Photoenzymatic Catalytic Cascade System of a Pyromellitic Diimide/g-C₃N₄ Heterojunction to Efficiently Regenerate NADH for Highly Selective CO₂ Reduction toward Formic Acid

Photocatalytic reduction of carbon dioxide (CO2) holds great promise for both clean energy and environment protection. However, the low activity and poor selectivity of photocatalysts are the main bottlenecks. Herein, inspired by artificial photosynthesis and taking advantages of high efficiency and specificity of bioenzymes, we marry photo with enzyme to synergistically solve the above problems. A metal-free heterojunction of pyromellitic diimide/g-C3N4 (PDI/CN) with an excellent visible light response (λ < 660 nm) is fabricated for achieving a photoenzymatic catalytic cascade system, which efficiently regenerates nicotinamide adenine dinucleotide (NADH) and selectively reduces CO2 to formic acid (HCOOH). The highest NADH yield of the PDI/CN hybrid achieved is 75%, and the HCOOH generation rate achieved is 1.269 mmol g–1 h–1 with nearly 100% selectivity, which is much higher than those of the reported materials. The excellent photocatalytic performance is attributed to the unique photoenzymatic catalytic cascade system, heterointerface effect, good conductivity, and a wide sunlight response range of the PDI/CN heterojunction. This work provides an efficient strategy and a corresponding photocatalyst for the directional conversion of CO2 to HCOOH.