Modulating microenvironment of active moiety in Prussian blue analogues via surface coordination to enhance CO2 photoreduction

Well-arranged photosensitive units and catalytic sites in closeness are critical for enhancing charge separation effectiveness and promoting photocatalysis. Here, a heterogeneous interface is constructed, which binds a deprotonated carboxyl group on perylene diimide (PDI) photosensitizer to unsaturated metal sites generated by etching of different Prussian blue analogues (PBAs). The atomically-dispersed metal sites and anchored photosensitive units greatly accelerate charge transfer. Typically, the S-scheme heterojunction built by etched NiCo PBA and PDI (NCSP) possesses bond of O-Ni. Density functional theory (DFT) and in-situ technology reveals the electron density of the Ni active site is optimized. Consequently, activation barrier of CO 2 on the Ni site was reduced, thus improving the CO generation (60.0 μmol g −1 ) up to about 9 times than NiCo PBA. This work reveals key insights into the precise modulation of active moiety for efficient photocatalytic CO 2 conversion.