Pore size modulation of cobalt-corrole-based porous organic polymers for boosted electrocatalytic oxygen reduction reaction

The highly active and selective oxygen reduction reaction (ORR) is vital to promote the performance of advanced energy conversion systems, such as fuel cells and other electrochemical devices. Porous framework materials have the capability to combine the catalytic performance of catalytic active units with their porous characteristics, making them promising oxygen reduction catalysts. However, due to the difficulty in designing and synthesizing catalytic active units, the pore size modulation of framework materials is primarily achieved by altering the linkers. We herein report the design and synthesis of three cobalt-corrole-based porous organic polymers (Co-POP-1, Co-POP-2 and Co-POP-3) with different pore sizes, which were obtained by extending 5,15-meso substituents of Co corroles. Compared to Co-POP-1 and Co-POP-2, Co-POP-3 has the largest pore size. Benefiting from the enhanced mass transfer and the highly exposed active sites, Co-POP-3 displayed remarkably boosted activity for the selective four-electron/four-proton (4e⁻/4 H⁺) ORR with a half-wave potential of E_1/2 = 0.89 V versus reversible hydrogen electrode (RHE) in 0.1 M KOH solutions. This work not only presents a cobalt-corrole-based porous organic polymer catalyst with high ORR activity and selectivity but also provides a new strategy to moderate the pore size of porous framework materials.