How do defects affect hydrogen spillover on graphene-supported Pt? A DFT study

Hydrogen dissociation, adsorption, and spillover on Pt4 supported on defective graphene that contains vacancy defects, such as single and di-vacancy graphenes (SVG and DVG), have been studied using density functional theory (DFT) with dispersion correction (Grimme-D3). Vacancy defects lead to n-type doping of graphene from the Pt4 cluster, which is contrary to the p-type doping on pristine graphene. Also, the metal–support interactions increase with the presence of a vacancy defect as indicated by more negative Pt4 binding energies on the SVG, and 5-8-5, 5555-6-7777, and 555–777 DVGs of −8.60, −4.51, −4.15 and −3.63 eV, respectively, compared to that on pristine graphene (−2.16 eV). Atomic hydrogen adsorption is more stable on all defective graphenes with adsorption energies of −2.24, −0.16, 0.05, and −0.27 eV for SVG, 5-8-5, 5555-6-7777, and 555–777 DVGs, respectively, as compared to that on pristine graphene (+1.38 eV). Spontaneous hydrogen dissociative adsorption on the two-fold coordinated C site of bare SVG occurs with an adsorption energy per hydrogen atom of −1.77 eV, while those on the three types of DVGs are in the range of ∼0.03–0.29 eV; these are all more stable than those on pristine graphene that fall in the range of 0.89–1.53 eV. The energy barriers for hydrogen spillover from Pt4 to the defective graphene are 0.91, 1.09, 0.90, and 0.71 eV for SVG, 5-8-5, 5555-6-7777, and 555–777 DVGs, respectively. Ab initio molecular dynamics (AIMD) simulations show that the adsorption of up to six hydrogen molecules, with and without spillover, on the four Pt4/defective graphene systems, is stable at room temperature. This study demonstrates that the presence of vacancy defects on graphene could improve hydrogen adsorption and spillover. A trend is discovered—when the magnitude of binding energies of metal–support interaction is stronger than −3.5 eV and the adsorption energies of atomic hydrogen on the support are negative or close to zero, there is potential to facilitate the occurrence of hydrogen spillover, correlating with the hydrogen storage capacity of the materials. Thus, our findings could provide useful criteria for designing hydrogen storage materials and a fundamental understanding of the correlation between metal–support interactions and hydrogen spillover mechanisms.