NH 2 -UIO-66 负载 RuCuMo 纳米催化剂 的制备及其催化产氢 张翊青, 刘 梨, 张淑娟, 万正睿, 刘红英, 周立群 (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, 武 汉 430062) 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 NH 2 -UIO-66, 并利用 浸渍还原法成功负载 RuCuMo 纳米粒子, 制备了 RuCuMo@NH 2 -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 NH 2 -UIO-66、RuCuMo@NH 2 -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, Ru 1 Cu 2 Mo 0.5 @NH 2 -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 NH 2 -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(E a ) 为 30.1 kJmol -1 , 转化频率(TOF)为 180.83 2 1 1 H R u mol mol min , 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。 关 键 词: 金属有机骨架(NH 2 -UIO-66); RuCuMo@NH 2 -UIO-66; 溶剂热法; 协同催化; 产氢性能 中图分类号: O643 文献标识码: A Abstract: Amine-functionalize metal organic framework (NH 2 -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@NH 2 -UIO-66 catalysts. The structure, morphology, composition and specific surface area of the above catalysts were characterized. Ru 1 Cu 2 Mo 0.5 @NH 2 -UIO-66 catalyst exhibits 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 (E a ) and turnover frequency values (TOF) are 30.1 kJmol -1 and 180.83 mol H 2 min -1 (mol Ru) -1 , respectively. Addition of 第 12 期 张翊青, 等: NH 2 -UIO-66 负载 RuCuMo 纳米催化剂的制备及其催化产氢 1317 Cu and Mo can significantly enhance the catalytic activity of Ru counterparts, owing to the synergistic effect among Ru, Cuand Mo atoms, bi-functional effect generated between RuCuMo NPs and NH 2 -UIO-66 support, and the amine as anchoring groups in the NH 2 -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.