金属掺杂TiO_(2)催化剂制备及其催化合成N-甲基氧化吗啉  

Preparation of metal-doped TiO_(2) catalysts and their application in synthesis of N-methylmorpholine-N-oxide

作　　者：李永威 刘建伟 李玉波 刘丹 桂建舟[1,4] LI Yongwei;LIU Jianwei;LI Yubo;LIU Dan;GUI Jianzhou(State Key Laboratory of Separation Membranes&Membrane Processes,Tianjin Key Laboratory of Green Chemical Technology and Process Engineering,School of Material Science and Engineering,Tiangong University,Tianjin 300387,China;Shandong Jinyingli New Material Technology Co.,Ltd.,Weifang 262714,Shandong,China;School of Chemistry,Tiangong University,Tianjin 300387,China;School of Chemical Engineering and Technology,Tian Gong University,Tianjin 300387,China)

机构地区：[1]分离膜与膜过程省部共建国家重点实验室,天津市绿色化工过程工程重点实验室,天津工业大学材料科学与工程学院,天津300387 [2]山东金英利新材料科技股份有限公司,山东潍坊262714 [3]天津工业大学化学学院,天津300387 [4]天津工业大学化学工程与技术学院,天津300387

出　　处：《精细化工》2022年第2期337-344,共8页Fine Chemicals

基　　金：国家自然科学基金项目(21576211);天津市科技发展计划项目(21ZYJDJC00100)。

摘　　要：以H_(2)Ti_(3)O_(7)纳米线为前驱体,通过简单的离子交换和高温焙烧两步制备了具有不同金属掺杂的y M/TiO_(2)催化剂(M=Fe、Co、Ni,y=0.25%、0.75%、1.25%、1.75%、2.25%,y表示金属M的质量百分比)。通过XRD、SEM、TEM、XPS对催化剂进行了表征,考察了y M/TiO_(2)催化剂在以H_(2)O_(2)为氧化剂催化氧化N-甲基吗啉(NMM)合成N-甲基氧化吗啉(NMMO)反应中的催化性能。结果显示,掺杂的金属元素均匀分散在制备的TiO_(2)纳米线基体表面,y M/TiO_(2)催化剂形貌为纳米线/纳米棒。当掺杂的金属Fe含量为1.75%时,催化剂表面缺陷氧含量高达16.86%,催化性能最佳,在反应温度为35℃、反应3 h后NMMO产率达到97.5%,表明金属离子的掺入造成TiO_(2)晶体结构中局部晶格扭曲,导致催化剂表面形成较多的氧空位,提升了催化活性。y M/TiO_(2) catalysts(M=Fe,Co,Ni,y=0.25%,0.75%,1.25%,1.75%,2.25%,y is mass percent of metal M)with different metal-doped were prepared using H2Ti3O7 nanowires as precursors by simple ion exchange and high temperature calcination,and characterized by XRD,SEM,TEM and XPS.The catalytic performance of y M/TiO_(2) catalysts in the synthesis of N-methylmorpholine(NMM)to N-methylmorpholine-N-oxide(NMMO).The results showed that the doped metal elements were evenly dispersed on the surface of the prepared TiO_(2) nanowire matrix.y M/TiO_(2) catalysts were in the forms of nanowire/nanorod morphology.When the doped metal Fe content was 1.75%,the surface defect oxygen content of the catalyst was as high as 16.86%,and the catalytic performance was the best.The yield of NMMO reached 97.5%after reaction at 35℃for 3 h,indicating that the doping of metal ions caused the distortion of local lattice in the TiO_(2) crystal structure,resulting in the formation of more oxygen vacancies on the catalyst surface and improved the catalytic activity.

关 键 词：yM/TiO_(2) 掺杂 N-甲基氧化吗啉 催化氧化 选择性 催化技术 

分 类 号：TQ032.4[化学工程]