PW11M（M=Cu、 Co）@TiO2多相催化剂的制备及氧化脱硫性能  

Preparation of PW11M（M=Cu, Co）@TiO2 Heterogeneous Catalysts and Oxidative Desulfurization Performance

作　　者：高洪成[1] 王秀艳[1] 张晓飞[1] 刘云鹤[1] 祁强[1] 宋晓静 GAO Hong-cheng;WANG Xiu-yan;ZHANG Xiao-fei;LIU Yun-he;QI Qiang;SONG Xiao-jing(Department of Chemical Engineering,Chengde Petroleum College,Chengde 067000,China;Nanyang Institute of Technology,College of Biological and Chemical Engineering,Nanyang 473004,China)

机构地区：[1]承德石油高等专科学校化学工程系,河北承德067000 [2]南阳理工学院生物与化学工程学院,河南南阳473004

出　　处：《分子催化》2019年第5期438-446,共9页Journal of Molecular Catalysis(China)

基　　金：河北省自然科学青年基金(B2017411009)~~

摘　　要：以过渡金属(Cu,Co)取代磷钨酸为模板剂,硫酸钛为钛源,通过一步模板法合成出一类多酸基PW11M(M=Cu、Co)@TiO2材料,采用FT-IR、XRD、XPS、Raman、SEM和TEM表征手段对材料进行了结构表征.结果表明,PW11M(M=Cu、Co)被引入到TiO2中,形成了球形核壳结构.N2吸附-脱附测试表明,PW11Co@TiO2具有介孔结构:孔径大小为3.3 nm,比表面积为72.4 m2/g.在以H2O2为氧化剂,乙腈为溶剂的氧化脱硫反应体系中考察了其催化活性,结果表明:复合材料PW11M(M=Cu、Co)@TiO2表现出良好的催化性能.其中催化剂PW11Co@TiO2在投入量为40 mg,反应底物为500 ppm,反应温度60℃,反应40 min后,DBT的脱硫率达到99.7%.中断和循环实验表明,催化剂PW11Co@TiO2具有良好的稳定性,在相同的反应条件下,循环反应5次后,催化剂的催化活性没有明显下降.A polyoxometalate-based materials has been synthesized though the one-step template using transition metal(Cu,Co)substituted phosphotungstic acid as template and titanium sulfate as titanium source,denoted as PW11M(M=Cu,Co)@TiO2.Multiple characterization methods namely FT-IR,XRD,XPS,Raman,SEM and TEM were used to characterize the resultant materials,and results indicated that PW11M(M=Cu,Co)is introduced into TiO2,forming core-shell spherical structure.N2 adsorption-desorption test showed that PW11Co@TiO2 was mesoporous material with pore size of 3.3 nm and specific surface area of 72.4 m2/g.The catalytic properties of these materials were investigated in the oxidative desulfurization reaction system with H2O2 as oxidant and acetonitrile as solvent.The results showed that the PW11M(M=Cu,Co)@TiO2 exhibited good catalytic performance.The S-removal of DBT reached 99.7%after 40 min reaction at a temperature of 60℃when dosage of catalyst PW11Co@TiO2 was 40 mg and reaction substrate was 500 mg/kg.Leaching and recycling experiments revealed that catalyst PW11Co@TiO2 had excellent stability,and there was no significant decrease in S-removal after five cycles under same reaction conditions.

关 键 词：过渡金属 多金属氧酸盐 TIO2 多相催化 氧化脱硫 

分 类 号：O643.3[理学—物理化学]