Jia-Jia Zheng, Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa, Shigeyoshi Sakaki
The gate-opening adsorption mechanism and sigmoidal adsorption isotherm were theoretically investigated taking CO adsorption into porous coordination polymers, [Fe(ppt)] (PCP-N, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) and [Fe(dpt)] (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 adsorption. CO adsorption at site I occurs in a one by one manner with a Langmuir adsorption isotherm. CO adsorption at sites II and III occurs through a gate-opening adsorption mechanism, because the crystal deformation energy ( E) at these sites is induced largely by the first CO adsorption but induced much less by the subsequent CO adsorption. Interestingly, nine CO molecules are adsorbed simultaneously at these sites because a large E cannot be overcome by adsorption of one CO molecule but can be by simultaneous adsorption of nine CO molecules. For such CO adsorption, the Langmuir-Freundlich sigmoidal adsorption isotherm was derived from the equilibrium equation for CO adsorption. A very complicated CO adsorption isotherm, experimentally observed, is reproduced by combination of the Langmuir and Langmuir-Freundlich adsorption isotherms. In PCP-C, CO adsorption occurs only at site I with the Langmuir adsorption isotherm. Sites II and III of PCP-C cannot be used for CO adsorption because a very large E cannot be overcome by simultaneous adsorption of nine CO molecules. Factors necessary for gate-opening adsorption mechanism are discussed on the basis of differences between PCP-N and PCP-C.
