Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated el...Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.展开更多
Azoxy dyes and their copper complexes with maximum dichroism in the spectrum range from 550nm to 700nm were synthesized and used to prepare polyvinyl alcohol (PVA) polarizing films. These films showed excellent polari...Azoxy dyes and their copper complexes with maximum dichroism in the spectrum range from 550nm to 700nm were synthesized and used to prepare polyvinyl alcohol (PVA) polarizing films. These films showed excellent polarizing ability. In addition, a neutral gray polarizing film was prepared by mixing synthesized dichromatic dyes with other dyes. The obtained polarizable film for gray shade was little pervious to light over the visible radiation wavelength region, ranging from 400nm to 700nm at cross state, and excellent in the polarizing activities and stable to moisture and heat.展开更多
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 by the National Key R&D Program of China(2024YFA1211004)the National Natural Science Foundation of China(22402150,22072107)+1 种基金the Natural Science Foundation of Shanghai(23ZR1464800,24ZR1470200)the Foundation of State Key Laboratory of Pollution Control and Resource Reuse(Tongji University)。
文摘Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.
基金Scientific Fundation of Anhui University of Technology and Science,China (No.2007YQ001)
文摘Azoxy dyes and their copper complexes with maximum dichroism in the spectrum range from 550nm to 700nm were synthesized and used to prepare polyvinyl alcohol (PVA) polarizing films. These films showed excellent polarizing ability. In addition, a neutral gray polarizing film was prepared by mixing synthesized dichromatic dyes with other dyes. The obtained polarizable film for gray shade was little pervious to light over the visible radiation wavelength region, ranging from 400nm to 700nm at cross state, and excellent in the polarizing activities and stable to moisture and heat.
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.
