4.6 Article

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

Journal

JOURNAL OF PHYSICAL CHEMISTRY C
Volume 126, Issue 35, Pages 14801-14812

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.2c03194

Keywords

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Funding

  1. National Science Foundation [1626619]
  2. Alliance for Sustainable Energy, LLC
  3. National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) [DE-AC36- 08GO28308]
  4. Hydrogen Materials Advanced Research Consortium (HyMARC) , established as part of the Energy Materials Network under the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office
  5. Div Of Chem, Bioeng, Env, & Transp Sys
  6. Directorate For Engineering [1626619] Funding Source: National Science Foundation

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This study reports the synthesis of a Cu(I)-loaded COF material with subnanometer pores and a three-dimensional network morphology, and investigates the sorption mechanisms of hydrogen, ethylene, and carbon monoxide with this material. The results show that all three gases desorb near or above room temperature, and can be desorbed on-demand by irradiation with ultraviolet light. This work represents a step towards developing more practical ambient temperature gas storage and efficient regeneration of sorbents.
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 pi-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 pi-accepting gases through the use of external photostimuli.

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