Spectroscopic Characterization of Bio-inspired Ni-based Proton Reduction Catalyst Bearing Pentadentate N2S3 Ligand with Improved Photocatalytic Activity - Laboratoire brestois de mécanique et des systèmes Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2019

Spectroscopic Characterization of Bio-inspired Ni-based Proton Reduction Catalyst Bearing Pentadentate N2S3 Ligand with Improved Photocatalytic Activity

Ally Aukauloo
Philipp Gotico
Dooshaye Moonshiram
  • Fonction : Auteur
Cunming Liu
Xiaoyi Zhang
  • Fonction : Auteur
Régis Guillot
Zakaria Halime

Résumé

Inspired by the sulphur-rich environment found in active hydrogenase enzymes, a novel Ni-based proton reduction catalyst with pentadentate N 2 S 3 ligand was synthesized. When coupled with a [Ru(bpy) 3 ] 2+ 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 to a homologous counterpart with a tetradentate N 2 S 2 ligand. The mechanistic pathway of photo-induced hydrogen evolution was comprehensively analysed through optical transient absorption (OTA) and time-resolved X-ray absorption spectroscopy (tr-XAS) revealing important electronic and structural changes in the catalytic system during photo-irradiation. It was found that the Ni (II) catalyst undergoes a photo-induced metal-centred reduction to form a Ni (I) intermediate bearing a distorted square bipyramidal geometry. Further kinetic analyses pointed out differences in charge separation dynamics between the pentadentate and tetradentate homologues.
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Dates et versions

hal-02379389 , version 1 (10-11-2020)

Identifiants

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Annamaria Quaranta, Winfried Leibl, Ally Aukauloo, Philipp Gotico, Dooshaye Moonshiram, et al.. Spectroscopic Characterization of Bio-inspired Ni-based Proton Reduction Catalyst Bearing Pentadentate N2S3 Ligand with Improved Photocatalytic Activity. Chemistry - A European Journal, 2019, ⟨10.1002/chem.201904934⟩. ⟨hal-02379389⟩
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