The electrochemical N₂ reduction reaction (ENRR), driven by renewable electricity and run under ambient conditions, offers a promising sustainable avenue for carbon-neutral NH₃ production. Yet, to efficiently bind and activate the inert N₂ remains challenge. Herein, effective and stable electrochemical NH₃ synthesis on Sm(OH)₃ via enhanced adsorption of hydrogen and dinitrogen by dual integration of sulfur dopants and oxygen vacancies (V_O) is reported. The resulting S-doped lanthanide electrocatalyst attains both a good NH₃ yield rate, exceeding 21 μg_NH3 h⁻¹ mg_cat.⁻¹, and an NH₃ faradaic efficiency of over 29% at −0.3 V (vs reversible hydrogen electrode) in an H-type cell using a neutral electrolyte, figures of merit that are largely maintained after 2 days of consecutive polarization. Density functional theory calculations show that the adsorption energy barrier of N₂ on S-Sm(OH)₃(V_O) is greatly lowered by the introduction of V_O. In addition, the S sites improve the adsorption of hydrogen produced via the Volmer reaction, which is conducive to the formation of the *N–NH intermediate (i.e., the potential determining step, PDS) on adjacent Sm sites, and thereby significantly promotes the reaction kinetics of ENRR. The PDS free energy for the catalyst is comparable with the values at the peak of the ENRR volcano plots of leading transition metal catalyst surfaces.

中文翻译：

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同时增强氢和氮的吸附，实现 Sm(OH)3 上高效电化学 NH3 合成

由可再生电力驱动并在环境条件下运行的电化学 N ₂还原反应 (ENRR) 为碳中性 NH ₃生产提供了一条有前途的可持续途径。然而，有效地结合和激活惰性N ₂仍然是一个挑战。在此，报道了通过硫掺杂剂和氧空位（V _O ）的双重整合增强氢和氮的吸附，在Sm(OH) ₃上有效且稳定地电化学合成NH _{3 。}所得S掺杂镧系元素电催化剂获得了良好的NH ₃产率，超过21 μg _NH3  h ^-1  mg _cat。^-1，并且在使用中性电解质的H型电池中在-0.3V（相对于可逆氢电极）下NH _{3法拉第效率超过29%，连续极化2天后基本保持了品质因数。密度泛函理论计算表明，V O}的引入大大降低了N ₂在S-Sm(OH) ₃ (V _O )上的吸附能垒。此外，S位点提高了Volmer反应产生的氢气的吸附，有利于相邻Sm位点上*N–NH中间体（即电位决定步骤，PDS）的形成，从而显着促进了ENRR 的反应动力学。催化剂的 PDS 自由能与主要过渡金属催化剂表面的 ENRR 火山图峰值处的值相当。