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
In this paper, the membrane capacitance (Cm), which was obtained from the electro- chemical impedance spectroscopy (EIS) method, was used to characterize the effect of pH value on the self-assembled monolayers (SAMs) ...In this paper, the membrane capacitance (Cm), which was obtained from the electro- chemical impedance spectroscopy (EIS) method, was used to characterize the effect of pH value on the self-assembled monolayers (SAMs) of octadecanethiol(18SH) for the first time. The results not only strongly proved that inorganic ions could penetrate the SAMs of 18SH, but also ascertained that SAMs of 18SH were not an absolute of free of ion-penetration. Verifying the existence of pin-holes in the octadecanethiol SAMs was the main contribution of this paper, which coincided with the former conjecture very well.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).
基金This work was supported by the NNSFC (29973026).
文摘In this paper, the membrane capacitance (Cm), which was obtained from the electro- chemical impedance spectroscopy (EIS) method, was used to characterize the effect of pH value on the self-assembled monolayers (SAMs) of octadecanethiol(18SH) for the first time. The results not only strongly proved that inorganic ions could penetrate the SAMs of 18SH, but also ascertained that SAMs of 18SH were not an absolute of free of ion-penetration. Verifying the existence of pin-holes in the octadecanethiol SAMs was the main contribution of this paper, which coincided with the former conjecture very well.
