Effect of Pd Coordination and Isolation on the Catalytic Reduction of O₂ to H₂O₂ over PdAu Bimetallic Nanoparticles

Abstract

The direct synthesis of hydrogen peroxide (H₂ + O₂ → H₂O₂) may enable low-cost H₂O₂ production and reduce environmental impacts of chemical oxidations. Here, we synthesize a series of Pd₁Au_<i>x</i> nanoparticles (where 0 ≤ <i>x</i> ≤ 220, ∼10 nm) and show that, in pure water solvent, H₂O₂ selectivity increases with the Au to Pd ratio and approaches 100% for Pd₁Au₂₂₀. Analysis of <i>in situ</i> XAS and <i>ex situ</i> FTIR of adsorbed ¹²CO and ¹³CO show that materials with Au to Pd ratios of ∼40 and greater expose only monomeric Pd species during catalysis and that the average distance between Pd monomers increases with further dilution. <i>Ab initio</i> quantum chemical simulations and experimental rate measurements indicate that both H₂O₂ and H₂O form by reduction of a common OOH* intermediate by proton-electron transfer steps mediated by water molecules over Pd and Pd₁Au_<i>x</i> nanoparticles. Measured apparent activation enthalpies and calculated activation barriers for H₂O₂ and H₂O formation both increase as Pd is diluted by Au, even beyond the complete loss of Pd-Pd coordination. These effects impact H₂O formation more significantly, indicating preferential destabilization of transition states that cleave O-O bonds reflected by increasing H₂O₂ selectivities (19% on Pd; 95% on PdAu₂₂₀) but with only a 3-fold reduction in H₂O₂ formation rates. The data imply that the transition states for H₂O₂ and H₂O formation pathways differ in their coordination to the metal surface, and such differences in site requirements require that we consider second coordination shells during the design of bimetallic catalysts.