Adsorption and Dissociation of H₂O₂ on Pt and Pt−Alloy Clusters and Surfaces

Abstract

The adsorption of H(2)O(2) on Pt and Pt-M alloys, where M is Cr, Co, or Ni, is investigated using density functional theory. Binding energies calculated with a hybrid DFT functional (B3PW91) are in the range of -0.71 to -0.88 eV for H(2)O(2) adsorbed with one of the oxygen atoms on top Pt positions of Pt(3), Pt(2)M, and PtM(2), and enhanced values in the range of -0.81 to -1.09 eV are found on top Ni and Co sites of the Pt(2)M clusters. Adsorption on top sites of Pt(10) yields a weaker binding of -0.48 eV, whereas on periodic Pt(111) and Pt(3)Co(111) surfaces, H(2)O(2) generally dissociates into two OH radicals. On the other hand, attempts to attach H(2)O(2) on bridge sites cause spontaneous dissociation of H(2)O(2) into two adsorbed OH radicals, suggesting that stable adsorptions on bridge sites are not possible for any of the clusters or extended surfaces that are being studied. We also found that the water-H(2)O(2) interaction reduces the strength of the adsorption of H(2)O(2) on these clusters and surfaces.

Pt(111)-Alloy Surfaces for Non-Activated OOH Dissociation

“…We also note that the broadening of the adsorbate states are more evident for PtRuMo. This charge transfer mechanism has long been correlated with O-O elongation for many other oxygenated species [13,[29][30][31]. In particular, for OOH on Pt cluster, the relationship between increasing PtPt distance and elongation of the O-O bond is established [13].…”

Efficient and Continuous Decomposition of Hydrogen Peroxide Using a Silica Capillary Coated with a Thin Palladium or Platinum Layer

“…13,40 In all experiments afterwards, we used Pd capillary with oxidized surface. Once the surface of Pd is oxidized, it maintains its activity for H 2 O 2 decomposition.…”

Catalytic performance of carbon nanotubes in H2O2 decomposition: Experimental and quantum chemical study

“…Decomposition of hydrogen peroxide over a solid surface is a complex homolytic chain process [29,34,35]. The limiting step of this reaction is the disintegration of H 2 O 2 molecule into two HO • radicals through a radical mechanism.…”