Imaging interface-controlled bulk oxygen spillover

As one dynamic aspect of catalysis, spillover is known as species diffusion between an active metal and its support^1-3, especially in reactions involving hydrogen and oxygen^4-8. Spillover confined on the catalyst surface has been investigated extensively^9,10; however, it remains unclear whether the bulk catalyst participates in the reactions through non-surface spillover. Here we track the oxygen spillover in Ru/TiO₂ catalysts using in situ environmental transmission electron microscopy. Lattice oxygen was found to transport directly from the TiO₂ substrate to the supported Ru particles through the Ru/TiO₂ interface instead of the traditionally expected surface diffusion¹¹. As a result, the TiO₂ lattice at the subsurface was strained reversibly to provide channels for oxygen transport, as detected by the picometre-precision tracing of atomic displacement. The structural adaptability at the metal-support interface is critical for controlling oxygen spillover, which is switched on in Ru/rutile-TiO₂ but switched off in Ru/anatase-TiO₂. As shown by the real-time atom-resolved evidence, this bulk oxygen spillover is generally viable in supported metal catalysts of an interfacial epitaxy nature and demonstrates the significance of rationally engineered metal-support interfaces for activating the oxygen in bulk catalyst to contribute to reactions.