ABSTRACT
The conversion of CO2 into value-added chemicals and fuels using stable, cost-effective, and eco-friendly metal-free catalysts is a promising technology to mitigate the global environmental crisis. In the Calvin cycle of natural photosynthesis, CO2 reduction (CO2R) is achieved using the cofactor NADPH as the reducing agent through 2e-/1H+ or H- transfer. Consequently, inspired by NAD(P)H, a series of organohydrides with adjustable reducibility show remarkable potential for efficient metal-free CO2R. In this review, we first summarize the photosensitizers for NAD(P)H regeneration and list the representative photoenzyme CO2R system. Then, we introduce the NAD(P)H-inspired organohydrides and their applications in redox reactions. Furthermore, we discuss recent progress and breakthroughs by utilizing organohydrides as metal-free CO2R catalysts. Moreover, we delve into the reaction mechanisms and applications of these organohydrides, shedding light on their potential as sustainable alternatives to metal-based CO2R catalysts. Finally, we offer insights into the prospects and potential directions for advancing this intriguing avenue of organohydride-based catalysts for CO2R.
ABSTRACT
An artificial photocatalyst with a Rh complex immobilized onto polymeric carbon nitride (CN) through non-covalent interaction was constructed for photocatalytic NADH regeneration. DFT calculations verified the adsorption of the bipyridine ligand onto the CN photocatalyst. By further coupling the in situ formed NADH with FDH immobilized on a hydrophobic membrane, an enhanced HCOOH production (3.1 mM) from CO2 could be realized on the gas-liquid-solid three-phase interface. This work provides an alternative and efficient strategy for promoting artificial photosynthesis.
