The influence of iodide on the solution-phase growth of Cu microplates: a multi-scale theoretical analysis from first principles

Kim, Junseok; Fichthorn, Kristen A.

doi:10.1039/d1fd00091h

Cited by 5 publications

(6 citation statements)

References 62 publications

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“…On the other hand, Ag Ih are rarely synthesized in EG solution with PVP, and this is consistent with their relatively low fraction in Figure . Although SCSF nanocrystal seeds can grow into nano- or microplates, , this is apparently uncommon in the Ag+EG+PVP system, likely because of the lack of a driving force for the {111} facets dominating such structures. This indicates that the small SCSF nanocrystals observed in our study would grow kinetically to cubes.…”

Section: Resultsmentioning

confidence: 99%

Minimum Free-Energy Shapes of Ag Nanocrystals: Vacuum vs Solution

Yan,

Zhang,

Fichthorn

2023

ACS Nano

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We use two variants of replica-exchange molecular dynamics (MD) simulations, parallel tempering MD and partial replica exchange MD, to probe the minimum free-energy shapes of Ag nanocrystals containing 100−200 atoms in a vacuum, ethylene glycol (EG) solvent, and EG solvent with a PVP polymer containing 100 repeat units. Our simulations reveal a shape intermediate between a Dh and an Ih, a Dh-Ih, that has distinct structural signatures and magic sizes. We find several prominent features associated with entropy: pure FCC nanocrystals are less common than FCC crystals containing stacking faults, and crystals with the minimum potential energy are not always preferred over the range of relevant temperatures. The shapes of the nanocrystals in solution are influenced by the chemical identities of the solution-phase molecules. Comparing Ag nanocrystal shapes in EG to those in an EG+PVP solution, we find more icosahedra in EG and more decahedra in EG+PVP across all of the nanocrystal sizes probed in this study. At certain critical sizes, nanocrystal shapes can change dramatically with the addition and removal of a single atom or with a change in temperature at a fixed size. The information in our study could be useful in efforts to devise processing routes to achieve selective nanocrystal shapes.

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Section: Resultsmentioning

confidence: 99%

Minimum Free-Energy Shapes of Ag Nanocrystals: Vacuum vs Solution

Yan,

Zhang,

Fichthorn

2023

ACS Nano

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“…As an example, one class of models involves tracking the diffusive hopping of a single particle on a discrete array of lattice sites, possibly in the presence of trap sites . In a related application, MEQ have been applied to assess transit times of diffusing surface adatoms between facets during the growth of metallic NCs (where periphery sites of the target facet are designated as trap sites), thereby elucidating nontrivial faceted NC growth shapes. − In our application, however, the discrete states of the system are entire configurations of the NCs (which might be regarded as elements of a high-dimensional space). In addition, the essential stochastic dynamics which must be assessed is not so much transitioning irreversibly into adsorbing trap states, but rather surmounting a “nucleation barrier”.…”

Section: Master Equation-based Analysismentioning

confidence: 99%

Thermal Shape Stability of fcc Metal Nanocrystals Synthesized with Faceted Nonequilibrium Shapes

Lai,

Liu,

Huang

et al. 2024

J. Phys. Chem. C

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Highly refined capabilities of the shape-controlled solution-phase synthesis of metal nanocrystals (NCs) allow the generation of NCs with faceted nonequilibrium shapes, which optimize properties for target applications such as catalysis and plasmonics. Often, for such applications and also for TEM analysis, the NCs are removed from the solution-phase environment. We explore the postsynthesis evolution of these metastable NCs in a high-vacuum TEM environment. Specifically, we analyze their reshaping toward the equilibrium Wulff shapes mediated by surface diffusion, where such reshaping degrades the above-mentioned optimized properties. Typical sizes for these NCs range from 5 to 30 nm or 10 3 −10 6 atoms, and reshaping often occurs on the time scale of minutes for temperatures around, say, 400 °C. We discuss the development of predictive stochastic atomistic-level models for NC evolution with a realistic description of surface diffusion. These models, in contrast to Molecular Dynamics, can naturally address the relevant time and length scales for these systems. KMC simulation results for the stochastic models are described, focusing on the reshaping of slightly elongated nanorods and of mildly truncated octahedra and nanocubes. In addition, we review appropriate theoretical formulations for reshaping, which involves the nucleation and growth on 2D islands or layers on outer facets of the NC. We note the limitations of classical nucleation theory in some scenarios and demonstrate the successes of a more fundamental and general master equation-based analysis.

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“…For larger nanocrystals, surface diffusion on the facets can occur on the time scale of deposition. Studies have considered this scenario. − …”

Section: Kinetics Of Nanocrystal Structurementioning

confidence: 99%

“…Kim and Fichthorn applied a similar approach to the growth of Cu microplates mediated by iodide. 310 Experimentally, Cu microplates were grown in water, using hexadecylamine (HDA) as a capping agent and with NaI as an additive. 152 The plates have large {111} facets with dimensions in the micrometer range and a mixture of {111}, {100}, and likely higher index side facets with dimensions of around 100 nm.…”

Section: Kinetic Wulff Shapesmentioning

confidence: 99%

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Theory of Anisotropic Metal Nanostructures

Fichthorn

2023

Chem. Rev.

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A significant challenge in the development of functional materials is understanding the growth and transformations of anisotropic colloidal metal nanocrystals. Theory and simulations can aid in the development and understanding of anisotropic nanocrystal syntheses. The focus of this review is on how results from first-principles calculations and classical techniques, such as Monte Carlo and molecular dynamics simulations, have been integrated into multiscale theoretical predictions useful in understanding shape-selective nanocrystal syntheses. Also, examples are discussed in which machine learning has been useful in this field. There are many areas at the frontier in condensed matter theory and simulation that are or could be beneficial in this area and these prospects for future progress are discussed. CONTENTST 3.3. Kinetic Wulff Shapes V 4. Machine Learning AB 5. Conclusions and Outlook

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The influence of iodide on the solution-phase growth of Cu microplates: a multi-scale theoretical analysis from first principles

Abstract: We use first-principles density functional theory (DFT) to quantify the role of iodide in the solution-phase growth of Cu microplates. Our calculations show that a Cu adatom binds more strongly...

Cited by 5 publications

References 62 publications

Minimum Free-Energy Shapes of Ag Nanocrystals: Vacuum vs Solution

Minimum Free-Energy Shapes of Ag Nanocrystals: Vacuum vs Solution

Thermal Shape Stability of fcc Metal Nanocrystals Synthesized with Faceted Nonequilibrium Shapes

Theory of Anisotropic Metal Nanostructures

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