Tuning the surface reactivity of oxides by peroxide species.

The Mars-van Krevelen mechanism is the foundation for oxide-catalyzed oxidation reactions and relies on spatiotemporally separated redox steps. Herein, we demonstrate the tunability of this separation with peroxide species formed by excessively adsorbed oxygen, thereby modifying the catalytic activity and selectivity of the oxide. Using CuO as an example, we show that a surface layer of peroxide species acts as a promotor to significantly enhance CuO reducibility in favor of H2 oxidation but conversely as an inhibitor to suppress CuO reduction against CO oxidation. Together with atomistic modeling, we identify that this opposite effect of the peroxide on the two oxidation reactions stems from its modification on coordinately unsaturated sites of the oxide surface. By differentiating the chemical functionality between lattice oxygen and peroxide, these results are closely relevant to a wide range of catalytic oxidation reactions using excessively adsorbed oxygen to activate lattice oxygen and tune the activity and selectivity of redox sites.

Atomistic mechanisms of water vapor-induced surface passivation.

The microscopic mechanisms underpinning the spontaneous surface passivation of metals from ubiquitous water have remained largely elusive. Here, using in situ environmental electron microscopy to atomically monitor the reaction dynamics between aluminum surfaces and water vapor, we provide direct experimental evidence that the surface passivation results in a bilayer oxide film consisting of a crystalline-like Al(OH)3 top layer and an inner layer of amorphous Al2O3. The Al(OH)3 layer maintains a constant thickness of ~5.0 Å, while the inner Al2O3 layer grows at the Al2O3/Al interface to a limiting thickness. On the basis of experimental data and atomistic modeling, we show the tunability of the dissociation pathways of H2O molecules with the Al, Al2O3, and Al(OH)3 surface terminations. The fundamental insights may have practical significance for the design of materials and reactions for two seemingly disparate but fundamentally related disciplines of surface passivation and catalytic H2 production from water.