Guo Miao, Jayakumar Sanjeevi, Luo Mengfei, Kong Xiangtao, Li Chunzhi, Li He, Chen Jian, Yang Qihua
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
Nat Commun. 2022 Apr 1;13(1):1770. doi: 10.1038/s41467-022-29299-0.
The utilization of weak interactions to improve the catalytic performance of supported metal catalysts is an important strategy for catalysts design, but still remains a big challenge. In this work, the weak interactions nearby the Pd nanoparticles (NPs) are finely tuned by using a series of imine-linked covalent organic frameworks (COFs) with different conjugation skeletons. The Pd NPs embedded in pyrene-COF are ca. 3 to 10-fold more active than those in COFs without pyrene in the hydrogenation of aromatic ketones/aldehydes, quinolines and nitrobenzene, though Pd have similar size and surface structure. With acetophenone (AP) hydrogenation as a model reaction, systematic studies imply that the π-π interaction of AP and pyrene rings in the vicinity of Pd NPs could significantly reduce the activation barrier in the rate-determining step. This work highlights the important role of non-covalent interactions beyond the active sites in modulating the catalytic performance of supported metal NPs.
利用弱相互作用来提高负载型金属催化剂的催化性能是催化剂设计的重要策略，但仍然是一个巨大的挑战。在这项工作中，通过使用一系列具有不同共轭骨架的亚胺连接的共价有机框架（COF）对钯纳米颗粒（NP）附近的弱相互作用进行了精细调节。尽管钯纳米颗粒的尺寸和表面结构相似，但嵌入芘-COF中的钯纳米颗粒在芳香酮/醛、喹啉和硝基苯的氢化反应中的活性比不含芘的COF中的钯纳米颗粒高约3至10倍。以苯乙酮（AP）氢化为模型反应，系统研究表明，钯纳米颗粒附近的AP与芘环之间的π-π相互作用可显著降低速率决定步骤中的活化能垒。这项工作突出了活性位点之外的非共价相互作用在调节负载型金属纳米颗粒催化性能方面的重要作用。
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