Dirhodium(II,II)/NiO Photocathode for Photoelectrocatalytic Hydrogen Evolution with Red Light
- 11 January 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (3), 1610-1617
- https://doi.org/10.1021/jacs.0c12171
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 ∼800 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.Funding Information
- Basic Energy Sciences (DE-SC0020243)
This publication has 50 references indexed in Scilit:
- Advancing photosystem II photoelectrochemistry for semi-artificial photosynthesisNature Reviews Chemistry, 2019
- Photoelectrochemical Cells Based on Dye Sensitization for Electricity and Fuel ProductionChimia, 2019
- Recent advances in dye-sensitized photoelectrochemical cells for water splittingEnergyChem, 2019
- Water splitting dye-sensitized solar cellsNano Today, 2017
- Molecular cathode and photocathode materials for hydrogen evolution in photoelectrochemical devicesJournal of Photochemistry and Photobiology C: Photochemistry Reviews, 2015
- High‐Performance Photoelectrochemical Cells Based on a Binuclear Ruthenium Catalyst for Visible‐Light‐Driven Water OxidationChemSusChem, 2014
- Photoelectrochemical cellsNature, 2001
- A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 filmsNature, 1991
- Dynamics of light-induced water cleavage in colloidal systemsJournal of the American Chemical Society, 1981
- Electrochemical Photolysis of Water at a Semiconductor ElectrodeNature, 1972