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. 2018 Jun 18;3(6):6533-6539.
doi: 10.1021/acsomega.8b00779. eCollection 2018 Jun 30.

Metallic Nanocrystal Ripening on Inorganic Surfaces

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Free PMC article

Metallic Nanocrystal Ripening on Inorganic Surfaces

Priyadarshi Ranjan et al. ACS Omega. .
Free PMC article

Abstract

In this paper, we demonstrate the formation of hybrid nanostructures consisting of two distinctive components mainly in a one-to-one ratio. Thermolysis of inorganic nanotubes (INT) and closed-cage, inorganic fullerene-like (IF) nanoparticles decorated with a dense coating of metallic nanoparticles (M = Au, Ag, Pd) results in migration of relatively small NPs or surface-enhanced diffusion of atoms or clusters, generating larger particles (ripening). AuNP growth on the surface of INTs has been captured in real time using in situ electron microscopy measurements. Reaction of the AuNP-decorated INTs with an alkylthiol results in a chemically induced NP fusion process at room temperature. The NPs do not dissociate from the surfaces of the INTs and IFs, but for proximate IFs we observed fusion between AuNPs originating from different IFs.

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Schematic Rendering Showing the Homogeneous Decoration of the Surfaces of INT-WS2 and IF-MoS2 with MNPs (M = Au, Ag, Pd) Followed by Thermolysis or Chemically Induced Ripening of the MNPs on the Surfaces of the Inorganic Structures
Figure 1
Figure 1
SEM images showing examples of decorated MNP/INT-WS2 (a) M = Au; (c) M = Ag; (d) M = Pd) and AuNP/IF-MoS2 (b) with MNPs.
Figure 2
Figure 2
HAADF STEM tomography of a decorated AuNP/INT-WS2. (a) Single image taken from a full tilt series of images. (b–d) Slices from the tomogram showing orthogonal cut planes through the nanotube. The scale bars are 50 nm.
Figure 3
Figure 3
Thermolysis of AuNP/INT-WS2 on a Si[100] wafer at 150 °C in air. (a) Schematic showing the thermolysis process. (b,c) SEM images of AuNP/INT-WS2 after heating for 3 h. (d–h) SEM images taken at different stages of the thermolysis process. (i) Raman spectra taken at different stages of the thermolysis process. The inset shows an exponential increase of the diameter of the AuNPs during heating (R2 = 0.98).
Figure 4
Figure 4
Thermolysis of AuNP/IF-MoS2 on a Si[100] wafer at 150 °C in air. (a) Schematic showing the thermolysis process. (b) SEM images of AuNP/IF-MoS2 after heating for 3 h. The red circles emphasize the formed AuNP-nanodecahedrons. (c) SEM images of AuNP/IF-MoS2 after heating for 24 h. (d) TEM image showing a crystalline AuNP-nanodecahedron attached to the surface of IF-MoS2.
Figure 5
Figure 5
Thermolysis of MNP/INT-WS2 (M = Ag, Pd) on a Si[100] wafer at 150 °C in air. (a) SEM images of AgNP/INT-WS2 after heating for 5 h. (b,c) SEM images of PdNP/INT-WS2 after heating for 4 h.
Figure 6
Figure 6
Chemical-induced fusion of AuNPs. SEM (a,b) and TEM (c) images after reacting AuNP/INT-WS2 with 11-mercaptoundecanoic acid in toluene at room temperature.
Figure 7
Figure 7
Mechanical removal of AuNPs from AuNP/INT-WS2 by AFM. Top: Schematic showing the mechanical removal of AuNPs by the AFM tip from the surface of INT-WS2 (not to scale). Bottom: SEM image and inset showing the AuNP-decorated and mechanically removed INT-WS2 surface.

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