Photocatalytic reduction of CO2 using metal complexes

Synthesis, Structure and DFT Study of a Rhenium(I) Pyridylpyrazole Complex as a Potential Photocatalyst for CO2 Reduction

“…One of the reported means to utilised CO 2 is by photocatalytic reduction pathway (Yamazaki et al 2015). Typically, metal complexes are used in the reduction of CO 2 with relatively high quantum yields and selectivity.…”

“…These Re(I) complexes have since used as a benchmark for further structural modification to improve its catalytic activity. Several structural designs have been employed which focuses on either the substitution of axial L ligand with other groups or the implementation of ancillary extensions on the bpy ligand (Doherty et al 2009;Gibson & He 2001;Yamazaki et al 2015). In the CO 2 reductive cycle, the first step involves the formation of one-electron reduction species (OERS) of Re n-with the subsequent dissociation of L ligand from the Re metal centre (Agarwal et al 2011;Sahara & Ishitani 2015).…”

Mechanism of Water Oxidation Catalyzed by a Dinuclear Ruthenium Complex Bridged by Anthraquinone

“…Artificial photosynthesis is the conversion process from solar to chemical energy and includes carbon dioxide, proton, and nitrogen reduction by visible light irradiation, with water as the electron source [1][2][3][4][5][6][7][8][9][10]. Four-electron water oxidation to dioxygen is, therefore, an essential process for artificial photosynthesis, while there are several types of reduction processes.…”

“…DFT calculations of [Ru2(OH)2(t-Bu2q)2(btpyan)] 2+ (t-Bu2q: 3,6-di-tert-butyl-1,2-benzoquinone, [1] 2+ ) by Muckerman [49,52], Yamaguchi [55][56][57], and Baik [58] revealed intramolecular homo-coupling mechanisms. Resonance Raman spectra of the chemically and electrochemically oxidized forms of [Ru2(µ-Cl)(bpy)2(btpyan)] 3+ ( [2] 3+ , bpy = 2,2′-bipyridine) showed an O-O vibration band at 824 cm −1 , which was shifted to 780 cm −1 when chemical and electrochemical oxidation of [2] 3+ was conducted in H2 18 O [49,50]. Therefore, water oxidation catalyzed by [2] 3+ proceeds via intramolecular coupling of two high-valent Ru=O species.…”

“…Resonance Raman spectra of the chemically and electrochemically oxidized forms of [Ru2(µ-Cl)(bpy)2(btpyan)] 3+ ( [2] 3+ , bpy = 2,2′-bipyridine) showed an O-O vibration band at 824 cm −1 , which was shifted to 780 cm −1 when chemical and electrochemical oxidation of [2] 3+ was conducted in H2 18 O [49,50]. Therefore, water oxidation catalyzed by [2] 3+ proceeds via intramolecular coupling of two high-valent Ru=O species. However, the details of high-valent Ru=O coupling are not yet clear.…”