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
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.
