Bipolaronic Motifs Induced Spatially Separated Catalytic Sites for Tunable Syngas Photosynthesis From CO₂

Photocatalytic reduction of CO₂ into syngas is a promising way to tackle the energy and environmental challenges; however, it remains a challenge to achieve reaction decoupling of CO₂ reduction and water splitting. Therefore, efficient production of syngas with a suitable CO/H₂ ratio for Fischer-Tropsch synthesis can hardly be achieved. Herein, bipolaronic motifs including Co(II)-pyridine N motifs and Co(II)-imine N motifs are rationally designed into a crystalline imine-linked 1,10-phenanthroline-5,6-dione-based covalent organic framework (bp-Co-COF) with a triazine core. These featured structures with spatially separated active sites exhibit efficient photocatalytic performance toward CO₂-to-syngas conversion with a suitable CO/H₂ ratio (1:1-1:3). The bipolaronic motifs enable a highly separated electron-hole state, whereby the Co(II)-pyridine N motifs tend to be the active sites for CO₂ activation and accelerate the hydrogenation to form *COOH intermediates; whilst, the Co(II)-imine N motifs increase surface hydrophilicity for H₂ evolution. The photocatalytic reductions of CO₂ and H₂O thus decouple and proceed via a concerted way on the bipolaronic motifs of bp-Co-COF. The optimal bp-Co-COF photocatalyst achieves a high syngas evolution rate of 15.8 mmol g^-1 h^-1 with CO/H₂ ratio of 1:2, outperforming previously reported COF-based photocatalysts.