Liu Lunjie, Gao Mei-Yan, Yang Haofan, Wang Xiaoyan, Li Xiaobo, Cooper Andrew I
Department of Chemistry and Materials Innovation Factory, University of Liverpool, 51 Oxford Street, Liverpool L7 3NY, United Kingdom.
Department of Chemical Sciences, Bernal Institute, University of Limerick, Limerick V94 T9PX, Republic of Ireland.
J Am Chem Soc. 2021 Nov 24;143(46):19287-19293. doi: 10.1021/jacs.1c09979. Epub 2021 Nov 10.
Hydrogen peroxide (HO) is one of the most important industrial oxidants. In principle, photocatalytic HO synthesis from oxygen and HO using sunlight could provide a cleaner alternative route to the current anthraquinone process. Recently, conjugated organic materials have been studied as photocatalysts for solar fuels synthesis because they offer synthetic tunability over a large chemical space. Here, we used high-throughput experiments to discover a linear conjugated polymer, poly(3-4-ethynylphenyl)ethynyl)pyridine (DE7), which exhibits efficient photocatalytic HO production from HO and O under visible light illumination for periods of up to 10 h or so. The apparent quantum yield was 8.7% at 420 nm. Mechanistic investigations showed that the HO was produced via the photoinduced stepwise reduction of O. At longer photolysis times, however, this catalyst decomposed, suggesting a need to focus the photostability of organic photocatalysts, as well as the initial catalytic production rates.
过氧化氢（HO）是最重要的工业氧化剂之一。原则上，利用阳光通过光催化由氧气和HO合成过氧化氢可为当前的蒽醌法提供一条更清洁的替代路线。最近，共轭有机材料作为太阳能燃料合成的光催化剂受到了研究，因为它们在很大的化学空间内具有合成可调性。在此，我们通过高通量实验发现了一种线性共轭聚合物，聚（3 - 4 - 乙炔基苯基）乙炔基吡啶（DE7），它在可见光照射下能高效地由HO和O合成过氧化氢，持续时间长达10小时左右。在420nm处的表观量子产率为8.7%。机理研究表明，过氧化氢是通过光诱导的O逐步还原产生的。然而，在较长的光解时间下，这种催化剂会分解，这表明需要关注有机光催化剂的光稳定性以及初始催化产率。
