Monolayer protected gold nanoparticles: the effect of the headgroup–Au interaction

Olmos-Asar, Jimena A.; Ludueña, Martín; Mariscal, Marcelo M.

doi:10.1039/c4cp01963f

Cited by 30 publications

(33 citation statements)

References 46 publications

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“…The interactions between thiol ligand and noble metal are very strong (covalent). This is well experimentally demonstrated with Au NCs [27][28][29] and confirmed by atomistic simulation [30]. At the Au surface, significant damages and/or amorphous-like structures were observed [30].…”

Section: Ligand-atoms Interactionssupporting

confidence: 65%

“…The decrease of the ligands surface coverage may explain the drop of the mechanical properties mediated by ligand-ligand interactions of NPs assemblies. Furthermore, the drastic damages [30] due to interactions between thiol ligand and Au atoms could reduce the number of ligands attachment sites at the Au NCs surface. Consequently, the drop of the coverage could induce a drop in the E value on increasing the Au NCs size.…”

Section: Size Effect Of the Building Blocks (Ncs) Used To Producementioning

confidence: 99%

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Mechanical properties of supracrystals

Pileni¹

2017

EPL

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-The mechanical properties of three-dimensional self-assembled nanocrystals, as socalled supracrystals, are correlated with: i) the type of terminate groups of coating agents used to stabilize the nanocrystals; ii) their interactions with the nanocrystal surface atoms; iii) the nanocrystal morphology; iv) the interparticle distance between nanocrystals; v) translational and orientational ordering of atomic lattice planes of nanocrystals. The Young moduli evolve from a few MPa to GPa by controlling the various factors mentioned above.

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Section: Ligand-atoms Interactionssupporting

confidence: 65%

Section: Size Effect Of the Building Blocks (Ncs) Used To Producementioning

confidence: 99%

Mechanical properties of supracrystals

Pileni¹

2017

EPL

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“…Experimental data as well as theoretical calculations indicate that when the strength of the ligand-metal bond is similar to that of the metal-metal bond (strongly binding ligands), the M a n u s c r i p t 19 crystalline arrangement of surface atoms is altered [160]. This is for example the case of thiolate protected Au [161], Pt [99] or Ru [38] NPs which display a highly disordered surface while amine ligands that only weakly interact with Au or Ru atoms afford crystalline MNPs [68].…”

Section: Influence On the Size Shape And Structurementioning

confidence: 95%

Controlled metal nanostructures: Fertile ground for coordination chemists

Amiens

Ciuculescu-Pradines

Philippot

2016

Coordination Chemistry Reviews

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“…16 Results from molecular simulations suggest that the influence of the capping molecule can also reach deeper atomic layers in gold nanoparticles smaller than 2 nm. 17,18 In the case of planar palladium, DFT calculations show that when only thiolates are adsorbed on the surface, there is no reordering of the metal atoms in the first layers; 7,13 however, when sulfide is incorporated as an adsorbate, a considerable surface reconstruction takes place. This behavior is attributed to…”

Section: −14mentioning

confidence: 99%

Influence of Capping on the Atomistic Arrangement in Palladium Nanoparticles at Room Temperature

et al. 2014

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The role that protecting molecules have on the way that palladium atoms arrange themselves in nanoparticles prepared at room temperature was studied by the analysis of aberration-corrected scanning transmission electron microscopy images and atomistic Langevin dynamics simulations. It was found that the arrangement of Pd atoms is less ordered in thiolate-protected nanoparticles than in amine-protected ones. The experimental and theoretical data showed that the disorder in ∼3 nm thiolate-protected particles is promoted by the strong S−Pd bond in the sulfide layer that surrounds the nanoparticles. ■ INTRODUCTIONThe unique properties of thiolate self-assembled monolayers (SAMs) have provoked great interest in these assemblies, especially for their role in the stability and interfacial properties of thiolate-protected noble-metal nanoparticles (NPs).1,2 Gold nanoparticles are among the most studied metal nanoparticles, to the point of being considered the de facto model system in this field of research.3,4 However, some properties of other metals can be very different from those of gold, and the case of palladium is an example that fulfills this statement. For instance, the adsorption of alkanethiols on planar palladium surfaces produces a sulfide layer (with submonolayer coverage) lying at the interface between palladium and thiolate moieties. 5−7Density functional theory (DFT) calculations show that the sulfide layer comes from the S−C bond scission caused by a charge transfer from the palladium d band to antibonding thiolate orbitals. 7 In addition, it was recently shown that the chemical composition of the surface of alkanethiolate-protected palladium nanoparticles is very similar to that of alkanethiolatemodified bulk palladium: Pd(0) cores are surrounded by a submonolayer of sulfide species, which are protected by alkanethiolates. 8−10 Despite the fact that these particles have very interesting properties that can be exploited in catalysis 11 and sensing, 12 their detailed structure has been barely studied. Indeed, even in recent studies, the already known 5,8 chemical nature of the Pd−thiolate interface is ignored. 11−14It is well-known that thiolate species produce a reconstruction of the gold surface both in planar substrates 15 and in nanoparticles. 16 Results from molecular simulations suggest that the influence of the capping molecule can also reach deeper atomic layers in gold nanoparticles smaller than 2 nm. 17,18 In the case of planar palladium, DFT calculations show that when only thiolates are adsorbed on the surface, there is no reordering of the metal atoms in the first layers; 7,13 however, when sulfide is incorporated as an adsorbate, a considerable surface reconstruction takes place. This behavior is attributed to

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Monolayer protected gold nanoparticles: the effect of the headgroup–Au interaction

Cited by 30 publications

References 46 publications

Mechanical properties of supracrystals

Mechanical properties of supracrystals

Controlled metal nanostructures: Fertile ground for coordination chemists

Influence of Capping on the Atomistic Arrangement in Palladium Nanoparticles at Room Temperature

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