The dynamics of overlayer formation on catalyst nanoparticles and strong metal-support interaction

A platinum particle on a titania support in the first exposure to H2 at 600 °C (a, b) and the subsequent atmosphere change to O2 at 600 °C (c), a switch to H2 (d) and then a switch to O2 again (e), and interpretation of the phenomena based on the combined results of in situ transmission electron microscopy, in situ X-ray photoemission spectroscopy, and in situ powder X-ray diffraction (f–j). Insets for c–e show a magnified image of the overlayer structure observed. Scale bar is 5 nm.

Heterogeneous catalysts play a pivotal role in the chemical industry. The strong metal-support interaction (SMSI), which affects the catalytic activity, is a phenomenon researched for decades. However, detailed mechanistic understanding on real catalytic systems is lacking. Here, this surface phenomenon was studied on an actual platinum-titania catalyst by state-of-the-art in situ electron microscopy, in situ X-ray photoemission spectroscopy and in situ X-ray diffraction, aided by density functional theory calculations, providing a novel real time view on how the phenomenon occurs. The migration of reduced titanium oxide, limited in thickness, and the formation of an alloy are competing mechanisms during high temperature reduction. Subsequent exposure to oxygen segregates the titanium from the alloy, and a thicker titania overlayer forms. This role of oxygen in the formation process and stabilization of the overlayer was not recognized before. It provides new application potential in catalysis and materials science.

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