钛基金属-有机框架材料的改性及其催化性能研究

doi:10.11949/0438-1157.20191213

摘要/Abstract

摘要：

使用双氧水在一定温度下对钛基金属-有机框架材料NH₂-MIL-125进行改性处理，制备得到一系列材料，系统地研究了改性方法及改性条件对材料性能的影响。结果表明，经改性处理后的材料，在可见光催化苯甲醇氧化反应中的催化速率有显著提高；同时，改性过程中的双氧水用量及改性温度对材料的结构、性质和光催化性能都有十分重要的影响。当双氧水为10 ml、改性温度为50℃时，改性材料具有优异的催化活性、选择性以及良好的稳定性，其催化速率与NH₂-MIL-125相比提高近6倍。

关键词: 金属-有机框架, NH₂-MIL-125, 催化剂, 光化学, 氧化

Abstract:

A series of materials were prepared by modifying titanium based metal-organic framework material NH₂-MIL-125 with hydrogen peroxide at a certain temperature. The effects of modification methods and conditions on the properties of materials were studied systematically. However, NH₂-MIL-125 as a photocatalyst suffers from low catalytic activity and stability, which largely restrict its practical applications. In order to improve the catalytic activity of NH₂-MIL-125, a solvothermal route by using H₂O₂ was used to modify NH₂-MIL-125. A series of materials were synthesized by treating NH₂-MIL-125 with different volumes of H₂O₂ at different temperatures. X-ray diffraction, scanning electron microscope, transmission electron microscope, ultraviolet-visible light absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and N₂ adsorption analysis were used to characterize the structures and properties of the obtained product. Furthermore, their photocatalytic performances for the visible-light-driven oxidation of benzyl alcohol were tested. The results show that the product modified by 10 ml H₂O₂ at 50℃ exhibits excellent catalytic activity and selectivity. The maximum turnover frequency is nearly 6 times as high as that of NH₂-MIL-125 at the same experimental conditions. The partial loss of organic ligands and the introduction of peroxide groups could generate more catalytic-active sites, which is responsible for the improved catalytic activity.

Key words: metal-organic framework, NH₂-MIL-125, catalyst, photochemistry, oxidation

中图分类号:

TQ 028.8

曲云鹏, 张丙兴, 石金彪, 谭秀娘, 韩布兴, 杨冠英, 张建玲. 钛基金属-有机框架材料的改性及其催化性能研究[J]. 化工学报, 2020, 71(1): 283-289.

Yunpeng QU, Bingxing ZHANG, Jinbiao SHI, Xiuniang TAN, Buxing HAN, Guanying YANG, Jianling ZHANG. Study on modification of titanium-based metal-organic framework and catalytic performance[J]. CIESC Journal, 2020, 71(1): 283-289.

图/表 9

表1 样品改性处理条件

Table 1 Modification condition of samples

样品编号	NH₂-MIL-125质量/g	双氧水体积/ml	处理温度/℃
1	1.0	10	50
2	1.0	20	50
3	1.0	30	50
4	1.0	10	70
5	1.0	10	90

图1 NH2-MIL-125和样品1的SEM和TEM图

Fig.1 SEM and TEM images of NH2-MIL-125 and sample 1

图2 NH2-MIL-125和样品1的XRD谱图

Fig.2 XRD patterns of NH2-MIL-125 and sample 1

图3 NH2-MIL-125和样品1的氮吸附-脱附等温线和孔径分布

Fig.3 N2 adsorption-desorption isotherms and pore size distribution curves of NH2-MIL-125 and sample 1

图4 NH2-MIL-125和样品1的红外光谱图

Fig.4 IR spectra of NH2-MIL-125 and sample 1

图5 样品1的XPS谱图

Fig.5 XPS spectra of sample 1

图6 样品1和NH2-MIL-125的催化转化数TON随时间的变化

Fig.6 Turnover numbers (TONs) of sample 1 and NH2-MIL-125 vs time

图7 NH2-MIL-125和样品1的紫外-可见吸收光谱图

Fig.7 UV-Vis spectra of NH2-MIL-125 and sample 1

图8 改性处理条件对材料催化速率TOF的影响

Fig.8 Influences of modification conditions on turnover frequency (TOF)

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