Visible-Light-Driven Water Oxidation on Self-Assembled Metal-Free Organic@Carbon Junctions at Neutral pH

OLAYA, ASTRID J.; RIVA, JULIETA S.; BASTER, DOMINIKA; SILVA, WANDERSON O.; PICHARD, FRANÇOIS; GIRAULT, HUBERT H.

JACS Au

ACS Publications

Año: 2021 vol. 1 p. 2294 - 2294

2691-3704

ustainable water oxidation requires low-cost, stable, and efficient redox couples, photosensitizers, and catalysts. Here, we introduce the in situ self-assembly of metal-atom-free organic-based semiconductive structures on the surface of carbon supports. The resulting TTF/TTF?+@carbon junction (TTF = tetrathiafulvalene) acts as an all-in-one highly stable redox-shuttle/photosensitizer/molecular-catalyst triad for the visible-light-driven water oxidation reaction (WOR) at neutral pH, eliminating the need for metallic or organometallic catalysts and sacrificial electron acceptors. A water/butyronitrile emulsion was used to physically separate the photoproducts of the WOR, H+ and TTF, allowing the extraction and subsequent reduction of protons in water, and the in situ electrochemical oxidation of TTF to TTF?+ on carbon in butyronitrile by constant anode potential electrolysis. During 100 h, no decomposition of TTF was observed and O2 was generated from the emulsion while H2 was constant