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

Journal article

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 _x H _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.

Authors: Windle, CD; Wieczorek, A; Xiong, L; Sachs, M; Bozal-Ginesta, C

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Royal Society of Chemistry
• Journal: Chemical Science
• Volume: 11
• Issue: 32
• Pages: 8425-8432
• Publication date: 2020-07-24
• DOI: 10.1039/d0sc02986f
• EISSN: 2041-6539
• ISSN: 2041-6520
• Language: English
• Keywords: Polymer chemistry; Covalent bond; Carbon fibers; Photocatalysis; Catalysis; Grafting; Graphitic carbon nitride; Materials science; Chemistry; Organic chemistry; Carbon nitride; Nickel; Polymer