Electrocatalytic N₂ reduction provides an attractive alternative to Haber-Bosch process for artificial NH₃ synthesis. The difficulty of suppressing competing proton reduction, however, largely impedes its practical use. Herein, we design a hydrophobic octadecanethiol- modified Fe₃P nanoarrays supported on carbon paper (C18@Fe₃P/CP) to effectively repel water, concentrate N₂, and enhance N₂-to-NH₃ conversion. Such catalyst achieves an NH₃ yield of 1.80 × 10^–10 mol·s^–1·cm^–2 and a high Faradaic efficiency of 11.22% in 0.1 M Na₂SO₄, outperforming the non-modified Fe₃P/CP (2.16 × 10^-11 mol·s^–1·cm^–2, 0.9%) counterpart. Significantly, C18@Fe₃P/CP renders steady N₂-fixing activity/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 Fe₃P can be well tuned by the thiol modification, which facilitates N₂ electroreduction activity and catalytic formation of NH₃.

The advancement of cost-effective and selective electrocatalyst towards CO₂ to CO conversion is crucial for renewable energy conversion and storage, thus to achieve carbon-neutral cycle in a sustainable manner. In this communication, we report that Cu₂Sb decorated Cu nanowire arrays on Cu foil act as a highly active and selective electrocatalyst for CO₂ to CO conversion. In CO₂-saturated 0.1 M KHCO₃, it achieves a high Faraday efficiency (FE) of 86.5% for CO, at -0.90 V vs. reversible hydrogen electrode (RHE). The H₂/CO ratio is tunable from 0.08:1 to 5.9:1 by adjusting the potential. It is worth noting that HCOO^- product was totally suppressed on such catalyst, compared with Sb counterpart. The improving selectivity for CO could be attributed to the bimetallic effect and nanowire arrays structure.