Synergic catalysis of W and Ni originating from substitution of trivacant phosphotungstate for the selective oxidation of aniline to azoxybenzene  

作　　者：Sheng Cai Xiao-Yuan Wu Weiming Wu Sa-Sa Wang Can-Zhong Lu 

机构地区：[1]CAS Key Laboratory of Design and Assembly of Functional Nanostructures,and Fujian Provincial Key Laboratory of Nanomaterials,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350117,China [3]Xiamen Institute of Rare Earth Materials,Chinese Academy of Sciences,Xiamen 361021,China [4]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Chemical Letters》2024年第2期558-563,共6页中国化学快报(英文版)

基　　金：supported by the National Natural Science Foundation of China(Nos.21773247,22275185,21521061,21875252);the Natural Science Foundation of Fujian Province(No.2006L2005).

摘　　要：Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_(2)}{[Ni_(6)Cl(μ-OH)_(3)(H_(2)O)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))][Ni_(6)(μ-OH)_(3)(H_(2)O)_(2)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))]}Cl·27H_(2)O,(1,Dach=1,2-diaminocyclohexane)was synthesized.Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene(AOB)in water.The apparently different results from that with the matrix{PW_(9)O_(34)}({PW9})suggest the successful regulation of the catalytic property of{PW9}by the introduction of the{Ni6}cluster into the skeleton.The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites,which are respectively responsible for the oxidation and condensation steps in the production of AOB.The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites,respectively.

关 键 词：Polyoxometalate {Ni_(6)}cluster Modulated catalytic property Aniline oxidation AZOXYBENZENE 

分 类 号：TQ246.5[化学工程—有机化工] O643.36[理学—物理化学]