Feng Yunchao, Wang Hongtao, Chen Tianxiang, Lopez-Haro Miguel, He Feng, He Zhe, Marini Carlo, Lo Benedict Tsz Woon, Liu Lichen
Department of Chemistry, Engineering Research Center of Advanced Rare Earth Materials, Tsinghua University, 100084, Beijing, China.
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, 999077, Kowloon, Hong Kong, China.
Nat Commun. 2024 Oct 30;15(1):9373. doi: 10.1038/s41467-024-53475-z.
A fundamental understanding of the active sites in working catalysts can guide the rational design of new catalysts with improved performances. In this work, we have followed the evolution of homogeneous and heterogeneous Pd catalysts under the reaction conditions for aerobic oxidative coupling of toluene for the production of 4,4'-bitolyl. We have found that subnanometer Pd clusters made with a few Pd atoms are the working active sites in both homogeneous and heterogeneous catalytic systems. Moreover, water can promote the activity of Pd clusters by nearly one-order magnitude for oxidative coupling reaction by facilitating the activation of O. These new insights lead to the preparation of a catalyst made with Pd clusters supported on a two-dimensional zeolite, which expands the scope of the oxidative coupling of aromatics to larger substrates.
对工作催化剂中活性位点的基本理解可以指导合理设计性能更优的新型催化剂。在这项工作中，我们追踪了均相和非均相钯催化剂在甲苯有氧氧化偶联制4,4'-联甲苯反应条件下的演变。我们发现，由几个钯原子构成的亚纳米钯簇是均相和非均相催化体系中的工作活性位点。此外，水可通过促进氧的活化，使钯簇的氧化偶联反应活性提高近一个数量级。这些新的见解促使人们制备出一种由负载在二维沸石上的钯簇构成的催化剂，这将芳烃氧化偶联的范围扩展到了更大的底物。
