Constructing novel hyper-crosslinked conjugated polymers through molecular expansion for enhanced gas adsorption performance.

The porous organic polymers have been considered as effective materials for gas storage and adsorption. Herein, we synthesized highly crystalline nitrogen-rich covalent triazine frameworks (CTFs) by polycondensation for preparing the novel hyper-cross-linked conjugated polymers (HCCPs) with tunable specific surface area and pore volume through coupling Friedel-Crafts reaction, in which 1,4-Bis(chloromethyl)benzene and 4,4-Bis(chloromethyl)biphenyl as the expansion molecules were pillared between the layers of CTF-HUST. This technology not only increased the specific surface area and total pore volume of CTF-HUST by 2.56 and 4.68 times, but also greatly enhanced the utilization of adsorption sites of CTF-HUST. The HCCP2-1.25 exhibited the highest surface area (1349.29 mg) among these HCCPs and demonstrated excellent adsorption performance for ethyl acetate (1605.14 mg/g), ethanol (1371.49 mg/g), 1,2-Dichloroethane (1971.68 mg/g), benzene (1151.77 mg/g) and toluene (1024.28 mg/g) due to the multiple C-H…O, C-H…Cl, O-H…N and C-H…π interactions between volatile organic compounds (VOCs) and HCCPs framework. Moreover, CO and H storage capacities of the HCCP2-1.25 were 8.02 wt% and 1.54 wt%, 1.66 and 1.67 times higher than CTF-HUST, respectively. This study developed a simple and effective molecular expansion strategy to synthesize a series of novel high-surface-area porous polymers for potential applications in the environmental field.