  The detection, removal and reduction of hydrogen peroxide is of significant
importance for its increasing application in the areas of environment, food,
electrochemistry and clinical laboratory. Herein the dissociative adsorption
behavior of hydrogen peroxide on ultrathin magnesia (001) films deposited on
transition metal is uncovered for the first time by employing periodic
density-functional theory calculations with van der Waals corrections. The
hydrogen peroxide is dissociated smoothly and reduced to surface hydroxyls on
MgO(001)/TM, and the dissociative adsorption energies of all the considered
fragmentation configurations are substantially negative, demonstrating
dissociation and reduction of hydrogen peroxide on MgO(001)/TM is
thermodynamically favorable. The dissociative adsorption energy decreases
monotonously with increasing film thickness, demonstrating the lower reactivity
of thick oxide films. Moreover, we examined the suitability of several
transition metal slabs (molybdenum, silver, vanadium, tungsten and gold)
combined with magnesia for splitting hydrogen peroxide. The dissociative
adsorption energies enhance when the lattice constants of substrate slabs
increase, indicating the chemisorption strength can be tuned by category of
metal slabs as well as thickness of oxide film. The mechanism of reactivity
enhancement for energetically and dynamically favorable decomposition of
hydrogen peroxide on supported magnesia is elucidated by characterizing the
geometric structures and electronic properties. The fragmentation and reduction
of diethyl peroxide and peroxyacetone are also studied to reveal the catalytic
activity of ultrathin magnesia toward splitting organic peroxides. The results
are wished to provide useful clue for detecting and reducing hydrogen peroxide
and organic peroxides by employing oxide-metal hybrid nanostructure.
