NH2-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢  

Preparation and Dehydrogenation Property of NH2-UIO-66 Supported RuCuMo Nanocatalyst

作　　者：张翊青 刘梨 张淑娟 万正睿 刘红英[1] 周立群[1] ZHANG Yi-Qing;LIU Li;ZHANG Shu-Juan;WAN Zheng-Rui;LIU Hong-Ying;ZHOU Li-Qun(Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials,Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules,College of Chemistry and Chemical Engineering,Hubei University,Wuhan 430062,China)

机构地区：[1]湖北大学化学化工学院有机化工新材料湖北省协同创新中心有机功能分子合成与应用教育部重点实验室

出　　处：《无机材料学报》2019年第12期1316-1324,共9页Journal of Inorganic Materials

基　　金：湖北省自然科学基金(2010CDB04701);湖北省教育厅重点项目(D20101011);有机功能分子合成与应用教育部重点实验室项目(2016-KL-007);湖北省大学生创新创业训练项目(201510512030)~~

摘　　要：采用锆盐和2-氨基对苯二甲酸以溶剂热法成功制备了氨基化的金属有机骨架化合物NH2-UIO-66,并利用浸渍还原法成功负载RuCuMo纳米粒子,制备了RuCuMo@NH2-UIO-66催化剂。通过X射线粉末衍射仪(XRD)、透射电子显微镜(TEM)、场发射扫描电镜(SEM)等技术对NH2-UIO-66、RuCuMo@NH2-UIO-66的结构、形貌、组成和比表面积进行了表征,并对载体、多金属负载型催化剂以及无载体的RuCuMo纳米粒子的产氢性能进行了分析。结果显示,Ru1Cu2Mo0.5@NH2-UIO-66催化剂的催化活性最高,引入Cu和Mo能显著增强Ru对氨硼烷水解产氢的催化活性。这主要归因于RuCuMo纳米粒子之间强的协同作用,RuCuMo纳米粒子与载体NH2-UIO-66间的双功能效应,以及MOFs上氨基的锚锭作用,可以阻止金属粒子的团聚,促进超细粒子的形成。催化反应的活化能(Ea)为30.1 kJ mol 1,转化频率(TOF)为180.83 molH2 mol R1u min 1,非贵金属Cu和Mo的引入为催化活性的提高和工业应用提供了重要的研究价值。Amine-functionalize metal organic framework(NH2-UIO-66)was successfully synthesized by solvothermal method with zirconium salt and 2-aminoterephtalic acid.Tri-metallic RuCuMo nanoparticles(NPs)were immobilized by a facile impregnation-reduction method to prepare RuCuMo@NH2-UIO-66 catalysts.The structure,morphology,composition and specific surface area of the above catalysts were characterized.Ru1Cu2Mo0.5@NH2-UIO-66 catalyst exh-ibits the highest catalytic activity comparing with Ru,RuCu and CuMo counterparts as well as pure tri-metallic RuCuMo NPs in hydrolytic dehydrogenation of ammonia borane at room temperature,and the correspoding activation energy(Ea)and turnover frequency values(TOF)are 30.1 kJ mol 1 and 180.83 mol H2 min 1(mol Ru)1,respectively.Addition of Cu and Mo can significantly enhance the catalytic activity of Ru counterparts,owing to the synergistic effect among Ru,Cu and Mo atoms,bi-functional effect generated between RuCuMo NPs and NH2-UIO-66 support,and the amine as anchoring groups in the NH2-UIO-66 framework,which facilitate the formation and stabilization of ultra-small RuCuMo NPs by preventing their aggregation.The addition of non-noble metals Cu and Mo provides an important approach for the improvement of catalytic activity and industrial application.

关 键 词：金属有机骨架(NH2-UIO-66) RuCuMo@NH2-UIO-66 溶剂热法 协同催化 产氢性能 

分 类 号：O643[理学—物理化学]