Orientation-Dependent Oxygen Evolution on RuO[subscript 2] without Lattice Exchange

Abstract

RuO[subscript 2] catalysts exhibit record activities toward the oxygen evolution reaction (OER), which is crucial to enable efficient and sustainable energy storage. Here we examine the RuO[subscript 2] OER kinetics on rutile (110), (100), (101), and (111) orientations, finding (100) the most active. We assess the potential involvement of lattice oxygen in the OER mechanism with online electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO[subscript 2] films and particles, in contrast to previous work, suggesting lattice oxygen is not exchanged in catalyzing OER on crystalline RuO[subscript 2] surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by density functional theory, where more active facets bind oxygen more weakly. This new understanding of the active sites provides a design strategy to enhance the OER activity of RuO][subscript 2] nanoparticles by facet engineering.