CO2 Dominated Bifunctional Catalytic Sites for Efficient Industrial Exhaust Conversion

Abstract Converting industrial exhaust into valuable chemicals is crucial for sustainable economic development. Direct CO 2 photoreduction from real flue gas is an ideal clean and promising way, until now, without success. Here, photoreduction of exhaust gas from the power plant by Ni bridged COF (Ni@TPHH‐COF) is shown. Under visible light, syngas is produced with CO output reaching 2.1 mol kg −1 h −1 . The ideal conversion of flue gas is up to 672 L kg −1 h −1 . Of note, the system exhibits appealing yield and selectivity under 0.5–40% CO 2 and AQY achieves 3.96% under 10% CO 2 , ranking among the highest value of reported photocatalysts. Mechanism studies suggest CO 2 plays a dual function as both a component of a catalytic site and a reactant, which can not only selectively enrich CO 2 in catalytic sites but improve reaction rate significantly. This CO 2 ‐dominated bifunctional site prolongs electrons lifetime, stabilizes intermediates, and reduces free energy of reduction under diluted CO 2 .