酞菁敏化MIL-53(Al)光催化氧化脱硫性能  

Photocatalytic oxidative desulfurization performance of phthalocyanine sensitized MIL-53(Al)

作　　者：赵凯慧 张雨帆 朱亚芳 田敏[1] 杨嫣[1] 张改[1] ZHAO Kaihui;ZHANG Yufan;ZHU Yafang;TIAN Min;YANG Yan;ZHANG Gai(School of Materials and Chemical Engineering,Xi'an Technological University,Xi'an 710021,Shaanxi,China)

机构地区：[1]西安工业大学材料与化工学院,陕西西安710021

出　　处：《精细化工》2024年第10期2231-2237,共7页Fine Chemicals

基　　金：陕西省科技厅自然科学基金面上项目(2023-JC-YB-245)。

摘　　要：采用水热法将羧基取代金属酞菁(MTc Pc,M=Mn、Fe、Co、Ni、Cu、Zn)负载在金属有机框架MIL-53(Al)表面上,制备了复合材料MTcPc/MIL-53(Al)。通过SEM、XRD、FTIR、UV-Vis吸收光谱和XPS对MTcPc/MIL-53(Al)进行了表征,在常温常压、空气中氧气为氧化剂的条件下,测试其对噻吩/正辛烷为模拟燃油的光催化氧化脱硫性能。结果表明,MTcPc分子以有序晶态形式较均匀地分散在MIL-53(Al)表面上,其平面共轭结构对MIL-53(Al)晶体特定方向的生长具有明显诱导作用。与MTcPc相比,MTcPc/MIL-53(Al)的Q带存在一定程度的红移,扩展了光响应范围。MnTcPc/MIL-53(Al)表现出最佳的光催化脱硫性能,催化反应150 min,噻吩转化率100%,经4次循环后,噻吩转化率为93.01%。MTcPc与MIL-53(Al)之间的π-π堆积作用提高了MTcPc的分散,MIL-53(Al)的呼吸效应促进了噻吩分子和氧分子在MTcPc/MIL-53(Al)表面的强吸附富集作用,有利于活性中间体MIL-53(Al)/MTcPc–^(1)O_(2)的形成,从而提高了氧化脱硫的活性;MTcPc的共轭结构和中心离子的构型也是影响氧化脱硫效率的重要因素。Composite MTcPc/MIL-53(Al)were prepared by loading carboxyl substituted metal phthalocyanines(MTcPc,M=Mn,Fe,Co,Ni,Cu,Zn)on the surface of metal-organic framework MIL-53(Al)via hydrothermal method,characterized by SEM,XRD,FTIR,UV-Vis absorption spectrum and XPS,and evaluated for its photocatalytic oxidation desulfurization performance on thiophene/n-octane simulated fuel at room temperature and atmospheric pressure with oxygen in air as oxidant.The results showed that MTcPc molecules were evenly dispersed on the surface of MIL-53(Al)in an ordered crystalline form,with their planar conjugated structure inducing the growth of MIL-53(Al)crystal in a specific direction.Compared with that of MTcPc,the Q band of MTcPc/MIL-53(Al)displayed a certain degree of redshift,resulting in the extension of optical response range.MnTcPc/MIL-53(Al)showed the best photocatalytic desulfurization performance.After 150 min of catalytic reaction,the conversion rate of thiophene reached 100%,and maintained at 93.01%after 4 cycles.Theπ-πaccumulation between MTcPc and MIL-53(Al)improved the dispersion of MTcPc,and the respiration effect of MIL-53(Al)promoted the strong adsorption and enrichment of thiophene and oxygen molecules on MTcPc/MIL-53(Al)surface,which was beneficial to the formation of active intermediates MIL-53(Al)/MTcPc–^(1)O_(2),thus improving the activity of oxidative desulfurization.The conjugated structure of MTcPc and the configuration of the central ion also exhibited strong influence on the efficiency of oxidative desulfurization.

关 键 词：金属酞菁 MIL-53(Al) 水热法 光催化 氧化脱硫 催化技术 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]