Electrochemical carbon dioxide reduction reaction (CO2RR) to valuable fuels and chemical feedstock is a sustainable strategy to lower the anthropogenic CO2 concentration, thereby dynamising the carbon cycle in the environment. CH3OH on the other hand is undoubtedly the most desirable C1 product of CO2RR. However, selective electroreduction of CO2‐to‐CH3OH is very challenging and only limited catalysts are reported in literature. Pyrolyzing metal‐organic frameworks (MOFs) to generate carbon matrix impregnated with metal nanoparticles, heralds exciting electrocatalytic properties. This study unveiled the morphological evolution of a mixed‐ligand Ni‐MOF (Ni‐OBBA‐Bpy) during pyrolysis, to generate Ni nanoparticles anchored 0D porous hollow carbon superstructures (Pyr‐CP‐800 and Pyr‐CP‐600). This unique morphology invokes high specific surface area and surface roughness to the materials, which synergistically facilitates the selective electroreduction of CO2‐to‐CH3OH. In comparison to most of the previously reported Ni electrocatalysts that mainly produced CO, Pyr‐CP‐800 selectively yielded CH3OH with Faradaic efficiency (FE) of 32.46% at −0.60 V versus RHE (reversible hydrogen electrode) in 1.0 M KOH solution, which is highest among other reported Ni‐based electrocatalysts in the literature, to best of our knowledge. Additionally, insights from density functional theory (DFT) calculations revealed that Ni (111) plane to be the active site toward the electrochemical. CO2‐to‐CH3OH formation.

中文翻译：

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镍基空心 0D 碳上层结构的低电位电化学 CO2 还原为甲醇


电化学二氧化碳还原反应 （CO2RR） 与有价值的燃料和化学原料是降低人为 CO2 浓度的可持续策略，从而使环境中的碳循环充满活力。另一方面，CH3OH 无疑是 CO2RR 最理想的 C1 产物。然而，CO2 到 CH3OH 的选择性电还原非常具有挑战性，文献中仅报道了有限的催化剂。热解金属有机框架 （MOF） 以生成浸渍有金属纳米颗粒的碳基质，预示着令人兴奋的电催化特性。本研究揭示了混合配体 Ni-MOF （Ni-OBBA-Bpy） 在热解过程中的形态演变，以生成锚定 0D 多孔空心碳超结构 （Pyr-CP-800 和 Pyr-CP-600） 的 Ni 纳米颗粒。这种独特的形态使材料具有高比表面积和表面粗糙度，从而协同促进 CO2 选择性电还原为 CH3OH。与大多数以前报道的主要产生一氧化碳的镍电催化剂相比，Pyr-CP-800 在 -0.60 V 下选择性地产生 CH3OH，法拉第效率 （FE） 为 32.46%，而 RHE（可逆氢电极）在 1.0 M KOH 溶液中，据我们所知，这是文献中报道的其他镍基电催化剂中最高的。此外，来自密度泛函理论 （DFT） 计算的见解表明，Ni （111） 平面是电化学的活性位点。CO2 到 CH3OH 的形成。