Synergistic Effect in a Metal-Organic Framework Boosting the Electrochemical CO₂ Overall Splitting

It is a very important but still challenging task to develop bifunctional electrocatalysts for highly efficient CO₂ overall splitting. Herein, we report a stable metal-organic framework (denoted as PcNi-Co-O), composed of (2,3,9,10,16,17,23,24-octahydroxyphthalocyaninato)nickel(II) (PcNi-(O^-)₈) ligands and the planar CoO₄ nodes, for CO₂ overall splitting. When working as both cathode and anode catalysts (i.e., PcNi-Co-O||PcNi-Co-O), PcNi-Co-O achieved a commercial-scale current density of 123 mA cm^-2 (much higher than the reported values (0.2-12 mA cm^-2)) with a Faradic efficiency (CO) of 98% at a low cell voltage of 4.4 V. Mechanism studies suggested the synergistic effects between two active sites, namely, (i) electron transfer from CoO₄ to PcNi sites under electric fields, resulting in the raised oxidizability/reducibility of CoO₄/PcNi sites, respectively; (ii) the energy-level matching of cathode and anode catalysts can reduce the energy barrier of electron transfer between them and improve the performance of CO₂ overall splitting.