Probing the role of grain boundaries in single Cu nanoparticle oxidation by in situ plasmonic scattering
Artikel i vetenskaplig tidskrift, 2022
Grain boundaries determine physical properties of bulk materials including ductility, diffusivity, and electrical conductivity. However, the role of grain boundaries in nanostructures and nanoparticles is much less understood, despite the wide application of nanoparticles in nanophotonics, nanoelectronics, and heterogeneous catalysis. Here, we investigate the role of high-angle grain boundaries in the oxidation of Cu nanoparticles, using a combination of in situ single particle plasmonic nanoimaging and postmortem transmission electron microscopy image analysis, together with ab initio and classical electromagnetic calculations. We find an initial growth of a 5-nm-thick Cu2O shell on all nanoparticles, irrespective of different grain morphologies. This insensitivity of the Cu2O shell on the grain morphology is rationalized by extraction of Cu atoms from the metal lattice being the rate limiting step, as proposed by density functional theory calculations. Furthermore, we find that the change in optical scattering intensity measured from the individual particles can be deconvoluted into one contribution from the oxide layer growth and one contribution that is directly proportional to the grain boundary density. The latter contribution signals accumulation of Cu vacancies at the grain boundaries, which, as corroborated by calculations of the optical scattering, leads to increased absorption losses and thus a decrease of the scattering, thereby manifesting the role of grain boundaries as vacancy sinks and nuclei for Kirkendall void formation at a later stage of the oxidation process.
Författare
Sara Nilsson
Chalmers, Fysik, Kemisk fysik
Alvaro Posada Borbon
Chalmers, Fysik, Kemisk fysik
University of Wisconsin Madison
Mario Zapata-Herrera
Consejo Superior de Investigaciones Científicas (CSIC)
Alice Bastos da Silva Fanta
Danmarks Tekniske Universitet (DTU)
David Albinsson
Chalmers, Fysik, Kemisk fysik
Joachim Fritzsche
Chalmers, Fysik, Kemisk fysik
Vyacheslav M. Silkin
Basque Foundation for Science (Ikerbasque)
Donostia International Physics Center
Universidad del Pais Vasco / Euskal Herriko Unibertsitatea
Javier Aizpurua
Consejo Superior de Investigaciones Científicas (CSIC)
Donostia International Physics Center
Henrik Grönbeck
Chalmers, Fysik, Kemisk fysik
Ruben Esteban
Consejo Superior de Investigaciones Científicas (CSIC)
Donostia International Physics Center
Christoph Langhammer
Chalmers, Fysik, Kemisk fysik
Physical Review Materials
24759953 (eISSN)
Vol. 6 4 045201The Competence Centre for Catalysis, KCK 2022-2026
Preem AB (KCK2022-2026), 2022-01-01 -- 2026-12-31.
Scania AB (Dnr:2021-036543Pnr:52689-1), 2022-01-01 -- 2026-12-31.
Volvo Group (PO:2435702-000), 2022-01-01 -- 2026-12-31.
Umicore Denmark ApS (KCK2022-2026), 2022-01-01 -- 2026-12-31.
Johnson Matthey (2500123383), 2022-01-01 -- 2026-12-31.
Styrkeområden
Nanovetenskap och nanoteknik
Ämneskategorier (SSIF 2011)
Keramteknik
Materialkemi
Den kondenserade materiens fysik
Infrastruktur
C3SE (-2020, Chalmers Centre for Computational Science and Engineering)
Chalmers materialanalyslaboratorium
Myfab (inkl. Nanotekniklaboratoriet)
DOI
10.1103/PhysRevMaterials.6.045201