Visible-light-responsive hybrid photocatalysts for quantitative conversion of CO 2 to highly concentrated formate solutions.

Autor: McQueen E; Department of Pure and Applied Chemistry, University of Strathclyde Thomas Graham Building, 295 Cathedral Street Glasgow G1 1XL UK sebastian.sprick@strath.ac.uk., Sakakibara N; Department of Chemistry, School of Science, Tokyo Institute of Technology 2-12-1-NE-2 Ookayama, Meguro Tokyo 152-8550 Japan nori.sakakibara@gmail.com., Kamogawa K; Department of Chemistry, School of Science, Tokyo Institute of Technology 2-12-1-NE-2 Ookayama, Meguro Tokyo 152-8550 Japan nori.sakakibara@gmail.com., Zwijnenburg MA; Department of Chemistry, University College London 20 Gordon Street London WC1H 0AJ UK., Tamaki Y; Department of Chemistry, School of Science, Tokyo Institute of Technology 2-12-1-NE-2 Ookayama, Meguro Tokyo 152-8550 Japan nori.sakakibara@gmail.com., Ishitani O; Department of Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University 1-3-1 Kagamiyama, Higashi-Hiroshima Hiroshima 739 8526 Japan iosamu@hiroshima-u.ac.jp., Sprick RS; Department of Pure and Applied Chemistry, University of Strathclyde Thomas Graham Building, 295 Cathedral Street Glasgow G1 1XL UK sebastian.sprick@strath.ac.uk.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2024 Oct 07. Date of Electronic Publication: 2024 Oct 07.
DOI: 10.1039/d4sc05289g
Abstrakt: Photocatalysts can use visible light to convert CO 2 into useful products. However, to date photocatalysts for CO 2 conversion are limited by insufficient long-term stability and low CO 2 conversion rates. Here we report hybrid photocatalysts consisting of conjugated polymers and a ruthenium(ii)-ruthenium(ii) supramolecular photocatalyst which overcome these challenges. The use of conjugated polymers allows for easy fine-tuning of structural and optoelectronic properties through the choice of monomers, and after loading with silver nanoparticles and the ruthenium-based binuclear metal complex, the resulting hybrid systems displayed remarkably enhanced activity for visible light-driven CO 2 conversion to formate. In particular, the hybrid photocatalyst system based on poly(dibenzo[ b , d ]thiophene sulfone) drove the very active, durable and selective photocatalytic CO 2 conversion to formate under visible light irradiation. The turnover number was found to be very high (TON = 349 000) with a similarly high turnover frequency (TOF) of 6.5 s -1 , exceeding the CO 2 fixation activity of ribulose-1,5-bisphosphate carboxylase/oxygenase in natural photosynthesis (TOF = 3.3 s -1 ), and an apparent quantum yield of 11.2% at 440 nm. Remarkably, quantitative conversion of CO 2 (737 μmol, 16.5 mL) to formate was achieved using only 8 mg of the hybrid photocatalyst containing 80 nmol of the supramolecular photocatalyst at standard temperature and pressure. The system sustained photocatalytic activity even after further replenishment of CO 2 , yielding a very high concentration of formate in the reaction solution up to 0.40 M without significant photocatalyst degradation within the timeframe studied. A range of experiments together with density functional theory calculations allowed us to understand the activity in more detail.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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