Phototriggered Desorption of Hydrogen, Ethylene, and Carbon Monoxide from a Cu(I)-Modified Covalent Organic Framework

Materials that are capable of adsorbing and desorbing gases near ambient conditions are highly sought after for many applications in gas storage and separations. While the physisorption of typical gases to high surface area covalent organic frameworks (COFs) occurs through relatively weak intermolecular forces, the tunability of framework materials makes them promising candidates for tailoring gas sorption enthalpies. The incorporation of open Cu(I) sites into framework materials is a proven strategy to increase gas uptake closer to ambient conditions for gases that are capable of π-back-bonding with Cu. Here, we report the synthesis of a Cu(I)-loaded COF with subnanometer pores and a three-dimensional network morphology, namely Cu(I)-COF-301. This study focused on the sorption mechanisms of hydrogen, ethylene, and carbon monoxide with this material under ultrahigh vacuum using temperature-programmed desorption and Kissinger analyses of variable ramp rate measurements. All three gases desorb near or above room temperature under these conditions, with activation energies of desorption (E_des) calculated as approximately 29, 57, and 68 kJ/mol, for hydrogen, ethylene, and carbon monoxide, respectively. Despite these strong Cu(I)-gas interactions, this work demonstrated the ability to desorb each gas on-demand below its normal desorption temperature upon irradiation with ultraviolet (UV) light. While thermal imaging experiments indicate that bulk photothermal heating of the COF accounts for some of the photodriven desorption, density functional theory calculations reveal that binding enthalpies are systematically lowered in the COF-hydrogen matrix excited state initiated by UV irradiation, further contributing to gas desorption. This work represents a step toward the development of more practical ambient temperature storage and efficient regeneration of sorbents for applications with hydrogen and π-accepting gases through the use of external photostimuli.