Electrocatalytic N_(2) reduction provides an attractive alternative to Haber-Bosch process for artificial NH_(3) synthesis.The difficulty of suppressing competing proton reduction,however,largely impedes its practical...Electrocatalytic N_(2) reduction provides an attractive alternative to Haber-Bosch process for artificial NH_(3) synthesis.The difficulty of suppressing competing proton reduction,however,largely impedes its practical use.Herein,we design a hydrophobic octadecanethiol-modified Fe_(3)P nanoarrays supported on carbon paper(C18@Fe_(3)P/CP)to effectively repel water,concentrate N_(2),and enhance N_(2)-to-NH_(3) conversion.Such catalyst achieves an NH_(3) yield of 1.80×10^(-10) mol s^(-1)·cm^(-2) and a high Faradaic efficiency of 11.22%in 0.1 M Na_(2)SO_(4),outperforming the non-modified Fe_(3)P/CP(2.16×10^(-11) mol s^(-1)·cm^(-2),0.9%)counterpart.Significantly,C18@Fe_(3)P/CP renders steady Nrfixing activlty/selectivity in cycling test and exhibits durability for at least 25 h.First-principles calculations suggest that the surface electronic structure and chemical activity of Fe_(3)P can be well tuned by the thiol modification,which facilitates N_(2) electroreduction activity and catalytic formation of NH_(3).展开更多
基金supported by the National Natural Science Foundation of China(No.22072015)Shanghai Scientific and Technological Innovation Project(No.18JC 1410604)Program for Science&Technology Innovation Talents in Universities of Henan Province(No.20HASTIT028).
文摘Electrocatalytic N_(2) reduction provides an attractive alternative to Haber-Bosch process for artificial NH_(3) synthesis.The difficulty of suppressing competing proton reduction,however,largely impedes its practical use.Herein,we design a hydrophobic octadecanethiol-modified Fe_(3)P nanoarrays supported on carbon paper(C18@Fe_(3)P/CP)to effectively repel water,concentrate N_(2),and enhance N_(2)-to-NH_(3) conversion.Such catalyst achieves an NH_(3) yield of 1.80×10^(-10) mol s^(-1)·cm^(-2) and a high Faradaic efficiency of 11.22%in 0.1 M Na_(2)SO_(4),outperforming the non-modified Fe_(3)P/CP(2.16×10^(-11) mol s^(-1)·cm^(-2),0.9%)counterpart.Significantly,C18@Fe_(3)P/CP renders steady Nrfixing activlty/selectivity in cycling test and exhibits durability for at least 25 h.First-principles calculations suggest that the surface electronic structure and chemical activity of Fe_(3)P can be well tuned by the thiol modification,which facilitates N_(2) electroreduction activity and catalytic formation of NH_(3).
