Catalyst support effects on hydrogen spillover

摘要

Hydrogen spillover(1) is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support(2). The phenomenon has been much studied(3-7) and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide(8-13). Here we use the enhanced precision of top-down nanofabrication(14,15) to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy(14) applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations(16,17), reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage(18,19) and catalytic reactions involving hydrogen(8,11-13), and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.