Charge-transfer regulated visible light driven photocatalytic H₂ production and CO₂ reduction in tetrathiafulvalene...

The much-needed renewable alternatives to fossil fuel can be achieved efficiently and sustainably by converting solar energy to fuels via hydrogen generation from water or CO₂ reduction. Herein, a soft processable metal-organic hybrid material is developed and studied for photocatalytic activity towards H₂ production and CO₂ reduction to CO and CH₄ under visible light as well as direct sunlight irradiation. A tetrapodal low molecular weight gelator (LMWG) is synthesized by integrating tetrathiafulvalene (TTF) and terpyridine (TPY) derivatives through amide linkages and results in TPY-TTF LMWG. The TPY-TTF LMWG acts as a linker, and self-assembly of this gelator molecules with Zn^II ions results in a coordination polymer gel (CPG); Zn-TPY-TTF. The Zn-TPY-TTF CPG shows high photocatalytic activity towards H₂ production (530 μmol g^-1h^-1) and CO₂ reduction to CO (438 μmol g^-1h^-1, selectivity > 99%) regulated by charge-transfer interactions. Furthermore, in situ stabilization of Pt nanoparticles on CPG (Pt@Zn-TPY-TTF) enhances H₂ evolution (14727 μmol g^-1h^-1). Importantly, Pt@Zn-TPY-TTF CPG produces CH₄ (292 μmol g^-1h^-1, selectivity > 97%) as CO₂ reduction product instead of CO. The real-time CO₂ reduction reaction is monitored by in situ DRIFT study, and the plausible mechanism is derived computationally.