Significance A collaborative approach containing reaction kinetics measurements under steady-state and transient conditions, electronic structure calculations employing density-functional theory, and microkinetic modeling on acetone hydrogenation is employed to provide insights into understanding the self-adjusting platinum surface for the hydrogenation of oxygenates over a wide range of reaction conditions. Elucidation of the repulsive interactions and the corresponding self-adjusting catalyst surface properties at various reaction conditions provides a basis to formulate rate expressions for heterogeneous catalytic processes used in the chemical industry.