Porous crystalline metal-organic frameworks (MOFs) are one class of promising electrode materials for CO₂ electroreduction reaction (CO₂RR) by virtue of their large CO₂ adsorption capacities and abundant tunable active sites, but their insulating nature usually leads to low current density. Herein, a two-dimensional (2D) Ni-phthalocyanine-based MOF (NiPc-Ni(NH)₄) that constructed by 2,3,9,10,16,17,23,24-octaaminophthalocyaninato nickel(II) (NiPc-(NH₂)₈) and nickel(II) ions attained high electrical conductivity due to the high overlap of d-π conjugation orbitals between the nickel node and the Ni-phthalocyanine substituted o-phenylenediamine. During CO₂RR, the NiPc-Ni(NH)₄ nanosheets achieved a high CO Faradaic efficiency of 96.4% at −0.7 V and a large CO partial current density of 24.8 mA cm⁻² at −1.1 V, which surpass all the reported two-dimensional MOF electrocatalysts evaluated in H-cell. The control experiments and density functional theory (DFT) calculations suggested that the Ni-N₄ units of the phthalocyanine ring are the catalytic active sites. This work provides a new route to the design of highly efficient porous framework materials for the enhanced electrocatalysis via improving electrical conductivity.

多孔结晶金属有机框架（MOFs）由于其大的 CO ₂吸附容量和丰富的可调活性位点，是一类有前途的 CO ₂电还原反应（CO ₂ RR）电极材料，但它们的绝缘性通常会导致低电流密度。在此，由 2,3,9,10,16,17,23,24-八氨基酞菁镍（II）（NiPc）构成的二维（2D）Ni-酞菁基MOF（NiPc-Ni(NH) ₄） -(NH ₂ ) ₈ )和镍(II)离子由于镍节点和Ni-酞菁取代的邻苯二胺之间d-π共轭轨道的高度重叠而获得高导电性。一氧化碳期间₂ RR，NiPc-Ni(NH) ₄纳米片在-0.7 V 下实现了 96.4% 的高 CO 法拉第效率和在 -1.1 V下实现了 24.8 mA cm ^-2的大 CO 分流密度，这超过了所有报道的两个-在 H 电池中评估的三维 MOF 电催化剂。对照实验和密度泛函理论 (DFT) 计算表明，酞菁环的 Ni-N ₄单元是催化活性位点。这项工作为通过提高电导率来设计用于增强电催化的高效多孔骨架材料提供了一条新途径。