Spectroscopic Characterisation of a Bio-Inspired Ni-Based Proton Reduction Catalyst Bearing a Pentadentate N2S3 Ligand with Improved Photocatalytic Activity
- Alternative Energies and Atomic Energy Commission (CEA), Saclay (France). Inst. de Biologie Integrative de la Cellule (I2BC)
- IMDEA Nanosciencia, Madrid (Spain)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. Paris-Sud, Orsay (France). Inst. de Chimie Moleculaire et Materiaux d'Orsay (ICMMO)
- Alternative Energies and Atomic Energy Commission (CEA), Saclay (France). Inst. de Biologie Integrative de la Cellule (I2BC); Univ. Paris-Sud, Orsay (France). Inst. de Chimie Moleculaire et Materiaux d'Orsay (ICMMO)
Inspired by the sulfur-rich environment found in active hydrogenase enzymes, a Ni-based proton reduction catalyst with pentadentate N2S3 ligand was synthesised. When coupled with [Ru(bpy)3]2+ (bpy=2,2 '-bipyridine) as photosensitiser and ascorbate as electron donor in a 1:1 mixture of dimethylacetamide and aqueous ascorbic acid/ascorbate buffer, the catalyst showed improved photocatalytic activity compared with a homologous counterpart bearing a tetradentate N2S2 ligand. The mechanistic pathway of photoinduced hydrogen evolution was comprehensively analysed through optical transient absorption and time-resolved X-ray absorption spectroscopy, which revealed important electronic and structural changes in the catalytic system during photoirradiation. Furthermore, the Ni-II catalyst undergoes a photoinduced metal-centred reduction to form a Ni-I intermediate with distorted square-bipyramidal geometry. Further kinetic analyses revealed differences in charge-separation dynamics between the pentadentate and tetradentate forms.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Commissariat a l’Energie Atomique (CEA); IMDEA - IMDEA Nanoscience Institute
- Grant/Contract Number:
- AC02-06CH11357; ANR-10-INSB-05-01; SEV-2016-0686
- OSTI ID:
- 1763722
- Journal Information:
- Chemistry - A European Journal, Vol. 26, Issue 13; ISSN 0947-6539
- Publisher:
- ChemPubSoc EuropeCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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