Mixed-Blocks-Driving Nickel–Porphyrin Covalent Organic Polymers for Photocatalytic Syngas Production from CO₂ with Fine Selectivity

CO 2 photoconversion to syngas with superb selectivity is a splendid and bright option to achieve environmental improvement, energy substitution, and industrial needs. Herein, a series of Ni–porphyrin covalent organic polymers (COPs) interspersed with furan and thiophene using a mixed-blocks-engineering strategy, named as O X S Y –Ni COPs ( X and Y refer to the relative amounts of furan and thiophene blocks, respectively), are synthesized for photocatalytic CO 2 -to-syngas. Ni-coordinated porphyrin cores prefer to act as mediators of CO 2 -to-CO photoconversion because of the higher adsorption capacity of CO 2 . Ni-free porphyrins work mainly as active sites of H 2 photoevolution. Furthermore, introducing different amounts of furan and thiophene modulates jointly the electronic structure of Ni–porphyrin COPs and optimizes the conduction band alignment. The above controllable variables achieve a wonderful syngas (CO/H 2 ) ratio range from 2:1.06 to 1:1.04 for the Fischer–Tropsch process within common industrial reactions. Notably, the COP of the O 1 S 3 –Ni COPs exhibits excellent photocatalytic CO 2 -to-syngas activity under visible light, with a syngas yield of 8442.5 μmol g –1 h –1 (CO/H 2 = 1:1.02) and an apparent quantum efficiency (AQE) of 1.92% at 450 nm. This strategy would provide a significance path to design functional and efficient organic semiconductors.