Chemically Activated Covalent Triazine Frameworks with Enhanced Textural Properties for High Capacity Gas Storage

Chemical activation of porous/nonporous materials to achieve high surface area sorbents with enhanced textural properties is a very promising strategy. The chemical activation using KOH, however, could lead to broad distribution of pores originating from the simultaneous pore deepening and widening pathways. Accordingly, establishing correlation between the chemical/textural properties of starting porous/nonporous materials and various pore formation mechanisms is quite critical to realize superior porosity and gas uptake properties. Here, we show that the chemical and textural properties of starting porous organic polymers, that is, covalent triazine frameworks (CTF), have profound effect on the resulting porosity of the frameworks. The chemical activation of microporous CTF-1 using KOH at 700 °C enabled the preparation of chemically activated CTF-1, caCTF-1-700, which predominantly showed pore deepening, leading to an increased surface area of 2367 m² g^-1 and significantly enhanced gas adsorption properties with CO₂ uptake capacities up to 6.0 mmol g^-1 at 1 bar and 1.45 mmol g^-1 at 0.15 bar and 273 K along with a isosteric heats of adsorption (Q_st) of 30.6 kJ mol^-1. In addition, a remarkable H₂ uptake capacity of 2.46 and 1.66 wt % at 77 and 87 K, 1 bar along with the Q_st value of 10.95 kJ mol^-1 at zero coverage was also observed for the caCTF-1-700. Notably, the activation of mesoporous CTF-2 under the same conditions was accompanied by a decrease in its surface area and also in the conversion of mesopores into the micropores, thus leading to a pore deepening/narrowing rather than widening. We attributed this result to the presence of reactive weak spots, triazine moieties, for the chemical activation reaction within the CTF backbone. These results collectively suggest the critical role of chemical and pore characteristics of porous organic polymers in chemical activation to realize solid-sorbents for high capacity gas storage applications.