Hydrogen spillover mechanism on covalent organic frameworks as investigated by ab initio density functional calculation

The hydrogen spillover mechanism, including the H chemisorption, diffusion, and H2 associative desorption on the surface of COFs and H atoms migration from metal catalyst to COFs, have been studied via density functional theory (DFT) calculation. The results described herein show that each sp2 C atom on COFs' surface can adsorb one H atom with the bond length dC–H between 1.11 and 1.14 Å, and the up-down arrangement of the adsorbed H atoms is the most stable configuration. By counting the chemisorption binding sites for these COFs, we can predict the saturation storage densities. High hydrogen storage densities show that the gravimetric uptakes of COFs are in the range of 5.13–6.06 wt%. The CI-NEB calculations reveal that one H atom diffusing along the C–C path on HHTP surface should overcome the 1.41–2.16 eV energy barrier. We chose tetrahedral Pt4 cluster and HHTP as the representative catalyst and substrate, respectively, to study the H migration from metal cluster to COFs. At most, two H atoms can migrate from Pt4 cluster to HHTP substrate. The migration reaction is an endothermic process, undergoing an activation barrier of 1.87 eV and 0.57 eV for the first and second H migration process, respectively. Three types of H2 associative desorption from hydrogenated COFs were studied: (I) the two H adatoms recombining to one H2 molecule with a recombination barrier of 4.28 eV, (II) the abstraction of adsorbed H atoms by gas-phase hydrogen atoms through ER type recombination reactions with a recombination barrier of 1.05 eV, (III) the H2 desorption through the reverse spillover mechanism with an energy barrier of 2.90 eV.