Photocatalytic Reduction of CO2 to CO in Aqueous Solution under Red-Light Irradiation by a Zn-Porphyrin-Sensitized Mn(I) Catalyst.

SHIPP, James, PARKER, Simon, SPALL, Steven, PERALTA-ARRIAGA, Samantha L, ROBERTSON, Craig C, CHEKULAEV, Dimitri, PORTIUS, Peter, TUREGA, Simon, BUCKLEY, Alastair, ROTHMAN, Rachael and WEINSTEIN, Julia A (2022). Photocatalytic Reduction of CO2 to CO in Aqueous Solution under Red-Light Irradiation by a Zn-Porphyrin-Sensitized Mn(I) Catalyst. Inorganic chemistry, 61 (34), 13281-13292.

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Abstract

This work demonstrates photocatalytic CO2 reduction by a noble-metal-free photosensitizer-catalyst system in aqueous solution under red-light irradiation. A water-soluble Mn(I) tricarbonyl diimine complex, [MnBr(4,4′-{Et2O3PCH2}2-2,2′-bipyridyl)(CO)3] (1), has been fully characterized, including single-crystal X-ray crystallography, and shown to reduce CO2 to CO following photosensitization by tetra(N-methyl-4-pyridyl)porphyrin Zn(II) tetrachloride [Zn(TMPyP)]Cl4 (2) under 625 nm irradiation. This is the first example of 2 employed as a photosensitizer for CO2 reduction. The incorporation of −P(O)(OEt)2 groups, decoupled from the core of the catalyst by a −CH2– spacer, afforded water solubility without compromising the electronic properties of the catalyst. The photostability of the active Mn(I) catalyst over prolonged periods of irradiation with red light was confirmed by 1H and 13C{1H} NMR spectroscopy. This first report on Mn(I) species as a homogeneous photocatalyst, working in water and under red light, illustrates further future prospects of intrinsically photounstable Mn(I) complexes as solar-driven catalysts in an aqueous environment.

Item Type:	Article
Uncontrolled Keywords:	0302 Inorganic Chemistry; 0306 Physical Chemistry (incl. Structural); 0399 Other Chemical Sciences; Inorganic & Nuclear Chemistry
Identification Number:	https://doi.org/10.1021/acs.inorgchem.2c00091
Page Range:	13281-13292
SWORD Depositor:	Symplectic Elements
Depositing User:	Symplectic Elements
Date Deposited:	08 Nov 2022 11:17
Last Modified:	12 Oct 2023 09:16
URI:	https://shura.shu.ac.uk/id/eprint/30995

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