Theoretical Insight into Gate-Opening Adsorption Mechanism and Sigmoidal Adsorption Isotherm into Porous Coordination Polymer

The gate-opening adsorption mechanism and sigmoidal adsorption isotherm were theoretically investigated taking CO 2 adsorption into porous coordination polymers, [Fe(ppt) 2 ] n ( PCP-N, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) and [Fe(dpt) 2 ] n ( PCP-C, Hdpt = 3-(2-pyridinyl)-5-(4-pyridyl)-1,2,4-triazole) as examples, where the hybrid method consisting of dispersion-corrected DFT for infinite PCP and a post-Hartree–Fock (SCS-MP2 and CCSD(T)) method for the cluster model was employed. PCP-N has site I (one-dimensional channel), site II (small aperture to site I), and site III (small pore) useful for CO 2 adsorption. CO 2 adsorption at site I occurs in a one by one manner with a Langmuir adsorption isotherm. CO 2 adsorption at sites II and III occurs through a gate-opening adsorption mechanism, because the crystal deformation energy ( E DEF ) at these sites is induced largely by the first CO 2 adsorption but induced much less by the subsequent CO 2 adsorption. Interestingly, nine CO 2 molecules are adsorbed simultaneously at these sites because a large E DEF cannot be overcome by adsorption of one CO 2 molecule but can be by simultaneous adsorption of nine CO 2 molecules. For such CO 2 adsorption, the Langmuir–Freundlich sigmoidal adsorption isotherm was derived from the equilibrium equation for CO 2 adsorption. A very complicated CO 2 adsorption isotherm, experimentally observed, is reproduced by combination of the Langmuir and Langmuir–Freundlich adsorption isotherms. In PCP-C, CO 2 adsorption occurs only at site I with the Langmuir adsorption isotherm. Sites II and III of PCP-C cannot be used for CO 2 adsorption because a very large E DEF cannot be overcome by simultaneous adsorption of nine CO 2 molecules. Factors necessary for gate-opening adsorption mechanism are discussed on the basis of differences between PCP-N and PCP-C .