Construction of one Ru_(2)W_(12)-cluster and six lacunary Keggin tungstoarsenate leading to the larger Ru-containing polyoxometalate photocatalyst  

作　　者：Huafeng Li Mengnan Yang Zelong Yuan Yahao Sun Pengtao Ma Jingyang Niu Jingping Wang 

机构地区：[1]Henan Key Laboratory of Polyoxometalate Chemistry,College of Chemistry and Chemical Engineering,Henan University,Kaifeng 475004,China

出　　处：《Chinese Chemical Letters》2022年第10期4664-4668,共5页中国化学快报（英文版）

基　　金：supported bythe National Natural Science Foundationof China(Nos.22171071,22071044,21771054,21571050)。

摘　　要：Construction of two Ru^(Ⅲ)cations and six lacunary Keggin fragments resulted in a novel Ru_(2)W_(12)-cluster{(RuO_(6))_(2)(WO_(3))_(12)(H_(2)O)_(12)}bridged polyoxometalate,NaH_(11)[(RuO_(6))(AsW_(9)O_(33))_(3){(W_(6)O_(3))(H_(2)O)_(6)}]_(2)53H_(2)O(NaH_(11)·1·53H_(2)O),which represent the largest cluster in all the Ru-containing polyoxometalates.The most interesting characteristic is that the symmetry-related Ru_(2)W_(12)-cluster-based hexamers contain two windmill-shaped[(RuO_(6))(AsW_(9)O_(33))_(3){(W_(6)O_(3))(H_(2)O)_(6)}]trimers or the Ru_(2)W_(12) cluster was tightly wrapped by six segments of B-β-AsW_(9)O_(33).The other remarkable feature is that there have one intriguing cubane structure:which is composed of the Ru(1,2)and W(1,28,50,51,52,53)atoms.The oxygenation reactions of anilines to azoxybenzenes was evaluated when NaH_(11)·1·53H_(2)O served as effective catalyst by probing various reaction.The inherent redox property of oxygen-rich polyoxometalate surfaces and high photocatalytic activity of the Ru-containing metal cluster imbedded in NaH_(11)·1·53H_(2)O provide sufficient driving force for the photocatalytic transformation from anilines to azoxybenzenes.The oxidation of anilines can be realized with higher selectivity to afford various azoxybenzene compounds.The durability test shows that Ru-doping catalyst displays excellent chemical stability during the photocatalytic process.

关 键 词：Ru-containing polyoxometalate PHOTOCATALYST Oxidation Azoxy compounds Durability 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]