Zhao Yiming, Zhou Yan, Lv Shanshan, Li Han, Wu Qikang, Liu Shaohuan, Li Wanying, Chen Taiyu, Chen Zheng
Key Laboratory of Functional, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University Wuhu 241000 China
Chem Sci. 2023 Mar 29;14(17):4620-4626. doi: 10.1039/d2sc06738b. eCollection 2023 May 3.
Single-atom Cu supported on CeO nanorod catalysts (Cu/CeO ) have been synthesized through the anchoring of copper by terminal hydroxyl groups on the CeO surface. The oxygen defect characteristics of the CeO nanorods promote electron transfer between Cu and CeO through a Ce-O-Cu interface, which realizes flexible electronic regulation of the Cu sites. Single-atom Cu species with an oxidation state of between +1 and +2 were formed, which was confirmed by X-ray photoelectron spectroscopy, X-ray fine structure spectroscopy, and electron paramagnetic resonance spectroscopy. Cu/CeO emerged as a catalyst with advanced catalytic performance for elemental sulfur in -arylation using aryl iodides, achieving 97.1% iodobenzene conversion and 94.8% selectivity toward diphenyl disulfide. The substituted iodobenzene with different electronic or steric groups successfully realized -arylation and produced the corresponding diaryl disulfides with high selectivity. The fully exposed single-atom Cu with flexible electronic characteristics successively realized oxidative addition or coordination of multiple substrates, making it possible to obtain diaryl disulfide with high selectivity.
通过铜与CeO₂表面末端羟基的锚定作用,合成了负载在CeO₂纳米棒催化剂(Cu/CeO₂)上的单原子铜。CeO₂纳米棒的氧缺陷特性通过Ce-O-Cu界面促进了铜与CeO₂之间的电子转移,从而实现了对铜位点的灵活电子调控。形成了氧化态介于+1和+2之间的单原子铜物种,这通过X射线光电子能谱、X射线精细结构光谱和电子顺磁共振光谱得到了证实。Cu/CeO₂作为一种对使用芳基碘化物进行芳基化反应中的元素硫具有先进催化性能的催化剂脱颖而出,实现了97.1%的碘苯转化率和94.8%对二苯基二硫醚的选择性。带有不同电子或空间基团的取代碘苯成功实现了芳基化反应,并以高选择性生成了相应的二芳基二硫醚。具有灵活电子特性的完全暴露单原子铜相继实现了多种底物的氧化加成或配位,使得能够以高选择性获得二芳基二硫醚。