Twin Pathways: Discerning the Origins of Multiply Twinned Colloidal Nanoparticles

Du, Jingshan S.; Zhou, Wenjie; Rupich, Sara M.; Mirkin, Chad A.

doi:10.1002/ange.202015166

Cited by 6 publications

(3 citation statements)

References 50 publications

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“…Multiply-twinned nanocrystals, including those with decahedral ( D 5h ) and icosahedral ( I h ) shapes (section ), are remarkable structures in terms of both geometric shape and atomic arrangement due to the unique assembly of different numbers of single-crystal apex- and facet-sharing tetrahedral subunits. These nanocrystals can be formed through at least two pathways: (i) direct nucleation into 5-fold and 20-fold twinned seeds and subsequent layer-by-layer growth, or (ii) stepwise formation of new twin boundaries on single-crystal seeds via atomic growth or attachment . The latter case can be considered as a case of symmetry reduction for single-crystal seeds, which is discussed in section .…”

Section: Case Studiesmentioning

confidence: 99%

“…These nanocrystals can be formed through at least two pathways: (i) direct nucleation into 5-fold and 20-fold twinned seeds and subsequent layer-by-layer growth, or (ii) stepwise formation of new twin boundaries on single-crystal seeds via atomic growth or attachment. 315 The latter case can be considered as a case of symmetry reduction for single-crystal seeds, which is discussed in section 4.1. Although the actual formation pathway of these nanocrystals is still under debate, their unique symmetry is widely used in seed-mediated growth to produce asymmetrical nanostructures hard to obtain through traditional means.…”

Section: Penta-twinned Decahedral Seedsmentioning

confidence: 99%

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Colloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry Breaking

et al. 2022

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Nanocrystals offer a unique platform for tailoring the physicochemical properties of solid materials to enhance their performances in various applications. While most work on controlling their shapes revolves around symmetrical growth, the introduction of asymmetrical growth and thus symmetry breaking has also emerged as a powerful route to enrich metal nanocrystals with new shapes and complex morphologies as well as unprecedented properties and functionalities. The success of this route critically relies on our ability to lift the confinement on symmetry by the underlying unit cell of the crystal structure and/or the initial seed in a systematic manner. This Review aims to provide an account of recent progress in understanding and controlling asymmetrical growth and symmetry breaking in a colloidal synthesis of noble-metal nanocrystals. With a touch on both the nucleation and growth steps, we discuss a number of methods capable of generating seeds with diverse symmetry while achieving asymmetrical growth for mono-, bi-, and multimetallic systems. We then showcase a variety of symmetry-broken nanocrystals that have been reported, together with insights into their growth mechanisms. We also highlight their properties and applications and conclude with perspectives on future directions in developing this class of nanomaterials. It is hoped that the concepts and existing challenges outlined in this Review will drive further research into understanding and controlling the symmetry breaking process.

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Section: Case Studiesmentioning

confidence: 99%

Section: Penta-twinned Decahedral Seedsmentioning

confidence: 99%

Colloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry Breaking

et al. 2022

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“…In this context, monolayer-protected metal clusters (MPCs, wherein the metallic core is protected by an organic layer) represent an intriguing category; their atomic precision (with X-ray single crystal diffraction, mass spectra, etc.) and the molecular-like physicochemical properties have provided sound proof to the traditional theories such as plasmonics and size-effect − and are pivotal to elucidating the inherent structure–property correlations at a molecular scale.…”

Section: Introductionmentioning

confidence: 99%

Motif-to-Core Nucleation in a Decahedral Evolution Pattern

Ma,

He,

et al. 2023

Inorg. Chem.

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The atomic precision of ultrasmall metal nanoclusters has opened the door to elucidating the structural evolution principles of metal nanomaterials at the molecular level. Here, we report a novel set of super-atomic Ag clusters, including [Ag19(TBBT)16(DPPP)4]+ (Ag19), [Ag22(DMAT)8(DPPM)4Cl8]2+ (Ag22), Ag26(SPh3,5‑CF3)15(DPPF)4Cl5 (Ag26), and [Ag30(DMAT)12(DPPP)4Cl8]2+ (Ag30). The core structures of these clusters correspond to one decahedral Ag7, perpendicular bi-decahedrons, three-dimensional penta-decahedrons, and hexa-decahedrons, respectively. The Ag atoms in AgS2 blocks show a strong correlation with the decahedral cores: the five equatorial Ag atoms in the decahedral Ag7 core of Ag19 all adopt the AgS2 coordination, while the Ag atoms in AgS2 blocks of Ag22, Ag26, and Ag30 unexceptionally constitute additional decahedral structures with the core Ag atoms. Specifically, two and four core Ag atoms of Ag26 and Ag30 clusters occupy positions that highly resemble that of Ag (in AgS2 motifs) of Ag22. The strong structural correlation demonstrates the motif-to-core evolution of the surface Ag (on AgS2) to build extra-decahedral blocks. Density functional theory calculations indicate that the 2e, 4e, 6e, and 8e clusters (from Ag19 to Ag30) adopt 1S2, 1S21P2, 1S21P4, and 1S21P6 electron configurations, all of which feature excellent super-atomic characters.

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Peptoid‐Directed Formation of Five‐Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization

Jin

Yan

et al. 2022

Angewandte Chemie

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While bio-inspired synthesis offers great potential for controlling nucleation and growth of inorganic particles, precisely tuning biomolecule-particle interactions is a long-standing challenge. Herein, we used variations in peptoid sequence to manipulate peptoid-Au interactions, leading to the synthesis of concave five-fold twinned, five-pointed Au nanostars via a process of repeated particle attachment and facet stabilization. Ex situ and liquid-phase TEM observations show that a balance between particle attachment biased to occur near the star points, preferential growth along the [100] direction, and stabilization of (111) facets is critical to forming star-shaped particles. Molecular simulations predict that interaction strengths between peptoids and distinct Au facets differ significantly and thus can alter attachment kinetics and surface energies to form the stars. This work provides new insights into how sequence-defined ligands affect particle growth to regulate crystal morphology.

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Twin Pathways: Discerning the Origins of Multiply Twinned Colloidal Nanoparticles

Cited by 6 publications

References 50 publications

Colloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry Breaking

Colloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry Breaking

Motif-to-Core Nucleation in a Decahedral Evolution Pattern

Peptoid‐Directed Formation of Five‐Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization

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