Cobalt-manganese bimetallic organic frameworks catalyzed solvent-free oxidation of benzyl C-H bonds with O_(2) as sole oxidant  

作　　者：Ke Cao Yan Zhou Shanshan Lv Mengmeng Feng Changjin Qian Zheng Chen 

机构地区：[1]Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241002, China [2]State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210023, China

出　　处：《Nano Research》2024年第11期9532-9539,共8页纳米研究（英文版）

基　　金：supported by the Key Research and Development Project of Anhui Province(No.2022a05020048);the Open Project of Anhui Provincial Key Laboratory for Degradation and Monitoring of Pollution of the Environment(No.FSKFKT007D);the State Key Laboratory of Heavy Oil Processing(No.SKLHOP202202007);the Excellent Youth Research Project in Universities of Anhui Province(No.2023AH030050);the University Collaborative Innovation Project of Anhui Province(No.GXXT-2023-034).

摘　　要：The selective oxidation of hydrocarbons can be used to produce oxygen-containing functional compounds such as alcohols, aldehydes or ketones and its efficient and green conversion lies in the development of efficient catalysts that activate C-H bonds and O_(2) simultaneously. In this work, the bimetallic organic framework (CoMnBDC) material with morphology of stacked nanosheets was synthesized using terephthalic acid as ligands to coordinate with Co^(2+) and Mn^(2+) cations under solvothermal conditions. As revealed by spectroscopic characterizations, the electron transfer from Mn to Co in the CoMnBDC resulted in the reduction of the Co average oxidation state and increase of the Mn average oxidation state. The CoMnBDC nanosheets were used as catalyst in catalytic oxidation of ethylbenzene, in which the redox effect promotes the effective electron transfer, the activation of O_(2) and benzyl C-H bond. The 96.2% conversion of ethylbenzene and 98.0% selectivity towards acetophenone could be obtained with oxygen as sole oxidant and solvent-free condition. The excellent catalytic performance is related to the structure of CoMnBDC and is also the best when compared with reported results. Various types of aromatic hydrocarbons containing benzyl C-H bonds can be effectively oxidized by CoMnBDC to produce corresponding ketone products. The density functional theory (DFT) calculation revealed that the redox effect leads to the relative enrichment of electrons on Co in CoMnBDC, which is conducive to the activation of O_(2);Mn with higher oxidation state is beneficial for the adsorption of ethylbenzene and activation of C-H bonds. The CoMnBDC has a lower energy barrier for transition state, making it easier for the ethylbenzene oxidation to produce acetophenone.

关 键 词：metallic organic framework transition metal NANOCATALYSIS oxidation KETONE 

分 类 号：O62[理学—有机化学]