Conjugated Microporous Polymers as Heterogeneous Photocatalysts for Efficient Degradation of a Mustard-Gas Simulant.

Abstract

Compared with traditional metal-based photosensitizers, heterogeneous and organic photocatalysts with visible-light activity are more environmentally friendly and sustainable. The simultaneous introduction of electron-rich and electron-deficient units in donor-acceptor typed conjugated microporous polymer (CMP) photocatalysts can significantly enhance their visible-light harvesting and separation efficiency of photogenerated carriers. Here, two carbazole-based CMPs (CzBSe-CMP and CzBQn-CMP) were successfully constructed through a cost-effective process. They show inherent porosity with large Brunauer-Emmett-Teller surface area and excellent thermal and chemical stability. Their photoelectric properties, energy levels, optical band gaps, transient photocurrent response, and photocatalytic activity could be conveniently tailored through tuning the electron-deficient moiety in polymer networks. More importantly, CzBSe-CMP was found to be a superior solid photocatalyst for selective photo-oxidation of mustard gas simulant 2-chloroethyl ethyl sulfide into a nontoxic product by using molecular oxygen as a sustainable oxygen source under visible-light illumination. In addition, the obtained CMP-based photocatalysts also showed excellent recyclability and could be reutilized through adding more simulants or a simple separation procedure. The current contribution provides great application prospects for CMPs as metal-free, solid photocatalysts in organic transformation and environmental protection.