Inspired by the metal–sulfur (M‐S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N₂ availability on a catalytic surface, which suppresses the hydrogen evolution reaction (HER) and improves the rate of NH₃ production. Ruthenium nanocrystals anchored on reduced graphene oxide (Ru/rGO) are modified with different aliphatic thiols to achieve M‐S linkages. A high faradaic efficiency (11 %) with an improved NH₃ yield (50 μg h⁻¹ mg⁻¹) is achieved at −0.1 V vs. RHE in acidic conditions by using dodecanethiol. DFT calculations reveal intermediate N₂ adsorption and desorption of the product is achieved by electronic structure modification along with the suppression of the HER by surface modification. The modified catalyst shows excellent stability and recyclability for NH₃ production, as confirmed by rigorous control experiments including ¹⁵N isotope labeling experiments.

中文翻译：

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通过钌纳米晶体的有机束缚以增强电化学氮还原作用而实现的金属-硫键。

受固氮酶中金属-硫（M-S）键的启发，在此我们展示了一种表面修饰策略，可调节电子结构并改善催化表面上的N ₂利用率，从而抑制了氢气释放反应（HER）和提高了NH _3的产生速率。锚定在还原氧化石墨烯（Ru / rGO）上的钌纳米晶体用不同的脂肪族硫醇修饰以实现MS键。在酸性条件下，通过使用十二烷硫醇，相对于RHE，在-0.1 V时，具有较高的法拉第效率（11％）和更高的NH ₃收率（50μgh ^-1  mg ^-1）。DFT计算显示出中间N ₂产物的吸附和解吸是通过电子结构改性以及通过表面改性抑制H​​ER来实现的。经严格的控制实验（包括¹⁵ N同位素标记实验）证实，改性催化剂对NH _3的生产显示出极好的稳定性和可循环性。