Abstract
ZIF-7, built as an assembly of Zn(II) centers and benzimidazolate ligands, shows prominent S-shaped isotherms upon CO2 adsorption that can be attributed to sorbate-induced gate-opening phenomena involving a narrow-to-large pore phase transition. This peculiar sorption pattern can be captured via the formulation of thermodynamic isotherms, providing a direct enthalpic and entropic view of the gate-opening process. Relying on such an approach, an energy barrier with preferential enthalpic nature for CO2 adsorption/desorption in the gate-opening region could be unveiled. Moreover, the elastic energy involved during the gate-opening process was revisited to 1.4-2.8 kJ mol(-1) of solid in the temperature range 273-323 K, matching the value measured by isostatic compression of a ZIF-7_lp sample filled with DMF and showing a dominant entropic contribution.
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