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Title: Spectroscopic Characterisation of a Bio-Inspired Ni-Based Proton Reduction Catalyst Bearing a Pentadentate N2S3 Ligand with Improved Photocatalytic Activity

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [3];  [3];  [4];  [1];  [4];  [1];  [5]
  1. Alternative Energies and Atomic Energy Commission (CEA), Saclay (France). Inst. de Biologie Integrative de la Cellule (I2BC)
  2. IMDEA Nanosciencia, Madrid (Spain)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Univ. Paris-Sud, Orsay (France). Inst. de Chimie Moleculaire et Materiaux d'Orsay (ICMMO)
  5. 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)
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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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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray absorption spectroscopy
nickel
photochemistry
reaction mechanisms
time-resolved spectroscopy