The stabilization of supported nanoclusters is critical for different applications, including catalysis and plasmonics. Herein we investigate the impact of MoS 2 grain boundaries (GBs) on the nucleation and growth of Pt NCs. The optimum atomic structure of the metal clusters is obtained using an adaptive genetic algorithm that employs a hybrid approach based on atomistic force fields and density functional theory. Our findings show that GBs stabilize the NCs up to a cluster size of nearly ten atoms, and with larger clusters having a similar binding to the pristine system. Notably, Pt monomers are found to be attracted to GB cores achieving 60% more stabilization compared to the pristine surface. Furthermore, we show that the nucleation and growth of the metal seeds are facile with low kinetic barriers, which are of similar magnitude to the diffusion barriers of metals on the pristine surface. The findings highlight the need to engineer ultrasmall NCs to take advantage of enhanced stabilization imparted by the GB region, particularly to circumvent sintering behavior for high-temperature applications.
more »
« less
In situ study of nucleation and growth dynamics of Au nanoparticles on MoS 2 nanoflakes
Two-dimensional (2D) substrates decorated with metal nanoparticles offer new opportunities to achieve high-performance catalytic behavior. However, little is known on how the substrates control the nucleation and growth processes of the nanoparticles. This paper presents the visualization of dynamic nucleation and growth processes of gold nanoparticles on ultrathin MoS 2 nanoflakes by in situ liquid-cell transmission electron microscopy (TEM). The galvanic displacement resulting in Au nuclei formation on MoS 2 was observed in real time inside the liquid cell. We found that the growth mechanism of Au particles on pristine MoS 2 is in between diffusion-limited and reaction-limited, possibly due to the presence of electrochemical Ostwald ripening. A larger size distribution and more orientation variation is observed for the Au particles along the MoS 2 edge than on the interior. Differing from pristine MoS 2 , sulfur vacancies on MoS 2 induce Au particle diffusion and coalescence during the growth process. Density functional theory (DFT) calculations show that the size difference is because the exposed molybdenum atoms at the edge with dangling bonds can strongly interact with Au atoms, whereas sulfur atoms on the MoS 2 interior have no dangling bonds and weakly interact with gold atoms. In addition, S vacancies on MoS 2 generate strong nucleation centers that can promote diffusion and coalescence of Au nanoparticles. The present work provides key insights into the role of 2D materials in controlling the size and orientation of noble metal nanoparticles vital to the design of next generation catalysts.
more »
« less
- NSF-PAR ID:
- 10107284
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 10
- Issue:
- 33
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 15809 to 15818
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Mechanical exfoliation yields high‐quality 2D materials but is challenging to scale up due to the small lateral size and low yield of the exfoliated crystals. Gold‐mediated exfoliation of macroscale monolayer MoS2and related crystals addresses this problem. However, it remains unclear whether this method can be extended to other metals. Herein, mechanical exfoliation of MoS2on a range of metallic substrates is studied. It is found that Au outperforms all the other metals in their ability to exfoliate macroscale monolayer MoS2. This is rationalized by gold's ability to resist oxidation, which is compromised on other metals and leads to a weakened binding with MoS2. An anomalously high monolayer yield found for Ag suggests that the large interfacial strain in the metal–MoS2heterostructures measured by Raman spectroscopy also is a critical factor facilitating the exfoliation, while the relative differences in the metal–MoS2binding play only a minor role. These results provide a new incentive for investigations of 2D material‐substrate combinations applicable where high‐quality 2D crystals of macroscopic dimensions are of importance.
-
Despite the well-known tendency for many alloys to undergo ordering transformations, the microscopic mechanism of ordering and its dependence on alloy composition remains largely unknown. Using the example of Pt 85 Fe 15 and Pt 65 Fe 35 alloy nanoparticles (NPs), herein we demonstrate the composition-dependent ordering processes on the single-particle level, where the nanoscale size effect allows for close interplay between surface and bulk in controlling the phase evolution. Using in situ electron microscopy observations, we show that the ordering transformation in Pt 85 Fe 15 NPs during vacuum annealing occurs via the surface nucleation and growth of L1 2 -ordered Pt 3 Fe domains that propagate into the bulk, followed by the self-sacrifice transformation of the surface region of the L1 2 Pt 3 Fe into a Pt skin. By contrast, the ordering in Pt 65 Fe 35 NPs proceeds via an interface mechanism by which the rapid formation of an L1 0 PtFe skin occurs on the NPs and the transformation boundary moves inward along with outward Pt diffusion. Although both the “nucleation and growth” and the “interface” mechanisms result in a core–shell configuration with a thin Pt-rich skin, Pt 85 Fe 15 NPs have an L1 2 Pt 3 Fe core, whereas Pt 65 Fe 35 NPs are composed of an L1 0 PtFe core. Using atomistic modeling, we identify the composition-dependent vacancy-assisted counterdiffusion of Pt and Fe atoms between the surface and core regions in controlling the ordering transformation pathway. This vacancy-assisted diffusion is further demonstrated by oxygen annealing, for which the selective oxidation of Fe results in a large number of Fe vacancies and thereby greatly accelerates the transformation kinetics.more » « less
-
more » « less
Abstract Ag nanorods receive intensive attention due to the excellent plasmonic properties. However, the difficulty in synthesis of monodisperse Ag nanorods with broad aspect ratios has limited their in‐depth applications. Here, a seed‐mediated method is reported for the synthesis of Ag nanorods with lengths from 65 to 5000 nm, corresponding to aspect ratios from 2 to 156. The plasmonic resonance is tuned from visible to mid‐infrared wavelength. The synthesis protocol relies on robust Au seeds synthesized in
N ,N ‐dimethylformamide (DMF), which induces the one‐dimensional (1D) growth of Ag atoms. To maintain symmetry breaking initiated by the Au seeds, the reduction rate of Ag+is decreased by adding hexadecyltrimethylammonium chloride (CTAC) to form AgCl particles. The optimized conditions to prevent the homogeneous nucleation of Ag nanoparticles and residue of AgCl particles in products are identified, under which the conversion efficiency of Ag ions to Ag nanorods is evaluated about 48%. More importantly, the anisotropic Ag nanorods are self‐assembled into monolayers at interfaces with the long axis of Ag nanorods perpendicular or parallel to the interfaces, respectively. The as‐fabricated monolayers exhibit uniform and reproducible surface‐enhanced Raman scattering (SERS) activities. The optimal SERS performance is achieved from Ag nanorod monolayer with vertical orientation and the longest rod length. -
more » « less
Abstract Realizing stimulated emission from defects in 2D‐layered semiconductors has the potential to enhance the sensitivity of characterizing their defects. However, stimulated emission from defects in layered materials presents a different set of challenges in carrier lifetime and energy level design and is not achieved so far. Here, photoluminescence (PL) spectroscopy, Raman spectroscopy, and first‐principles theory are combined to reveal an anomalous PL intensity–temperature relation and strong polarization effects at a defect emission peak in annealed multilayer MoS2, suggesting defect‐based stimulated emission. The emergence of stimulated emission behavior is also controllable (by temperature) and reversible. The observed stimulated emission behavior is supported by a three‐level system involving two defect levels from chalcogen vacancies and a pump level from the conduction band edge. First‐principles calculations show that the special indirect gap that enables stimulated emission is not native to pristine bulk MoS2and only emerges under thermal strain.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8nr03519a
