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基于铋的金属有机框架上由于协同光催化和光热效应而增强的一氧化碳与环氧化物之间的环加成反应。

Enhanced cycloaddition between CO and epoxide over a bismuth-based metal organic framework due to a synergistic photocatalytic and photothermal effect.

作者信息

Zhou Xiaolu, Zhang Honggang, Cheng Hefeng, Wang Zeyan, Wang Peng, Zheng Zhaoke, Dai Ying, Xing Danning, Liu Yuanyuan, Huang Baibiao

机构信息

State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.

School of Physics, Shandong University, Jinan 250100, China.

出版信息

J Colloid Interface Sci. 2024 Mar 15;658:805-814. doi: 10.1016/j.jcis.2023.12.112. Epub 2023 Dec 20.

Abstract

The cycloaddition reaction between CO and epoxide is an efficient way to convert CO into high value-added chemicals. Therefore, it is particularly important to develop efficient catalysts that can catalyze the reaction under mild conditions. In this work, a metal-organic framework (Bi-HHTP, consisting of bismuth (Bi) as metal dots and 2,3,6,7,10,11-hexahydroxy-triphenylene (HHTP) as organic linkers) with zigzagging corrugated topology was successfully synthesized, which shows excellent catalytic activity under visible light irradiation. Various characterizations suggest that the excellent activity is derived from the following reasons: (1) the abundant exposed Bi sites provide Lewis sites for adsorption of epoxides and CO; (2) the free holes produced over Bi-HHTP under light irradiation which could oxidize epoxide, which consequently facilitateing the subsequent ring-opening reaction; and (3) the existence of synergistic photocatalytic and photothermal effect in Bi-HHTP. This study provides a new avenue of developing bismuth-based metal organic frameworks to promote the efficiency of cycloaddition of CO under mild conditions.

摘要

一氧化碳与环氧化物之间的环加成反应是将一氧化碳转化为高附加值化学品的有效途径。因此,开发能够在温和条件下催化该反应的高效催化剂尤为重要。在这项工作中,成功合成了一种具有锯齿状波纹拓扑结构的金属有机框架(Bi-HHTP,由铋(Bi)作为金属点和2,3,6,7,10,11-六羟基三亚苯(HHTP)作为有机连接体组成),其在可见光照射下表现出优异的催化活性。各种表征表明,优异的活性源于以下原因:(1)大量暴露的铋位点为环氧化物和一氧化碳的吸附提供了路易斯位点;(2)光照下Bi-HHTP上产生的自由空穴可氧化环氧化物,从而促进随后的开环反应;(3)Bi-HHTP中存在协同光催化和光热效应。该研究为开发铋基金属有机框架以提高温和条件下一氧化碳环加成效率提供了一条新途径。

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