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...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.展开更多
基金supported bythe National Natural Science Foundationof China(Nos.22171071,22071044,21771054,21571050)。
文摘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.
基金supported by the National Science Fund for Distinguished Young Scholars of China(21825801)the National Natural Science Foundation of China(21972019,21978051).
