Charge-transfer regulated visible light driven photocatalytic H<sub>2</sub> production and CO<sub>2</sub> reduction in tetrathiafulvalene based coordination polymer gel.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 34916503.
- Also identified by DOI 10.1038/s41467-021-27457-4 and PMC identifier 8677803.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
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 CO<sub>2</sub> reduction. Herein, a soft processable metal-organic hybrid material is developed and studied for photocatalytic activity towards H<sub>2</sub> production and CO<sub>2</sub> reduction to CO and CH<sub>4</sub> 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<sup>II</sup> ions results in a coordination polymer gel (CPG); Zn-TPY-TTF. The Zn-TPY-TTF CPG shows high photocatalytic activity towards H<sub>2</sub> production (530 μmol g<sup>-1</sup>h<sup>-1</sup>) and CO<sub>2</sub> reduction to CO (438 μmol g<sup>-1</sup>h<sup>-1</sup>, selectivity > 99%) regulated by charge-transfer interactions. Furthermore, in situ stabilization of Pt nanoparticles on CPG (Pt@Zn-TPY-TTF) enhances H<sub>2</sub> evolution (14727 μmol g<sup>-1</sup>h<sup>-1</sup>). Importantly, Pt@Zn-TPY-TTF CPG produces CH<sub>4</sub> (292 μmol g<sup>-1</sup>h<sup>-1</sup>, selectivity > 97%) as CO<sub>2</sub> reduction product instead of CO. The real-time CO<sub>2</sub> reduction reaction is monitored by in situ DRIFT study, and the plausible mechanism is derived computationally.