Quantitative Analysis of the Coverage Density of Br<sup>–</sup> Ions on Pd{100} Facets and Its Role in Controlling the Shape of Pd Nanocrystals

Peng, Hsin‐Chieh; Xie, Shuifen; Park, Jinho; Xia, Xiaohu; Xia, Younan

doi:10.1021/ja400301k

Cited by 157 publications

(204 citation statements)

References 35 publications

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“…In addition, the presence of Br − ions shifted the equilibrium to the right based on Equation (8) , further promoting the galvanic replacement. Owing to the selective adsorption of Br − ions on Pd{100} facets, [ 76,91 ] the PtBr 6 2− complex was expected to have a higher concentration in the vicinity of the {100} facets. As a result, Pd atoms on the {100} facets of a nanocube were preferentially oxidized and dissolved by reacting with PtBr 6 2− ( Figure 5 A), leading to the formation of Pd-Pt concave nanocubes ( Figure 5 , B-D) and eventually octapods (Figure 5 E).…”

Section: Progress Reportmentioning

confidence: 99%

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

et al. 2013

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This article provides a progress report on the use of galvanic replacement for generating complex hollow nanostructures with tunable and well-controlled properties. We begin with a brief account of the mechanistic understanding of galvanic replacement, specifically focused on its ability to engineer the properties of metal nanostructures in terms of size, composition, structure, shape, and morphology. We then discuss a number of important concepts involved in galvanic replacement, including the facet selectivity involved in the dissolution and deposition of metals, the impacts of alloying and dealloying on the structure and morphology of the final products, and methods for promoting or preventing a galvanic replacement reaction. We also illustrate how the capability of galvanic replacement can be enhanced to fabricate nanomaterials with complex structures and/or compositions by coupling with other processes such as co-reduction and the Kirkendall effect. Finally, we highlight the use of such novel metal nanostructures fabricated via galvanic replacement for applications ranging from catalysis to plasmonics and biomedical research, and conclude with remarks on prospective future directions.

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Section: Progress Reportmentioning

confidence: 99%

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

et al. 2013

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“…To date, CAs have played an important role on shape‐controlled synthesis of NCs,137, 138, 139, 140, 141, 142 and there are many successful examples in preparing Cu 2 O NCs 7, 8, 75, 107, 122, 125, 143. We will introduce some classic synthetic routes of Cu 2 O NCs enclosed by low‐index facets.…”

Section: Basic Growth Strategies For Cu2o Polyhedramentioning

confidence: 99%

Facet‐Controlled Synthetic Strategy of Cu₂O‐Based Crystals for Catalysis and Sensing

2015

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Shape‐dependent catalysis and sensing behaviours are primarily focused on nanocrystals enclosed by low‐index facets, especially the three basic facets ({100}, {111}, and {110}). Several novel strategies have recently exploded by tailoring the original nanocrystals to greatly improve the catalysis and sensing performances. In this Review, we firstly introduce the synthesis of a variety of Cu2O nanocrystals, including the three basic Cu2O nanocrystals (cubes, octahedra and rhombic dodecahedra, enclosed by the {100}, {111}, and {110} facets, respectively), and Cu2O nanocrystals enclosed by high‐index planes. We then discuss in detail the three main facet‐controlled synthetic strategies (deposition, etching and templating) to fabricate Cu2O‐based nanocrystals with heterogeneous, etched, or hollow structures, including a number of important concepts involved in those facet‐controlled routes, such as the selective adsorption of capping agents for protecting special facets, and the impacts of surface energy and active sites on reaction activity trends. Finally, we highlight the facet‐dependent properties of the Cu2O and Cu2O‐based nanocrystals for applications in photocatalysis, gas catalysis, organocatalysis and sensing, as well as the relationship between their structures and properties. We also summarize and comment upon future facet‐related directions.

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“…62 Removal of PVP from noble metal surfaces generally requires more forcing conditions. 63 Several studies have shown that charge transfer and the co-ordination mode of PVP molecules with noble metal nanoparticles to be size dependent.…”

Section: Oxidation and Interaction Of Pvp With Pd Nanocrystalsmentioning

confidence: 99%

Stability, Oxidation, and Shape Evolution of PVP-Capped Pd Nanocrystals

et al. 2014

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Access to the full text of the published version may require a subscription. Rights © 2014 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form AbstractA critical aspect in the practical application and enhanced catalytic performance of shape controlled nanocrystals is their stability and morphology retention under ambient conditions.Changes to the morphology of shape-controlled Pd nanocrystals capped by PVP are assessed by TEM and surface oxidation was evaluated by X-ray photoelectron spectroscopy (XPS), over 12 months. Surface oxidation of PVP-capped Pd nanocrystals resulted in loss of edge and corner sites and transition to spherical morphologies. The shape stability of the nanocrystals was found to follow the trend cubic < cuboctahedra < octahedral ~ concave cubes. For low index planes, {111} surfaces are more resistant to oxidation compared to {100} facets, correlating with the surface free energy of the nanocrystals. Cubic and cuboctahedral nanocrystals transitioned to spherical particles while octahedral nanocrystals retained their morphology. The presence of high energy {110} facets were observed in the cubic nanocrystals which undergo surface reconstruction. The presence of surface defects such as stacking faults were also found to influence the rate of the structural changes.Concave cubic nanocrystals, which possess high index facets and surface energies were consistently found to display excellent morphology retention. The concave cubic 2 nanocrystals displayed superior shape stability and reduced oxidation compared to cubic and cuboctahedral nanocrystals. XPS analysis further determined that PVP capping ligands on different Pd surface facets strongly influences the morphological consistency. The stability of the concave cubes can be attributed to stronger chemisorption of PVP capping ligands to the high index plane making them less susceptible to oxidation.

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Quantitative Analysis of the Coverage Density of Br^– Ions on Pd{100} Facets and Its Role in Controlling the Shape of Pd Nanocrystals

Cited by 157 publications

References 35 publications

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

Facet‐Controlled Synthetic Strategy of Cu₂O‐Based Crystals for Catalysis and Sensing

Stability, Oxidation, and Shape Evolution of PVP-Capped Pd Nanocrystals

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Quantitative Analysis of the Coverage Density of Br– Ions on Pd{100} Facets and Its Role in Controlling the Shape of Pd Nanocrystals

Cited by 157 publications

References 35 publications

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

Facet‐Controlled Synthetic Strategy of Cu2O‐Based Crystals for Catalysis and Sensing

Stability, Oxidation, and Shape Evolution of PVP-Capped Pd Nanocrystals

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Quantitative Analysis of the Coverage Density of Br^– Ions on Pd{100} Facets and Its Role in Controlling the Shape of Pd Nanocrystals

Facet‐Controlled Synthetic Strategy of Cu₂O‐Based Crystals for Catalysis and Sensing