Microporous Hyper-Cross-Linked Aromatic Polymers Designed for Methane and Carbon Dioxide Adsorption

A Friedel−Crafts reaction was used to obtain covalent aromatic networks with high surface area and microporosity suited for CO2 and CH4 adsorption, even at low pressures. Starting from tetraphenylmethane and formaldehyde dimethyl acetal in different concentrations, the reaction yields porous polymers which were characterized with a wealth of experimental and computational methods. Thermogravimetry, infrared spectroscopy, and solid-state NMR were used to study the material structure. The pore distributions were measured by applying nonlocal density functional theory analysis to the adsorption isotherms of N2 at 77 K and Ar at 87 K (the latter being more suited for pore widths less than 10 Å). Carbon dioxide and methane were adsorbed at 273 and 298 K to evaluate the performance of these systems in gas capture, separation, and storage. A theoretical model of the porous network was defined to describe the ordered fraction of the material, with particular attention to ultramicropores. Ar, CO2, and CH4 adsorption in this model material was simulated by Monte Carlo techniques with a purposely optimized force field