High-efficiency electrocatalysts for CO₂ reduction reaction are extremely desirable to produce valuable hydrocarbon productions, as well as addressing the current environmental challenges. In this work, we introduce a Cu-based metal–organic framework as a catalyst for the efficient and selective reduction of CO₂ to CH₄ in neutral aqueous electrolytes. Detailed examination of [Cu₄ZnCl₄(btdd)₃] (Cu₄-MFU-4l, H₂btdd = bis(1H-1,2,3-triazolo-[4,5-b],[4′,5′-i])dibenzo-[1,4]-dioxin) revealed the highest activity for yielding methane with a Faradaic efficiency of 92%/88% and a partial current density of 9.8/18.3 mA cm^–2 at a potential of −1.2/–1.3 V (vs RHE). In situ X-ray absorption and infrared spectroscopy spectra, as well as density functional theory calculations, revealed that the in situ generated trigonal pyramidal Cu(I)N₃ acts as the electrochemical active site and that the strong coordination ability of the Cu(I)N₃ site and the synergistic effect of adjacent aromatic hydrogen atoms, via hydrogen-bonding interactions, play an important role in stabilizing the key intermediates of carbon dioxide reduction and inhibiting the hydrogen evolution reaction, thus showing a high performance of electroreduction of CO₂ to CH₄.

中文翻译：

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通过具有三角锥 Cu(I)N3 活性位点的金属-有机骨架将 CO2 高效电转化为 CH4

用于 CO ₂还原反应的高效电催化剂对于生产有价值的烃类产品以及应对当前的环境挑战非常理想。在这项工作中，我们引入了一种基于铜的金属-有机骨架作为催化剂，用于在中性水性电解质中将CO ₂有效和选择性地还原为 CH ₄。[Cu ₄ ZnCl ₄ (btdd) ₃ ] ( Cu ₄ -MFU-4 l , H ₂ btdd = bis(1 H -1,2,3- triazolo- [4,5- b ],[4')的详细检查,5′- i]) 二苯并-[1,4]-二恶英) 显示出最高的甲烷活性，法拉第效率为 92%/88%，部分电流密度为 9.8/18.3 mA cm ^–2，电位为 -1.2/– 1.3V（相对于 RHE）。原位X 射线吸收光谱和红外光谱，以及密度泛函理论计算表明，原位生成的三角锥状 Cu(I)N ₃作为电化学活性位点，Cu(I)N具有很强的配位能力。 )N ₃位点和相邻芳族氢原子的协同作用，通过氢键相互作用，在稳定二氧化碳还原的关键中间体和抑制析氢反应中起重要作用，从而显示出将 CO ₂电还原为 CH _{4 的}高性能。