This paper reports on the structural basis of CO₂ adsorption in a representative model of flexible metal-organic framework (MOF) material, Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN)₄] (NiBpene or PICNIC-60). NiBpene exhibits a CO₂ sorption isotherm with characteristic hysteresis and features on the desorption branch that can be associated with discrete structural changes. Various gas adsorption effects on the structure are demonstrated for CO₂ with respect to N₂, CH₄ and H₂ under static and flowing gas pressure conditions. For this complex material, a combination of crystal structure determination and density functional theory (DFT) is needed to make any real progress in explaining the observed structural transitions during adsorption/desorption. Possible enhancements of CO₂ gas adsorption under supercritical pressure conditions are considered, together with the implications for future exploitation. In situ operando small-angle neutron and X-ray scattering, neutron diffraction and X-ray diffraction under relevant gas pressure and flow conditions are discussed with respect to previous studies, including ex situ, a priori single-crystal X-ray diffraction structure determination. The results show how this flexible MOF material responds structurally during CO₂ adsorption; single or dual gas flow results for structural change remain similar to the static (Sieverts) adsorption case, and supercritical CO₂ adsorption results in enhanced gas uptake. Insights are drawn for this representative flexible MOF with implications for future flexible MOF sorbent design.
Keywords: X-ray diffraction; density functional theory; dual gas flow sorption; flexible metal-organic frameworks; gate-opening effects; in situ operando studies; neutron diffraction; small-angle X-ray scattering; small-angle neutron scattering; supercritical CO2 adsorption.