DFT calculations and in situ characterization. This work provided a valuable insight into the photocatalytic N₂ fixation process with porous materials.

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具有二铑(II)光还原中心的二维金属共价有机聚合物用于高效固氮

光催化固氮是一种将N2转化为NH3的绿色方法，但由于缺乏有效的光催化剂，它仍然是一项具有挑战性的任务。本文合理构建了一系列具有双核铑（II）催化中心集成的多孔金属共价有机聚合物（mcop），用于光催化固氮。有趣的是，多孔mcop具有双层二维（2D）结构，配位的Rh（II）为配位点。光催化实验表明，具有明显供体-受体（D−A）特征的Rh-TAPA对NH3的产率为319.8 μmol g−1 h−1，具有较高的活性。通过DFT计算和原位表征等综合表征，进一步研究了rhcop的电子转移过程、N2吸附和活化机理。这项工作为多孔材料光催化固氮过程提供了有价值的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ChemNanoMat Energy-Energy Engineering and Power Technology

CiteScore

6.10

自引率

2.60%

发文量

236

期刊介绍： ChemNanoMat is a new journal published in close cooperation with the teams of Angewandte Chemie and Advanced Materials, and is the new sister journal to Chemistry—An Asian Journal.