Kaneda Kiyotomi, Mitsudome Takato
Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan.
Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan.
Chem Rec. 2017 Jan;17(1):4-26. doi: 10.1002/tcr.201600036. Epub 2016 Jul 26.
Metal-support cooperative catalysts have been developed for sustainable and environmentally benign molecular transformations. The active metal centers and supports in these catalysts could cooperatively activate substrates, resulting in high catalytic performance for liquid-phase reactions under mild conditions. These catalysts involved hydrotalcite-supported gold and silver nanoparticles with high catalytic activity for organic reactions such as aerobic oxidation, oxidative carbonylation, and chemoselective reduction of epoxides to alkenes and nitrostyrenes to aminostyrenes using alcohols and CO/H O as reducing reagents. This high catalytic performance was due to cooperative catalysis between the metal nanoparticles and basic sites of the hydrotalcite support. To increase the metal-support cooperative effect, core-shell nanostructured catalysts consisting of gold or silver nanoparticles in the core and ceria supports in the shell were designed. These core-shell nanocomposite catalysts were effective for the chemoselective hydrogenation of nitrostyrenes to aminostyrenes, unsaturated aldehydes to allyl alcohols, and alkynes to alkenes using H as a clean reductant. In addition, these solid catalysts could be recovered easily from the reaction mixture by simple filtration, and were reusable with high catalytic activity.
金属-载体协同催化剂已被开发用于可持续且环境友好的分子转化。这些催化剂中的活性金属中心和载体能够协同活化底物,从而在温和条件下对液相反应表现出高催化性能。这些催化剂包括水滑石负载的金和银纳米颗粒,它们对有机反应具有高催化活性,例如需氧氧化、氧化羰基化,以及使用醇和CO/H₂O作为还原剂将环氧化物化学选择性还原为烯烃、将硝基苯乙烯化学选择性还原为氨基苯乙烯。这种高催化性能归因于金属纳米颗粒与水滑石载体碱性位点之间的协同催化作用。为了增强金属-载体协同效应,设计了核壳纳米结构催化剂,其核由金或银纳米颗粒组成,壳由二氧化铈载体组成。这些核壳纳米复合催化剂使用H₂作为清洁还原剂,对将硝基苯乙烯化学选择性氢化为氨基苯乙烯、将不饱和醛氢化为烯丙醇以及将炔烃氢化为烯烃均有效。此外,这些固体催化剂可通过简单过滤轻松从反应混合物中回收,并且可重复使用且具有高催化活性。