Nitrate–methanol co-electrolysis involving the cathodic nitrate reduction reaction (NO₃RR) combined with the anodic methanol oxidation reaction (MOR) is a viable way to synchronously produce ammonia (NH₃) and formate via gentle, sustainable and energy-saving “E-refining” and “E-reforming” means. An efficient bifunctional catalyst for the NO₃RR and MOR is pivotal to achieve such a goal. In this work, a nitrogen-doped carbon-encapsulated nickel iron phosphide hybrid (Ni₂FeP@NC) was prepared as a bifunctional catalyst for the NO₃RR and MOR, and its electrochemical performance for nitrate–methanol co-electrolysis was investigated. The Ni₂FeP@NC catalyst exhibited a high NH₃ yield (0.47 mmol h⁻¹ cm⁻² at −0.35 V) and faradaic efficiency (FE, 93% at −0.15 V) for the NO₃RR and simultaneously demonstrated high MOR efficiency for formate production (yield of 1.62 mmol h⁻¹ cm⁻² at 1.7 V and FE of around 95%). The bifunctional catalytic features of the nitrate–methanol co-electrolysis system enabled the concurrent production of NH₃ and formate at low input voltage. This work provides a viable paradigm for pairwise electrosynthesis of valuable chemicals via “E-refining” and “E-reforming” through the rational design of bifunctional catalysts.

中文翻译：

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在氮掺杂碳包埋镍铁磷化物上通过硝酸盐电还原结合甲醇电氧化实现氨和甲酸盐共合成


涉及阴极硝酸盐还原反应 （NO₃RR） 的硝酸盐-甲醇共电解与阳极甲醇氧化反应 （MOR） 相结合，是通过温和、可持续和节能的“E-refining”和“E-reforming”手段同步生产氨 （NH₃） 和甲酸盐的可行方法。NO₃RR 和 MOR 的高效双功能催化剂对于实现这一目标至关重要。本工作制备了氮掺杂碳包埋镍铁磷化物 （Ni₂FeP@NC） 作为 NO₃RR 和 MOR 的双功能催化剂，并研究了其硝酸盐-甲醇共电解的电化学性能。Ni₂FeP@NC催化剂对 NO₃RR 表现出高 NH₃产率（-0.35 V 时 0.47 mmol ^{h-1 cm-2}）和法拉第效率（FE，-0.15 V 时为 93%），同时表现出甲酸盐生产的高 MOR 效率（产率为 1.62 mmol ^{h-1 cm-2}在 1.7 V 和 FE 约为 95% 时。硝酸盐-甲醇共电解系统的双功能催化特性能够在低输入电压下同时产生 NH₃ 和甲酸盐。这项工作通过合理设计双功能催化剂，为通过 “E-refining” 和 “E-reforming” 对有价值的化学品进行成对电合成提供了一种可行的范例。