Transition from chemisorption to physisorption of H2 on Ti functionalized [2,2,2]paracyclophane: A computational search for hydrogen storage

Abstract: In this work, we studied the hydrogen adsorption-desorption properties and storage capacities of Ti functionalized [2,2,2]paracyclophane (PCP222) using density functional theory and molecular dynamic simulation. The Ti atom was bonded strongly with the benzene ring of PCP222 via Dewar interaction. Subsequently, the calculation of the diffusion energy barrier revealed a significantly high energy barrier of 5.97 eV preventing the Ti clustering over PCP222 surface. On adsorption of hydrogen, the first H2 molecule was chemisorbed over PCP222 with a binding energy of 1.79 eV with the Ti metals. Further addition of H2 molecules, however, exhibited their physisorption over PCP222-Ti through the Kubas type H2 interaction. The charge transfer mechanism during the hydrogen adsorption was explored by the Hirshfeld charge analysis and electrostatic potential map, and the PDOS, and Baders topological analysis revealed the nature of the interaction between Ti and H2. The PCP222 functionalized with three Ti atoms showed a maximum hydrogen uptake capacity of up to 7.37 wt%, which was fairly above the US-DOE criterion. The practical H2 storage estimation revealed that at ambient conditions, the gravimetric density of up to 6.06 wt% H2 molecules could be usable, and up to 1.31 wt% of adsorbed H2 molecules were retained with the host. The ADMP molecular dynamics simulations assured the reversibility by desorption of adsorbed H2 and the structural integrity of the host material at sufficiently above the desorption temperature (300K and 500K). Therefore, the Ti-functionalized PCP222 can be considered as a thermodynamically viable and potentially reversible H2 storage material.