Characteristics of hydrogen storage by spillover on Pt-doped carbon and catalyst-bridged metal organic framework

Metal dispersion is a crucially important factor for hydrogen spillover storage on metal/carbon materials. For Pt on carbon (Pt/C), dispersion into nearly 2 nm clusters or nanoparticles is necessary to facilitate spillover. On an effective Pt/C spillover sorbent, temperature-programmed desorption (TPD) results reveal the highest hydrogen signal is from the high-energy Pt edges, steps or (110) surfaces, even though the (111) faces are more abundant. Previous theoretical studies showed the high-energy sites (including the 110 face) are by far the most preferred for effective splitting of hydrogen. These are in significantly smaller fractions for larger particles, and thus the larger particles are less efficient. In addition, the rate-limiting step for spillover on effective Pt/C is identified by the susceptibility to isotopic differences, first-order behavior and isolation from catalyzed H₂/HD/D₂ equilibrium measurements; we conclude it is the spillover step or surface diffusion. We extended our analysis to a review of our previous work, spillover on metal organic frameworks (MOFs). This has been achieved by bridging a commercial H₂ dissociation catalyst (Pt/C) to MOFs, large enhancement factors (up to 8) were observed. Unlike Pt/C sorbents, sample-to-sample consistency in storage capacity on the bridged MOF samples is difficult to achieve. Inconsistency in the enhancements by spillover is shown; however, significant enhancement factors are still observed when samples are prepared and activated properly. Common pitfalls (and their consequences) in sample preparation for both Pt/C and bridged MOFs are discussed in detail.