中科院化学所曹昌燕团队报道了石墨烯负载氧化亚铜纳米团簇催化剂中电子氧化物-负载强相互作用。相关研究成果发表在2023年1月13日出版的《美国化学会杂志》。

负载型催化剂中的界面相互作用对于多相催化具有重要意义，因为它可以诱导电荷转移，调节活性位点的电子结构，影响反应物吸附行为，并最终影响催化性能。它在金属/氧化物催化剂和氧化物/金属反催化剂中得到了很好的理论和实验解释，但由于传统碳材料的惰性，很少在碳负载催化剂中报道。

使用石墨烯负载的氧化亚铜纳米簇催化剂（Cu₂O NCs/GDY）的实例，研究人员证明了它们之间的强电子相互作用，并提出了一种新型的电子氧化物——石墨烯强相互作用，类似于氧化物/金属反催化剂中的电子氧化物/金属强相互作用的概念。这种电子氧化物-石墨烯二炔的强相互作用不仅可以使Cu₂O NCs稳定在低氧化状态，而不会在环境条件下聚集和氧化，还可以改变其电子结构，从而优化反应物/中间体的吸附能，从而提高Cu（I）催化的叠氮化物-炔环加成反应的催化活性。

研究结果将有助于全面理解负载型催化剂中的界面相互作用。

附：英文原文

Title: Electronic Oxide–Support Strong Interactions in the Graphdiyne-Supported Cuprous Oxide Nanocluster Catalyst

Author: Jia Yu, Weiming Chen, Feng He, Weiguo Song, Changyan Cao

Issue&Volume: January 13, 2023

Abstract: The interfacial interaction in supported catalysts is of great significance for heterogeneous catalysis because it can induce charge transfer, regulate electronic structure of active sites, influence reactant adsorption behavior, and eventually affect the catalytic performance. It has been theoretically and experimentally elucidated well in metal/oxide catalysts and oxide/metal inverse catalysts, but is rarely reported in carbon-supported catalysts due to the inertness of traditional carbon materials. Using an example of a graphdiyne-supported cuprous oxide nanocluster catalyst (Cu2O NCs/GDY), we herein demonstrate the strong electronic interaction between them and put forward a new type of electronic oxide–graphdiyne strong interaction, analogous to the concept of electronic oxide/metal strong interactions in oxide/metal inverse catalysts. Such electronic oxide–graphdiyne strong interaction can not only stabilize Cu2O NCs in a low-oxidation state without aggregation and oxidation under ambient conditions but also change their electronic structure, resulting in the optimized adsorption energy for reactants/intermediates and thus leading to improved catalytic activity in the Cu(I)-catalyzed azide–alkyne cycloaddition reaction. Our study will contribute to the comprehensive understanding of interfacial interactions in supported catalysts.

DOI: 10.1021/jacs.2c10976

Source: https://pubs.acs.org/doi/10.1021/jacs.2c10976