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
Li-rich Mn-based cathode materials have attracted extensive attention due to their remarkable energy density contributed by additional anionic redox.However,they always suffer from some undesired problems impeding the...Li-rich Mn-based cathode materials have attracted extensive attention due to their remarkable energy density contributed by additional anionic redox.However,they always suffer from some undesired problems impeding their further commercialization such as irreversible oxygen loss,transition metal migration,sluggish kinetics and so on.Fortunately,the above issues can be relieved effectively when 3d metal Mn is replaced by 4d metal Ru.We focus on the recent progress of Ru-containing cathode materials and make a detailed summary in this review.At first,we attempt to combine and elucidate the relationship between oxygen and Ru redox.Subsequently,the up-to-date materials of Ru-based cathode materials for Li^(+)/Na^(+)batteries are concluded systematically.Afterward,the effects of Ru are discussed in depth including enhancing the reversibility of anionic redox and structural stability,modulating the ratio between cationic and anionic redox,improving the kinetics of Li^(+)/Na^(+),inhibiting the transition metal migration and so on.More importantly,the future designs of Ru-containing cathode materials are also proposed enlighteningly.We hope this review could offer some new perspectives to comprehend the layered oxides involving anionic redox and provide useful guidelines to achieve better Li^(+)/Na^(+)rechargeable batteries.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This work was supported by the National Natural Science Foundation of China(grant no.22005274 and 21975225)the China Postdoctoral Science Foundation(grant nos.2023T160591)the National Key Research and Development Program of China(2022YFB2402200).
文摘Li-rich Mn-based cathode materials have attracted extensive attention due to their remarkable energy density contributed by additional anionic redox.However,they always suffer from some undesired problems impeding their further commercialization such as irreversible oxygen loss,transition metal migration,sluggish kinetics and so on.Fortunately,the above issues can be relieved effectively when 3d metal Mn is replaced by 4d metal Ru.We focus on the recent progress of Ru-containing cathode materials and make a detailed summary in this review.At first,we attempt to combine and elucidate the relationship between oxygen and Ru redox.Subsequently,the up-to-date materials of Ru-based cathode materials for Li^(+)/Na^(+)batteries are concluded systematically.Afterward,the effects of Ru are discussed in depth including enhancing the reversibility of anionic redox and structural stability,modulating the ratio between cationic and anionic redox,improving the kinetics of Li^(+)/Na^(+),inhibiting the transition metal migration and so on.More importantly,the future designs of Ru-containing cathode materials are also proposed enlighteningly.We hope this review could offer some new perspectives to comprehend the layered oxides involving anionic redox and provide useful guidelines to achieve better Li^(+)/Na^(+)rechargeable batteries.
