The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
作者:Francisco R. Fortea-Pérez、Marta Mon、Jesús Ferrando-Soria、Mercedes Boronat、Antonio Leyva-Pérez、Avelino Corma、Juan Manuel Herrera、Dmitrii Osadchii、Jorge Gascon、Donatella Armentano、Emilio Pardo
DOI:10.1038/nmat4910
日期:2017.7
The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metalâorganic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes. Mixed-valence clusters of Pd4 organized within a metalâorganic framework exhibit robust catalytic capacities during carbene-mediated chemical reactions.
开发能够辅助工业重要化学过程的催化剂是一个高度重要的话题。鉴于小金属簇的催化能力,研究工作集中在合成具有这种活性位点的新型催化剂上。我们在此报告了一种异相催化剂,由具有混合价态0/+1的Pd4簇组成,这些簇在金属有机框架(MOF)的墙壁内被稳定并均匀组织。所得的固体催化剂在以烯基化合物介导的二氮酸乙酯反应中,优于最先进的金属催化剂,获得了高于90%的产率和高达100,000的周转数。此外,MOF支持的Pd4簇在重复的批量和流动反应中保持了其催化活性(超过20个周期)。我们的研究结果表明,这种合成方法如何能够指导未来异相催化剂的设计,以便用于其他重要过程。组织在金属有机框架内的Pd4混合价簇在以烯基化合物为介导的化学反应中表现出强大的催化能力。