Abstract
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 ZnII 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.
Highlights
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
The TPY-TTF low molecular weight gelator (LMWG) was synthesized by the amide coupling reaction between 2,2′:6′,2′′-terpyridin-4′-yl-propane-1,3-diamine (TPY-NH2)[47] and 1,3,6,8-tetrakis tetrathiafulvalene (TTF(COOH)4)[48] (details are provided in method section and supplementary information (SI)), Supplementary Figs. 1–2)
A low energy absorption band appeared at 520 nm that can be ascribed to intramolecular charge-transfer (CT) interaction between TTF core and benzoamide moiety[48]
Summary
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. There is a huge lacuna in designing and developing such versatile photocatalyst materials that can reduce both, water and CO2 efficiently To this end, developing soft hybrid materials, such as coordination polymer gel (CPG), assembled by the low molecular weight gelator (LMWG) based linker and suitable metal ions, could be an excellent design approach in the realm of photocatalysis[30,31]. Such hierarchical soft nanofibrous materials[1,32,33] can facilitate the facile diffusion of reactants to the active sites and will show efficient electron transfer between different components[34,35,36]. Coordination driven array of donor–acceptor pairs would further improve photocatalytic performances by enhancing charge transfer to the catalytic centre
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