Para-Fluoro-Thiol Reaction: Powerful Tool for the Versatile Functionalization of Microporous Materials

Hyper-cross-linked polystyrene-like polymers (HCPs) represent a cost-effective, highly stable, and scalable class of porous materials with significant potential for environmental remediation, catalysis, gas storage, and separation applications. Herein, we demonstrate that the introduction of pentafluorostyrene in the precursor HCP formulation and the subsequent para-fluoro-thiol reaction is an efficient and energy-saving strategy to functionalize these materials. The important quantity of thiol compounds available in the market offers a wide variety of chemical functions accessible for microporous materials and tailors the properties of HCPs to the specific sorption application. In this study, the proportion of the three building blocks used in the polymerization is first optimized to obtain HCPs exhibiting high microporosity, large Brunauer–Emmett–Teller surface areas, and pore volumes independent of the incorporated functional groups (hexyl, alcohol, amine, or sulfonate). The efficiency and versatility of the para-fluoro-thiol coupling reaction are then demonstrated. Finally, the HCPs′ CO2 adsorption capacity was accessed, as an analyte example, using a manometric setup. At ambient pressure, uptake capacity is predominantly governed by surface chemistry alongside textural properties, while at higher pressure, the uptake capacity is correlated with pore volume, with a probable influence of the swelling of the material upon adsorption.