配体羟基改性增强UiO-66的光热催化氧化VOCs性能

doi:10.15541/jim20250157

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 663-672.DOI: 10.15541/jim20250157 CSTR: 32189.14.jim20250157

所属专题：【能源环境】金属有机框架材料MOF(202512)

配体羟基改性增强UiO-66的光热催化氧化VOCs性能

陈笑晨¹^,²(), 王阳², 杨彬¹, 王敏², 阿博涵², 王蔓², 张玲霞¹^,²()

¹ 国科大杭州高等研究院化学与材料科学学院, 杭州 310024
² 中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2025-04-13 修回日期:2025-06-26 出版日期:2025-07-31 网络出版日期:2025-07-31
通讯作者: 张玲霞, 教授. E-mail: zhlingxia@mail.sic.ac.cn
作者简介:陈笑晨(1999-), 男, 硕士研究生. E-mail: chenxiaochen22@mails.ucas.ac.cn

Ligand-hydroxylated UiO-66 for Enhanced Photothermally Catalytic VOCs Oxidation

CHEN Xiaochen¹^,²(), WANG Yang², YANG Bin¹, WANG Min², A Bohan², WANG Man², ZHANG Lingxia¹^,²()

¹ School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China
² Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2025-04-13 Revised:2025-06-26 Published:2025-07-31 Online:2025-07-31
Contact: ZHANG Lingxia, professor. E-mail: zhlingxia@mail.sic.ac.cn
About author:CHEN Xiaochen (1999-), male, Master candidate. E-mail: chenxiaochen22@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(22405287);Science and Technology Commission of Shanghai(24DZ2201600);Science and Technology Commission of Shanghai(24ZR1475800);China Postdoctoral Science Foundation(2024M760699)

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, 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(LMCT)效应, 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 (initial concentrations 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 prospects 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, 2026, 41(5): 663-672.

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, 2026, 41(5): 663-672.

图/表 15

Fig. 1 (a) Schematic diagram of the synthesis procedure, (b) XRD patterns and (c) FT-IR spectra of UiO-66 and UiO-66-X

Fig. 2 (a, b) Photothermal catalytic performance of UiO-66-X and UiO-66 for oxidation of (a) toluene and (b) benzene, and (c, d) cycle stability of UiO-66-OH for photothermal catalytic oxidation of (c) toluene and (d) benzene

Fig. 3 (a) Surface temperature of the catalysts, (b) schematic band structure, (c) O1s XPS spectra, and (d) active species trapping experiments of UiO-66-OH

Fig. 4 In-situ FT-IR spectra of UiO-66-OH for oxidation of toluene under different successive conditions (a) In dark without O2; (b) In dark with O2; (c, d) With O2 and irradiation

Fig. 5 In-situ FT-IR spectra of UiO-66-OH for oxidation of benzene under different successive conditions (a) In dark without O2; (b) In dark with O2; (c, d) With O2 and irradiation

Table S1 Hydrothermal conditions for the synthesis of UiO-66 and UiO-66-X catalysts

Sample	Temperature/℃	Time/h
UiO-66	120	24
UiO-66-NDC	120	24
UiO-66-NO₂	120	24
UiO-66-NH₂	120	12
UiO-66-OH	80	12

Table S2 Performance comparison of relevant catalysts on benzene and toluene oxidation

Catalyst	VOC	Concentration/(mg∙L^-1)	Catalyst amount/mg	Light intensity/(mW∙cm^-2)	Conversion/%
Pt/TiO₂^[S2]	Benzene	0.96	100	300	84.5
Pt/g-C₃N₄^[S3]	Benzene	0.96	150	500	95
This work	Benzene	0.064	100	300	90
MnO_x-TiO₂^[S4]	Toluene	0.02	500	-	72
TiO₂-UiO-66-NH₂^[9]	Toluene	0.094	100	50	73
Pt/MnO_x^[S5]	Toluene	0.75	100	200	90
This work	Toluene	0.075	100	300	97

Fig. S1 FT-IR spectrum of UiO-66-NH2 in the range of 2000-4000 cm-1

Fig. S2 (a, b) SEM images and (c) XRD patterns of UiO-66-OH (a) before and (b) after five catalytic cycles

Fig. S3 N2 adsorption-desorption isotherms at 77 K with inset showing pore-size distributions of UiO-66 and UiO-66-OH

Fig. S4 (a) UV-Vis absorption spectra; (b) Tauc plots; (c, d) Mott-Schottky plots of (c) UiO-66 and (d) UiO-66-OH

Fig. S5 (a) PL spectra, (b) photocurrent response spectra and (c) Nyquist plots of UiO-66 and UiO-66-OH

Fig. S6 (a, b) Zr3d XPS spectra of (a) UiO-66 and (b) UiO-66-OH, (c) EPR spectra of UiO-66 and UiO-66-OH, and(d) comparison of toluene and benzene conversion by photothermal catalysis and thermal catalysis

Fig. S7 In-situ FT-IR spectra of UiO-66 for oxidation of (a) toluene and (b) benzene under O2 and irradiation conditions

Fig. S8 Possible oxidation reaction pathways of toluene and benzene on UiO-66-OH

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配体羟基改性增强UiO-66的光热催化氧化VOCs性能

Ligand-hydroxylated UiO-66 for Enhanced Photothermally Catalytic VOCs Oxidation

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