TY - JOUR
T1 - Gas-Phase Synthesis of Trimetallic Nanoparticles
AU - Mattei, Jean Gabriel
AU - Grammatikopoulos, Panagiotis
AU - Zhao, Junlei
AU - Singh, Vidyadhar
AU - Vernieres, Jerome
AU - Steinhauer, Stephan
AU - Porkovich, Alexander
AU - Danielson, Eric
AU - Nordlund, Kai
AU - Djurabekova, Flyura
AU - Sowwan, Mukhles
N1 - Publisher Copyright:
© Copyright 2019 American Chemical Society.
PY - 2019/3/26
Y1 - 2019/3/26
N2 - To this day, engineering nanoalloys beyond bimetallic compositions has scarcely been within the scope of physical deposition methods due to the complex, nonequilibrium processes they entail. Here, we report a gas-phase synthesis strategy for the growth of multimetallic nanoparticles: Magnetron-sputtering inert-gas condensation from neighboring monoelemental targets provides the necessary compositional flexibility, whereas in-depth atomistic computer simulations elucidate the fast kinetics of nucleation and growth that determines the resultant structures. We fabricated consistently trimetallic Au-Pt-Pd nanoparticles, a system of major importance for heterogeneous catalysis applications. Using high-resolution transmission electron microscopy, we established their physical and chemical ordering: Au/Pt-rich core@Pd-shell atomic arrangements were identified for particles containing substantial amounts of all elements. Decomposing the growth process into basic steps by molecular dynamics simulations, we identified a fundamental difference between Au/Pt and Pd growth dynamics: Au/Pt electronic arrangements favor the formation of dimer nuclei instead of larger-size clusters, thus significantly slowing down their growth rate. Consequently, larger Pd particles formed considerably faster and incorporated small Au and Pt clusters by means of in-flight decoration and coalescence. A broad range of icosahedral, truncated-octahedral, and spheroidal face-centered cubic trimetallic nanoparticles were reproduced in simulations, in good agreement with experimental particles. Comparing them with their expected equilibrium structures obtained by Monte Carlo simulations, we identified the particles as metastable, due to out-of-equilibrium growth conditions. We aspire that our in-depth study will constitute a significant advance toward establishing gas-phase aggregation as a standard method for the fabrication of complex nanoparticles by design.
AB - To this day, engineering nanoalloys beyond bimetallic compositions has scarcely been within the scope of physical deposition methods due to the complex, nonequilibrium processes they entail. Here, we report a gas-phase synthesis strategy for the growth of multimetallic nanoparticles: Magnetron-sputtering inert-gas condensation from neighboring monoelemental targets provides the necessary compositional flexibility, whereas in-depth atomistic computer simulations elucidate the fast kinetics of nucleation and growth that determines the resultant structures. We fabricated consistently trimetallic Au-Pt-Pd nanoparticles, a system of major importance for heterogeneous catalysis applications. Using high-resolution transmission electron microscopy, we established their physical and chemical ordering: Au/Pt-rich core@Pd-shell atomic arrangements were identified for particles containing substantial amounts of all elements. Decomposing the growth process into basic steps by molecular dynamics simulations, we identified a fundamental difference between Au/Pt and Pd growth dynamics: Au/Pt electronic arrangements favor the formation of dimer nuclei instead of larger-size clusters, thus significantly slowing down their growth rate. Consequently, larger Pd particles formed considerably faster and incorporated small Au and Pt clusters by means of in-flight decoration and coalescence. A broad range of icosahedral, truncated-octahedral, and spheroidal face-centered cubic trimetallic nanoparticles were reproduced in simulations, in good agreement with experimental particles. Comparing them with their expected equilibrium structures obtained by Monte Carlo simulations, we identified the particles as metastable, due to out-of-equilibrium growth conditions. We aspire that our in-depth study will constitute a significant advance toward establishing gas-phase aggregation as a standard method for the fabrication of complex nanoparticles by design.
UR - http://www.scopus.com/inward/record.url?scp=85063086681&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.9b00129
DO - 10.1021/acs.chemmater.9b00129
M3 - 文章
AN - SCOPUS:85063086681
SN - 0897-4756
VL - 31
SP - 2151
EP - 2163
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 6
ER -