Novel cerium-based MOFs photocatalyst for photocarrier collaborative performance under visible light

Abstract A novel cerium-based metal-organic framework crystal (Ce-TBAPy) was developed via a one-pot solvothermal method. Interestingly, the Ce-TBAPy photocatalyst material demonstrated an enhanced collaborative photoredox performance in terms of acetaldehyde degradation and water reduction, and the photoreaction rates of Ce-TBAPy shown about 5.06-times and 3.94-times higher, respectively, than those when untreated H4TBAPy was used. A significant finding is that the apparent quantum efficiency value of Ce-TBAPy for CO2 generation from CH3CHO decomposition performs 5.12% at 420 nm. The accumulation of abundant separated holes on the pyrene macrocycles could oxidize CH3CHO to CO2 easily. Meanwhile, cerium integration with TBAPy4− ligands to form a π-conjugated construction further resulted in sufficient photoinduced electrons and exhibited effective interfacial charge separation, which harvesting the reduction of H2O to H2 efficiently. The electronic localization influence arising from the formation of -COO-Ce functional groups in Ce-TBAPy and the direction of electron migration in the photocatalytic system were further confirmed by DFT calculation. This work provides an effective strategy to obtain rare earth-based MOF photocatalysts with dual redox functions and holds promise for advancing the prospect of using MOF materials to convert solar energy into chemical energy.