Highly dispersive tetrahedral vanadium species on pure silica ZSM-12 zeolite boosting the selective oxidation of cyclohexane into cyclohexanone  

作　　者：Menglin Xie Ting Li Chao Wu Xiaoling Liu Jinling Ni Siqin Yao Yu Zhou Shibo Xi Jun Wang 

机构地区：[1]State Key Laboratory of Materials-Oriented Chemical Engineering,College of Chemical Engineering,Nanjing Tech University,Nanjing 211816,China [2]Institute of Sustainability for Chemicals,Energy and Environment(ISCE2),Agency for Science,Technology and Research(A*STAR),Singapore 627833,Republic of Singapore [3]College of Materials Science and Engineering,Sichuan University,Chengdu 610065,China

出　　处：《Science China Chemistry》2024年第7期2206-2214,共9页中国科学（化学英文版）

基　　金：financially supported by the National Natural Science Foundation of China(22222806,22178162,and 22072065);the Distinguished Youth Foundation of Jiangsu Province(BK20220053);the Six Talent Peaks Project in Jiangsu Province(JNHB035)。

摘　　要：The selective oxidation of cyclohexane is a promising green route for the production of KA oil(cyclohexanol and cyclohexanone),but remains a huge challenge to design high-performing heterogeneous catalysts under mild conditions.Herein,a pure silica ZSM-12(MTW topology)zeolite was applied as the support to immobilize highly dispersive tetrahedrally coordinated vanadium(V)species and the constructed catalyst 1%V/SZ-12 exhibited high efficiency in the fast and selective oxidation of cyclohexane into cyclohexanone with H_(2)O_(2).The reaction completed within 30 s,affording the selectivity of 99%towards cyclohexanone and the extremely high turnover frequency(TOF)of 5,891 h^(-1).1%V/SZ-12 was facilely reused with stable activity and feasibly extended to the oxidation of various cyclohexane derivatives.The one-dimensional 12-membered ring microchannels contributed to the formation and accessibility of tetrahedrally coordinated high valent V5+species as the robust active centers,which activated H_(2)O_(2) to generate V–O–O·,the active oxygen species for the electrophilic attack on cyclohexane to produce cyclohexanone as the sole product.

关 键 词：ZEOLITE metal doping cyclohexane oxidation heterogeneous catalysis 

分 类 号：TQ234.21[化学工程—有机化工] O643.36[理学—物理化学]