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用于促进光催化CO还原的小共轭有机配体修饰的基于多金属氧酸盐的杂化材料

Small Conjugated Organic Ligand-Modified Polyoxometalate-Based Hybrid Materials for Boosting Photocatalytic CO Reduction.

作者信息

Dong Zhi-Ming, Zhu Yin-Hua, Zhou Jiu-Lin, Xiang Xin-Ying, Pan Jia-Hang, Mei Hua, Xu Yan

机构信息

College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.

出版信息

Inorg Chem. 2024 Sep 9;63(36):16791-16798. doi: 10.1021/acs.inorgchem.4c02424. Epub 2024 Aug 27.

Abstract

Photocatalytic carbon dioxide (CO) reduction to value-added chemicals is a multielectron transfer process, and the crucial step is the synthesis of photocatalysts. The introduction of small conjugated organic ligands can make the catalytic active site of the compound easier to be exposed in the reaction system and fully contact with the substrate, accelerating the photocatalytic reaction process. In this paper, we synthesized two isomorphic compounds, namely, {[Co(mtrz)·(HO)]·[SiWO]}·6HO () and {[Ni(mtrz)·(HO)]·[SiWO]}·6HO () (mtrz = 1-methyl-1,2,4-triazole). We found that compound has a great photocatalytic performance through a series of experiments, with a CO reduction yield of 7364.92 μmol g h and a CO selectivity of 82.5%. Furthermore, the high catalytic activity can be maintained over four cycle experiments. The catalytic mechanism of its photocatalytic system is also elucidated, which provides an idea for realizing efficient catalytic reduction of CO to CO.

摘要

光催化将二氧化碳(CO₂)还原为增值化学品是一个多电子转移过程,关键步骤是光催化剂的合成。引入小的共轭有机配体可使化合物的催化活性位点在反应体系中更易暴露,并与底物充分接触,加速光催化反应过程。本文中,我们合成了两种同构化合物,即{[Co(mtrz)₃·(H₂O)₃]·[SiW₁₂O₄₀]}·6H₂O(Ⅰ)和{[Ni(mtrz)₃·(H₂O)₃]·[SiW₁₂O₄₀]}·6H₂O(Ⅱ)(mtrz = 1-甲基-1,2,4-三唑)。通过一系列实验,我们发现化合物Ⅰ具有优异的光催化性能,CO₂还原产率为7364.92 μmol g⁻¹ h⁻¹,CO选择性为82.5%。此外,在四个循环实验中其高催化活性均可保持。还阐明了其光催化体系的催化机理,为实现将CO₂高效催化还原为CO提供了思路。

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