Hydrogen production from water splitting is nowadays recognized as a target, fundamental reaction for the production of clean fuels. Indeed, tremendous efforts have been devoted towards the research of suitable catalysts capable of performing this reaction. With respect to heterogeneous systems, molecular catalysts such as metal complexes are amenable to chemical functionalization in order to fine tune the catalytic properties. In this paper a new class of tris(2-pyridylmethyl)-amine (TPMA) cobalt(II) complexes (CoL0-4) has been synthesized and employed as hydrogen evolving catalysts under photochemical conditions taking advantage of Ru(bpy)(3)(2+) (where bpy is 2,2'-bipyridine) as a light-harvesting sensitizer and ascorbic acid as a sacrificial electron donor. Tuning of the photocatalytic activity has been attempted through the introduction of different substituents at the catalyst periphery rather than through a direct chemical modification of the chelating TPMA ligand. The results show that CoL0-4 behave as competent hydrogen evolving catalysts (HECs), although the effects played by the different substituents on the catalysis are relatively modest. Possible reasons supporting the observed behavior as well as possible improvements of the aforementioned tuning approach are discussed.

Photoinduced hydrogen evolution with new tetradentate cobalt(II) complexes based on the TPMA ligand

Badetti, Elena;Zonta, Cristiano
2016-01-01

Abstract

Hydrogen production from water splitting is nowadays recognized as a target, fundamental reaction for the production of clean fuels. Indeed, tremendous efforts have been devoted towards the research of suitable catalysts capable of performing this reaction. With respect to heterogeneous systems, molecular catalysts such as metal complexes are amenable to chemical functionalization in order to fine tune the catalytic properties. In this paper a new class of tris(2-pyridylmethyl)-amine (TPMA) cobalt(II) complexes (CoL0-4) has been synthesized and employed as hydrogen evolving catalysts under photochemical conditions taking advantage of Ru(bpy)(3)(2+) (where bpy is 2,2'-bipyridine) as a light-harvesting sensitizer and ascorbic acid as a sacrificial electron donor. Tuning of the photocatalytic activity has been attempted through the introduction of different substituents at the catalyst periphery rather than through a direct chemical modification of the chelating TPMA ligand. The results show that CoL0-4 behave as competent hydrogen evolving catalysts (HECs), although the effects played by the different substituents on the catalysis are relatively modest. Possible reasons supporting the observed behavior as well as possible improvements of the aforementioned tuning approach are discussed.
2016
45
File in questo prodotto:
File Dimensione Formato  
DaltonTransCo-2016.pdf

non disponibili

Descrizione: full text
Tipologia: Versione dell'editore
Licenza: Accesso chiuso-personale
Dimensione 1.19 MB
Formato Adobe PDF
1.19 MB Adobe PDF   Visualizza/Apri
Dalton-prereferaggio.pdf

accesso aperto

Descrizione: full text pre-print dell'autore
Tipologia: Documento in Pre-print
Licenza: Accesso gratuito (solo visione)
Dimensione 692.25 kB
Formato Adobe PDF
692.25 kB Adobe PDF Visualizza/Apri

I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/3702934
Citazioni
  • ???jsp.display-item.citation.pmc??? 9
  • Scopus 37
  • ???jsp.display-item.citation.isi??? 35
social impact