Direct observation of accelerating hydrogen spillover via surface-lattice-confinement effect

Abstract

AbstractUncovering how hydrogen transfers and what factors control hydrogen conductivity on solid surface is essential for enhancing catalytic performance of H-involving reactions, which is however hampered due to the structural complexity of powder catalysts, in particular, for oxide catalysts. Here, we construct stripe-like MnO(001) and grid-like Mn3O4(001) monolayers on Pt(111) substrate and investigate hydrogen spillover atop. Atomic-scale visualization demonstrates that hydrogen species from Pt diffuse unidirectionally along the stripes on MnO(001), whereas it exhibits an isotropic pathway on Mn3O4(001). Dynamic surface imaging in H2 atmosphere reveals that hydrogen diffuses 4 times more rapidly on MnO than the case on Mn3O4, which is promoted by one-dimension surface-lattice-confinement effect. Theoretical calculations indicate that a uniform and medium O-O distance favors hydrogen diffusion while low-coordinate surface O atom inhibits it. Our work illustrates the surface-lattice-confinement effect of oxide catalysts on hydrogen spillover and provides a promising route to improve the hydrogen spillover efficiency.