Probing the role of grain boundaries in single Cu nanoparticle oxidation by 
<i>in situ</i>
 plasmonic scattering

Nilsson, Sara; Posada-Borbón, Alvaro; Zapata-Herrera, Mario; Fanta, Alice Bastos da Silva; Albinsson, David; Fritzsche, Joachim; Silkin, V. M.; Aizpurua, Javier; Grönbeck, Henrik; Esteban, Rubén; Langhammer, Christoph

doi:10.1103/physrevmaterials.6.045201

Cited by 4 publications

(7 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We have recently shown that such accumulations of Cu vacancies can decrease scattering at the resonance at the expense of LSPR absorption decaying routes. 46 Cu vacancies are not included in this FDTD model, as we consider it to be outside of the scope of this report.…”

Section: †)mentioning

confidence: 99%

Competing oxidation mechanisms in Cu nanoparticles and their plasmonic signatures

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

Section: †)mentioning

confidence: 99%

Competing oxidation mechanisms in Cu nanoparticles and their plasmonic signatures

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Given the rough morphology and the polycrystalline nature of the oxide layer, we expect the displacement energy of Cu at the interface to be lower than the bulk value and E max in this case to be above the threshold to displace and mobilize Cu at the metal–oxide interface. Interestingly, previous studies have identified the extraction of Cu from the lattice to be the rate limiting step in its oxidation, supporting the significant role that electron beam knock-on damage to Cu can have on enhancing its oxidation rate. In contrast, we do not expect kinetic energy transfer from the electron beam to have the same favorable impact on the generation rate and transport of O 2– anions as the source is in gas form.…”

Section: Resultsmentioning

confidence: 75%

Electron Beam Induced Enhancement and Suppression of Oxidation in Cu Nanoparticles in Environmental Scanning Transmission Electron Microscopy

Ziashahabi,

Elsukova,

Nilsson

et al. 2023

ACS Nanosci. Au

Self Cite

View full text Add to dashboard Cite

We have investigated the effects of high-energy electron irradiation on the oxidation of copper nanoparticles in environmental scanning transmission electron microscopy (ESTEM). The hemispherically shaped particles were oxidized in 3 mbar of O 2 in a temperature range 100−200 °C. The evolution of the particles was recorded with sub-nanometer spatial resolution in situ in ESTEM. The oxidation encompasses the formation of outer and inner oxide shells on the nanoparticles, arising from the concurrent diffusion of copper and oxygen out of and into the nanoparticles, respectively. Our results reveal that the electron beam actively influences the reaction and overall accelerates the oxidation of the nanoparticles when compared to particles oxidized without exposure to the electron beam. However, the extent of this electron beam-assisted acceleration of oxidation diminishes at higher temperatures. Moreover, we observe that while oxidation through the outward diffusion of Cu + cations is enhanced, the electron beam appears to hinder oxidation through the inward diffusion of O 2− anions. Our results suggest that the impact of the high-energy electrons in ESTEM oxidation of Cu nanoparticles is mostly related to kinetic energy transfer, charging, and ionization of the gas environment, and the beam can both enhance and suppress reaction rates.

show abstract

“…In the analysis of the role of these grain boundaries on the Cu particle oxidation process under CO oxidation reaction conditions, from here onward, we group the particles prepared in this way into two classes: (i) single crystals, without any grain boundaries, and (ii) polycrystals, containing two or more grains (examples in the inset of Figure d). To this end, we have previously compared our methodology (see Methods Section for details) of measuring the grain boundary length in particles from TEM images with the analysis from transmission Kikuchi diffraction (TKD) of the same particles and found a median error of 23% when comparing 78 Cu particles . This means that our method allows us to estimate the grain boundary length from TEM images to below 23% error in half of the particles.…”

Section: Resultsmentioning

confidence: 96%

“…To this end, we have previously compared our methodology (see Methods Section for details) of measuring the grain boundary length in particles from TEM images with the analysis from transmission Kikuchi diffraction (TKD) of the same particles and found a median error of 23% when comparing 78 Cu particles. 21 This means that our method allows us to estimate the grain boundary length from TEM images to below 23% error in half of the particles. We should also consider that TKD has some uncertainty in measuring the grain boundary length, e.g., underestimating it by not recognizing small grains.…”

Section: Resultsmentioning

confidence: 97%

The Role of Grain Boundary Sites for the Oxidation of Copper Catalysts during the CO Oxidation Reaction

Nilsson,

El Berch,

Albinsson

et al. 2023

ACS Nano

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Probing the role of grain boundaries in single Cu nanoparticle oxidation by in situ plasmonic scattering

Cited by 4 publications

References 77 publications

Competing oxidation mechanisms in Cu nanoparticles and their plasmonic signatures

Competing oxidation mechanisms in Cu nanoparticles and their plasmonic signatures

Electron Beam Induced Enhancement and Suppression of Oxidation in Cu Nanoparticles in Environmental Scanning Transmission Electron Microscopy

The Role of Grain Boundary Sites for the Oxidation of Copper Catalysts during the CO Oxidation Reaction

Contact Info

Product

Resources

About