The search for metal-free organic photocatalysts for H2 production from water using visible light remains a key challenge. Reported herein is a molecular structural design of pure organic photocatalysts, derived from conjugated polybenzothiadiazoles, for photocatalytic H2 evolution using visible light. By alternating the substitution position of the electron-withdrawing benzothiadizole unit on the phenyl unit as a comonomer, various polymers with either one- or three-dimensional structures were synthesized and the effect of the molecular structure on their catalytic activity was investigated. Photocatalytic H2 evolution efficiencies up to 116 μmol h(-1) were observed by employing the linear polymer based on a phenyl-benzothiadiazole alternating main chain, with an apparent quantum yield (AQY) of 4.01 % at 420 nm using triethanolamine as the sacrificial agent.
A simple structural design principle and band position alignment of conjugated microporous polymers for enhanced photocatalytic efficiency is presented. The valence and conduction band positions of the polymer networks can be fine-tuned by altering the substitution positions on the centered phenyl unit to match the required redox potential of the catalytic reactions under visible light.
High surface area porous conjugated polymers were synthesized via the high internal phase emulsion polymerization technique and micropore engineering as efficient heterogeneous photocatalysts for highly selective oxidation of organic sulfides to sulfoxides under visible light.
Pure organic, heterogeneous, metal-free,
and visible light-active
photocatalysts offer a more sustainable and environmentally friendly
alternative to traditional metal-based catalysts. Here we report a
series of microporous organic polymers containing photoactive conjugated
organic semiconductor units as heterogeneous photocatalysts for a
visible-light-promoted, highly selective bromination reaction of electron-rich
aromatic compounds using HBr as a bromine source and molecular oxygen
as a clean oxidant. Via a simple Friedel–Crafts alkylation
reaction, the microporous organic polymers were obtained by cross-linking
of organic semiconductor compounds with defined valence and conduction
band positions. The utilization of the simply prepared porous polymer-based
photocatalytic systems opens new opportunities toward a sustainable
and efficient material design for catalysis.
A conjugated porous poly-benzobisthiadiazole network was synthesized via high internal phase emulsion polymerization as a highly active and stable heterogeneous photocatalyst. Under a household energy saving light bulb, dehalogenation of a-bromoacetophenones was performed in an almost quantitative manner at room temperature.Photocatalysts, which absorb mainly in the visible range of light, have established notable prominence in applications such as water splitting, solar energy storage, and photovoltaics.
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