McQueen, Ewan;
Sakakibara, Noritaka;
Kamogawa, Kei;
Zwijnenburg, Martijn A;
Tamaki, Yusuke;
Ishitani, Osamu;
Sprick, Reiner Sebastian;
(2024)
Visible-light-responsive hybrid photocatalysts for quantitative conversion of CO2 to highly concentrated formate solutions.
Chemical Science
, 15
(43)
pp. 18146-18160.
10.1039/d4sc05289g.
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Abstract
Photocatalysts can use visible light to convert CO2 into useful products. However, to date photocatalysts for CO2 conversion are limited by insufficient long-term stability and low CO2 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 CO2 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 CO2 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 CO2 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 CO2 (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 CO2, 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.
| Type: | Article |
|---|---|
| Title: | Visible-light-responsive hybrid photocatalysts for quantitative conversion of CO2 to highly concentrated formate solutions |
| Location: | England |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/d4sc05289g |
| Publisher version: | http://dx.doi.org/10.1039/d4sc05289g |
| Language: | English |
| Additional information: | This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
| Keywords: | Science & Technology, Physical Sciences, Chemistry, Multidisciplinary, Chemistry, BINUCLEAR RUTHENIUM(II) COMPLEX, POLYMER PHOTOCATALYSTS, HYDROGEN EVOLUTION, CARBON-DIOXIDE, FORMIC-ACID, REDUCTION, EFFICIENT, ENERGY, SEMICONDUCTOR, CAPTURE |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10199742 |
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