Theoretical assessments of Pd–PdO phase transformation and its impacts on H 2 O 2 synthesis and decomposition pathways
The direct synthesis of H 2 O 2 from O 2 and H 2 provides a green pathway to produce H 2 O 2 , a popular industrial oxidant. Here, in this study, we theoretically investigate the effects of Pd oxidation states, coordination environments, and particle sizes on primary H 2 O 2 selectivities, assessed by calculating the ratio of rate constants for the formation of H 2 O 2 (via OOH* reduction; k O–H ) and the decomposition of OOH* (via O–O cleavage; k O–O ). For Pd metals, the k O–H /k O–O ratio decreased from 10 -4 for Pd(111) to 10 -10 for the Pd 13 cluster at 300 K, indicating poorer H 2 O 2 selectivity as Pd particle size decreases and low primary selectivities for H 2 O 2 overall. As the oxygen chemical potential increases and metals form surface and bulk oxides, the perturbation of Pd–Pd ensemble sites by lattice O atoms results in selectivities that become dramatically higher than unity. For instance, at 300 K, the k O–H /k O–O ratio increases significantly from 10 -4 to 10 9 to 10 16 as Pd(111) oxidizes to Pd 5 O 4 /Pd(111) and to PdO(100), respectively. In contrast, such selectivity enhancements are not observed for surface and bulk oxides that persistently contain rows of more metallic, undercoordinated Pd–Pd ensemble sites, such as PdO(101)/Pd(100) and PdO(101). These Pd–Pd ensembles are also absent when smaller Pd nanoparticles fully oxidize, indicating that smaller PdO clusters can be more selective for H 2 O 2 synthesis. These trends for primary H 2 O 2 selectivities were found to inversely correlate with trends for H 2 O 2 decomposition rates via O–O bond cleavage, demonstrating that catalysts with high primary H 2 O 2 selectivity can also hinder H 2 O 2 decomposition. Ab initio thermodynamic calculations are used to estimate the thermodynamically favored phase among Pd, PdO/Pd and PdO in O 2 , H 2 O 2 /H 2 O, and O 2 /H 2 environments. These results are combined to show that smaller Pd nanoparticles are more prone to be oxidized at lower oxygen chemical potentials, upon which they become more selective than larger Pd particles for H 2 O 2 synthesis.