Dirhodium(II,II)/NiO Photocathode for Photoelectrocatalytic Hydrogen Evolution with Red Light.
J Am Chem Soc
; 143(3): 1610-1617, 2021 Jan 27.
Article
em En
| MEDLINE
| ID: mdl-33426881
ABSTRACT
A new Rh2(II,II) dimer has been synthesized and anchored onto a NiO photocathode. The dirhodium complex acts as both the sensitizer to inject holes into NiO and as catalyst for the production of hydrogen. The single-molecule design circumvents limitations of the conventional multicomponent approach with separate sensitizer and catalyst, thus simplifying the hydrogen production pathway and reducing energy losses associated with additional intermolecular charge transfer steps. The Rh2(II,II) complex absorbs strongly from the ultraviolet throughout the visible range and tails into the near-IR to â¼800 nm, permitting absorption of a significantly greater portion of the solar irradiance as compared to traditional dyes used in dye-sensitized solar cells and photoelectrosynthesis cells. The irradiation of the Rh2-NiO photoelectrode with 655 nm light (53 mW cm-2) results in a photocurrent that reaches 52 µA cm-2 at -0.2 V vs Ag/AgCl in the presence of p-toluenesulfonic acid (0.1 M), with Faradaic efficiencies of H2 production up to 85 ± 5% after 2.5 h without photoelectrode degradation. This work presents the first single-molecule photocatalyst, acting as both the light absorber and catalytic center on NiO, able to generate hydrogen from acidic solutions with red light when anchored to a p-type semiconductor, providing a promising new system for solar fuel production.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
Estados Unidos