Issue 7, 2017

Photoelectrocatalytic H2 evolution in water with molecular catalysts immobilised on p-Si via a stabilising mesoporous TiO2 interlayer

Abstract

The development of photoelectrodes capable of light-driven hydrogen evolution from water is an important approach for the storage of solar energy in the form of a chemical energy carrier. However, molecular catalyst-based photocathodes remain scarcely reported and typically suffer from low efficiencies and/or stabilities due to inadequate strategies for interfacing the molecular component with the light-harvesting material. In this study, we report the straightforward preparation of a p-silicon|mesoporous titania|molecular catalyst photocathode assembly that is active towards proton reduction in aqueous media with an onset potential of +0.4 V vs. RHE. The mesoporous TiO2 scaffold acts as an electron shuttle between the silicon and the catalyst, while also stabilising the silicon from passivation and enabling a high loading of molecular catalysts (>30 nmol (geometrical cm)−2). When a Ni bis(diphosphine)-based catalyst is anchored on the surface of the electrode, a high turnover number of ∼1 × 103 was obtained from photoelectrolysis under UV-filtered simulated solar irradiation at 1 Sun after 24 h at pH 4.5. Notwithstanding its aptitude for molecular catalyst immobilisation, the p-Si|TiO2 photoelectrode showed great versatility towards different catalysts and pH conditions, with photoelectrocatalytic H2 generation also being achieved with platinum and a hydrogenase as catalyst, highlighting the flexible platform it represents for many potential reductive catalysis transformations.

Graphical abstract: Photoelectrocatalytic H2 evolution in water with molecular catalysts immobilised on p-Si via a stabilising mesoporous TiO2 interlayer

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Mar 2017
Accepted
30 Apr 2017
First published
04 May 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 5172-5180

Photoelectrocatalytic H2 evolution in water with molecular catalysts immobilised on p-Si via a stabilising mesoporous TiO2 interlayer

J. J. Leung, J. Warnan, D. H. Nam, J. Z. Zhang, J. Willkomm and E. Reisner, Chem. Sci., 2017, 8, 5172 DOI: 10.1039/C7SC01277B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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