Highly effective electrocatalysts promoting CO₂ reduction reaction (CO₂RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN₄) and zinc-bis(dihydroxy) complex (ZnO₄) as linkage (PcCu-O₈-Zn). The PcCu-O₈-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s⁻¹ and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H₂/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO₄ complexes act as CO₂RR catalytic sites while CuN₄ centers promote the protonation of adsorbed CO₂ during CO₂RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO₂RR toward syngas synthesis.

促进CO ₂还原反应（CO ₂ RR）的高效电催化剂对于生产增值化学品/燃料同时应对当前的环境挑战是非常理想的。在此，我们开发了一种层堆叠的双金属二维共轭金属有机骨架（2D c -MOF），以铜酞菁作为配体（CuN ₄ ）和锌-双（二羟基）络合物（ZnO ₄ ）作为连接（PcCu -O ₈ -Zn)。 PcCu-O ₈ -Zn表现出88%的高CO选择性、0.39 s ^-1的周转频率和长期耐久性（>10 h），超越了迄今为止报道的基于MOF的电催化剂。 H ₂ /CO 摩尔比（1:7 至 4:1）可以通过改变金属中心和施加的电势来调节，使得 2D c -MOF 与合成气工业应用高度相关。对比实验结合原位光谱电化学和理论计算揭示了协同催化机制； ZnO ₄配合物充当CO ₂ RR催化位点，而CuN ₄中心在CO ₂ RR过程中促进吸附的CO ₂质子化。这项工作提供了开发双金属MOF电催化剂以协同催化CO ₂ RR合成气合成的策略。