The synthesis of porous carbon has been widely studied, as their large specific surface areas and tunable physical and chemical properties make their use advantageous in a myriad of applications, including catalysis, gas separation, water remediation, and energy storage. Recently, the production of porous carbon using polyolefins as precursors has been explored, as it utilizes widely accessible and cost-effective materials to generate high carbon content products. This method relies on a sulfonation-induced crosslinking mechanism which allows for the formation of thermally stable networks, ultimately generating highly carbonaceous structures upon pyrolysis. However, the hydrophobic nature of semicrystalline polyolefins limits the effectiveness of this mechanism, making the reaction a diffusion limited process. This work aims to mitigate the diffusion limitations of sulfonation of polyolefins by tailoring their structure to increase their hydrophilicity. This is achieved through grafting hydroxyl groups onto the polyolefin backbone, thereby significantly enhancing their sulfonation reaction kinetics. Specifically, by grafting hydroxyl groups onto a polyethylene-like polymer backbone, the carbon yield increases to values over 50 wt.% after 2 h of sulfonation relative to the 16 h required for the unfunctionalized control to obtain a similar yield. This result emphasizes the role that controlling polyolefin structure has in improving reaction kinetics and crosslinking efficiency and can be used in future applications to inform polymer design for the synthesis of carbon materials.
