配体羟基改性增强UiO-66的光热催化氧化VOCs性能

doi:10.15541/jim20250157

摘要/Abstract

摘要：

在室内和工业环境中，高效去除低浓度挥发性有机化合物（VOCs）依然是一个重大挑战。金属有机框架（MOFs）对低浓度VOCs具有优异的吸附富集能力，被认为是一种有潜力的氧化催化剂。本研究通过在配体中引入羟基，合成了UiO-66-OH催化剂，其对低浓度VOCs（甲苯质量浓度0.075 mg/L，苯质量浓度0.064 mg/L，空速(WHSV)30000 mL/(g∙h)）表现出优异的光热催化氧化性能，对甲苯和苯的转化率分别达到了97%和90%，优于已报道的金属氧化物和贵金属光热催化剂。其优异的催化活性主要归因于热催化与光催化的协同效应。配体羟基化优化了UiO-66的电子结构及配体-金属-电荷转移效应(LMCT)，从而增强了光吸收能力，提高了电子-空穴分离效率和光热性能。同时，引入羟基还促进了氧空位的生成，有利于O₂吸附活化，生成的超氧自由基（∙O₂^-）为主要活性氧物种。本研究不仅展示了MOFs在低浓度VOCs光热催化氧化中的应用潜力，也提供了一种通过配体工程调控电子结构来提升MOFs光热性能的有效策略。

关键词: 挥发性有机化合物, 低浓度, 金属-有机框架, 光热催化, 配体-金属电荷转移效应

Abstract:

The efficient removal of low-concentration volatile organic compounds (VOCs) in indoor and industrial environments remains a significant challenge. Metal-organic frameworks (MOFs) are potential oxidation catalysts due to their superior adsorption enrichment capability for low-concentration VOCs. In this work, hydroxyl-containing ligands were introduced into UiO-66, and the as-synthesized UiO-66-OH catalyst exhibited exceptional photothermal catalytic performance on oxidation of flowing low-concentration VOCs (an initial concentration of 0.075 mg/L for toluene and 0.064 mg/L for benzene, a weight hourly space velocity (WHSV) of 30000 mL/(g∙h)), achieving 97% and 90% conversion of toluene and benzene, respectively, surpassing the reported photothermal catalysts such as metal oxides and noble-metal-loaded catalysts. Such impressive activity is attributed to the synergy of thermal catalysis and photocatalysis. Ligand hydroxylation optimizes the electron structure and the ligand-to-metal charge transfer (LMCT) effect, enhancing light absorption, improving electron-hole separation efficiency and photothermal properties of UiO-66. Hydroxyl introduction promotes the formation of oxygen vacancies, facilitating oxygen adsorption/activation to sustain lattice oxygen (O_latt) and generate superoxide radical (∙O₂^-), which are the dominant reactive species in VOCs oxidation. This work not only presents the potential of MOFs as efficient photothermal catalysts for the oxidation of low-concentration VOCs but also shows prospective on facile modulation of electron structure by ligand engineering to enhance the photothermal properties of MOFs.

Key words: volatile organic compound, low concentration, metal-organic framework, photothermal catalysis, ligand-to-metal charge transfer effect

中图分类号:

TQ134

陈笑晨, 王阳, 杨彬, 王敏, 阿博涵, 王蔓, 张玲霞. 配体羟基改性增强UiO-66的光热催化氧化VOCs性能[J]. 无机材料学报, DOI: 10.15541/jim20250157.

CHEN Xiaochen, WANG Yang, YANG Bin, WANG Min, A Bohan, WANG Man, ZHANG Lingxia. Ligand-hydroxylated UiO-66 for Enhanced Photothermally Catalytic VOCs Oxidation[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250157.

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