Olaya Astrid J, Riva Julieta S, Baster Dominika, Silva Wanderson O, Pichard François, Girault Hubert H
Laboratory of Physical and Analytical Electrochemistry, EPFL Valais Wallis, École Polytechnique Fédérale de Lausanne, CH-1951 Sion, Switzerland.
Consejo Nacional de Investigaciones Científicas y Técnicas, CONICET, Facultad de Matemática, Astronomía, Física y Computación, Universidad Nacional de Córdoba, Medina Allende s/n, Ciudad Universitaria, X5000HUA, Córdoba, Argentina.
JACS Au. 2021 Nov 11;1(12):2294-2302. doi: 10.1021/jacsau.1c00408. eCollection 2021 Dec 27.
Sustainable water oxidation requires low-cost, stable, and efficient redox couples, photosensitizers, and catalysts. Here, we introduce the 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 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 O was generated from the emulsion while H was constantly produced in the aqueous phase. This work opens new perspectives for a new generation of metal-atom-free, low-cost, redox-driven water-splitting strategies.
可持续的水氧化需要低成本、稳定且高效的氧化还原对、光敏剂和催化剂。在此，我们介绍了在碳载体表面上无金属原子的有机基半导体结构的自组装。所得的TTF/TTF@碳结（TTF = 四硫富瓦烯）作为一种一体化的高度稳定的氧化还原穿梭体/光敏剂/分子催化剂三联体，用于在中性pH下可见光驱动的水氧化反应（WOR），无需金属或有机金属催化剂以及牺牲电子受体。使用水/丁腈乳液将WOR的光产物H和TTF物理分离，从而实现水中质子的提取和后续还原，以及通过恒阳极电位电解在丁腈中碳上TTF到TTF的电化学氧化。在100小时内，未观察到TTF分解，乳液中产生O，而水相中持续产生H。这项工作为新一代无金属原子、低成本、氧化还原驱动的水分解策略开辟了新的前景。
