Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

Highly effective electrocatalysts promoting CO(2) reduction reaction (CO(2)RR) 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 (CuN(4)) and zinc-bis(dihydroxy) complex (ZnO(4)) as linkage (PcCu-O(8)-Zn). The PcCu-O(8)-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 H(2)/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; ZnO(4) complexes act as CO(2)RR catalytic sites while CuN(4) centers promote the protonation of adsorbed CO(2) during CO(2)RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO(2)RR toward syngas synthesis.