Journal
ACS NANO
Volume -, Issue -, Pages -Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.3c06282
Keywords
grain boundary sites; CO oxidation; surfaceoxidation; single particle; plasmonic nanoimaging; DFT; copper nanoparticles
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The oxidation of transition metal surfaces is influenced by low-coordination sites and grain boundaries on nanofabricated Cu nanoparticles, affecting the oxidation rate and oxide nucleation locations. Surface coordination and CO oxidation behavior play crucial roles in the nucleation of oxide on Cu metal catalysts, with low coordination favoring Cu oxidation and high coordination favoring CO oxidation. These findings provide insights into the specific onset of Cu oxidation on individual particles and explain the widely distributed activity states of particles in catalyst ensembles.
The oxidation of transition metal surfaces is a process that takes place readily at ambient conditions and that, depending on the specific catalytic reaction at hand, can either boost or hamper activity and selectivity. Cu catalysts are no exception in this respect since they exhibit different oxidation states for which contradicting activities have been reported, as, for example, in the catalytic oxidation of CO. Here, we investigate the impact of low-coordination sites on nanofabricated Cu nanoparticles with engineered grain boundaries on the oxidation of the Cu surface under CO oxidation reaction conditions. Combining multiplexed in situ single particle plasmonic nanoimaging, ex situ transmission electron microscopy imaging, and density functional theory calculations reveals a distinct dependence of particle oxidation rate on grain boundary density. Additionally, we found that the oxide predominantly nucleates at grain boundary-surface intersections, which leads to nonuniform oxide growth that suppresses Kirkendall-void formation. The oxide nucleation rate on Cu metal catalysts was revealed to be an interplay of surface coordination and CO oxidation behavior, with low coordination favoring Cu oxidation and high coordination favoring CO oxidation. These findings explain the observed single particle-specific onset of Cu oxidation as being the consequence of the individual particle grain structure and provide an explanation for widely distributed activity states of particles in catalyst bed ensembles.
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