A stable covalent organic framework for photocatalytic carbon dioxide reduction

Fu, Zhiwei, Wang, Xiaoyan, Gardner, Adrian, Wang, Xue, Chong, Samantha Y, Neri, Gaia, Cowan, Alexander J, Liu, Lunjie, Li, Xiaobo, Vogel, Anastasia
et al (show 5 more authors) (2020) A stable covalent organic framework for photocatalytic carbon dioxide reduction. CHEMICAL SCIENCE, 11 (2). pp. 543-550.

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Photocatalytic conversion of CO<sub>2</sub> into fuels is an important challenge for clean energy research and has attracted considerable interest. Here we show that tethering molecular catalysts-a rhenium complex, [Re(bpy)(CO)<sub>3</sub>Cl]-together in the form of a crystalline covalent organic framework (COF) affords a heterogeneous photocatalyst with a strong visible light absorption, a high CO<sub>2</sub> binding affinity, and ultimately an improved catalytic performance over its homogeneous Re counterpart. The COF incorporates bipyridine sites, allowing for ligation of the Re complex, into a fully π-conjugated backbone that is chemically robust and promotes light-harvesting. A maximum rate of 1040 μmol g<sup>-1</sup> h<sup>-1</sup> for CO production with 81% selectivity was measured. CO production rates were further increased up to 1400 μmol g<sup>-1</sup> h<sup>-1</sup>, with an improved selectivity of 86%, when a photosensitizer was added. Addition of platinum resulted in production of syngas, hence, the co-formation of H<sub>2</sub> and CO, the chemical composition of which could be adjusted by varying the ratio of COF to platinum. An amorphous analog of the COF showed significantly lower CO production rates, suggesting that crystallinity of the COF is beneficial to its photocatalytic performance in CO<sub>2</sub> reduction.

Item Type: Article
Uncontrolled Keywords: 34 Chemical Sciences, 3406 Physical Chemistry, 7 Affordable and Clean Energy
Depositing User: Symplectic Admin
Date Deposited: 06 Dec 2019 15:50
Last Modified: 20 Jun 2024 16:59
DOI: 10.1039/c9sc03800k
Open Access URL: https://doi.org/10.1039/C9SC03800K
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URI: https://livrepository.liverpool.ac.uk/id/eprint/3065219