介孔SBA-15分子筛负载复合金属氧化物催化剂的制备及其苯甲醇选择氧化性能  

Preparation of mesoporous SBA-15 zeolite supported composite metal oxide catalysts and its catalytic performance in selective oxidation of benzaldehyde

作　　者：张号东 吴雅玲 叶思远 华懿炜 李鹏飞 谢凤静 孟岩 严政 Zhang Haodong;Wu Yaling;Ye Siyuan;Hua Yiwei;Li Pengfei;Xie Fengjing;Meng Yan;Yan Zheng(Anhui Province Key Laboratory of Optoelectronic and Magnetism Functional Materials,Key Laboratory of Functional Coordination Compounds of Anhui Higher Education Institutes,Anqing Normal University,Anqing 246011,Anhui,China;College of Biological,Chemical Sciences and Engineering,Jiaxing University,Jiaxing 314001,Zhejiang,China)

机构地区：[1]安庆师范大学,安徽省光电磁功能材料重点实验室,安徽高等学校功能配合物重点实验室,安徽安庆246011 [2]嘉兴学院生物与化学工程学院,浙江嘉兴314001

出　　处：《工业催化》2022年第7期31-39,共9页Industrial Catalysis

基　　金：国家自然科学基金项目(21601002);浙江省自然科学基金项目(LY19B010002);安徽省教育厅自然科学研究重点项目(KJ2020A0511);嘉兴市公益性科研项目(2021AY10058)。

摘　　要：发展非均相氧化法取代甲苯氯化水解法和甲苯液相氧化法,实现封闭条件下苯甲醇高效选择性氧化为苯甲醛的非均相催化体系,可以为建立环境友好的绿色合成工艺提供理论支撑。设计并采用纳米浇铸法合成一系列介孔SBA-15分子筛负载型铜基复合氧化物催化剂CuO/SBA-15和CuCoO_(x)/SBA-15,并将其应用于催化苯甲醇选择性氧化制备苯甲醛反应,采用SAXS、XRD、SEM、TEM、BET、XPS、IR、TG等手段对制备的氧化物催化剂进行表征。结果表明,合成的铜钴复合氧化物中均存在尖晶石结构;Cu是CuCoO_(x)/SBA-15催化苯甲醇氧化制苯甲醛的活性位点;钴的加入能够降低二价铜的电子结合能;CuCoO_(x)/SBA-15的高效催化性能源自于催化剂CuO与CuCo_(2)O_(4)的协同催化作用。n(Cu)∶n(Co)=2∶1时,二者的协同催化效果最好。Develop a heterogeneous catalytic system for the efficient and selective oxidation of benzyl alcohol to benzaldehyde under closed conditions to replace the chlorinated hydrolysis of toluene and the liquid-phase oxidation of toluene can provide theoretical support for the establishment of an environmentally friendly green synthesis process.In this study,a series of SBA-15 zeolite supported copper-based composite oxides,namely CuO/SBA-15 and CuCoO_(x)/SBA-15,were designed and synthesized by nano-casting method,and applied to catalyze the selective oxidation of benzyl alcohol to benzaldehyde.The prepared oxides were characterized by SAXS,XRD,SEM,TEM,BET,XPS,IR,TG,etc.The results show that the copper-cobalt composite oxides have spinel structure.Cu is the active site for CuCoO_(x)/SBA-15 catalyst to catalyze the oxidation of benzyl alcohol to benzaldehyde.The addition of cobalt can reduce the electronic binding energy of divalent copper.The efficient catalytic performance of CuCoO_(x)/SBA-15 catalyst is derived from the synergistic catalytic effect of CuO and CuCo_(2)O_(4).When n(Cu)∶n(Co)=2∶1,the synergistic effect is best.

关 键 词：催化化学 非均相催化 构效关系 纳米浇铸法 铜基复合氧化物 

分 类 号：TQ426.6[化学工程] TQ244.1