Covalent grafting of molecular catalysts on C3NxHy as robust, efficient and well-defined photocatalysts for solar fuel synthesis

Christopher D. Windle; Alexander Wieczorek; Lunqiao Xiong; Michael Sachs; Carlota Bozal-Ginesta; Hyojung Cha; Jeremy K. Cockcroft; James Durrant; Junwang Tang

doi:10.1039/D0SC02986F

Covalent grafting of molecular catalysts on C₃N_xH_y as robust, efficient and well-defined photocatalysts for solar fuel synthesis†

Christopher D. Windle,^a Alexander Wieczorek,

^b Lunqiao Xiong,

^a Michael Sachs,

^b Carlota Bozal-Ginesta,^b Hyojung Cha,

^b Jeremy K. Cockcroft,

^c James Durrant

^b and Junwang Tang

*^a

Author affiliations

* Corresponding authors

^a Department of Chemical Engineering, UCL Torrington Place, London, UK
E-mail: junwang.tang@ucl.ac.uk

^b Department of Chemistry and Centre for Processable Electronics, Imperial College London, White City Campus, London, UK

^c Department of Chemistry, University College London, 20 Gordon Street, London, UK

Abstract

The covalent attachment of molecules to 2D materials is an emerging area as strong covalent chemistry offers new hybrid properties and greater mechanical stability compared with nanoparticles. A nickel bis-aminothiophenol catalyst was grafted onto a range of 2D carbon nitrides (C₃N_xH_y) to form noble metal-free photocatalysts for H₂ production. The hybrids produce H₂ beyond 8 days with turnover numbers reaching 1360 based on nickel, a more than 3 fold higher durability than reported molecular catalyst-carbon nitride mixtures, and under longer wavelengths (>475 nm). Time-resolved spectroscopy reveals sub-microsecond electron transfer to the grafted catalyst, six orders of magnitude faster compared with similar reports of non-grafted catalysts. The photoelectrons on the catalyst have a ca. 1000 times longer half-time (7 ms) compared with bare carbon nitride (10 μs). The grafting strategy operates across a range of molecular catalyst-carbon nitride combinations, thus paving the way for robust efficient photocatalysts based on low-cost tunable components.

This article is part of the themed collection: 2020 Chemical Science HOT Article Collection

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DOI: https://doi.org/10.1039/D0SC02986F
Article type: Edge Article
Submitted: 27 May 2020
Accepted: 24 Jul 2020
First published: 24 Jul 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2020,11, 8425-8432

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Covalent grafting of molecular catalysts on C₃N_xH_y as robust, efficient and well-defined photocatalysts for solar fuel synthesis

C. D. Windle, A. Wieczorek, L. Xiong, M. Sachs, C. Bozal-Ginesta, H. Cha, J. K. Cockcroft, J. Durrant and J. Tang, Chem. Sci., 2020, 11, 8425 DOI: 10.1039/D0SC02986F

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