Search results for "NANOCLUSTERS"

Bulky Surface Ligands Promote Surface Reactivities of [Ag141X12(S-Adm)40]3+ (X = Cl, Br, I) Nanoclusters: Models for Multiple-Twinned Nanoparticles

2017

Surface ligands play important roles in controlling the size and shape of metal nanoparticles and their surface properties. In this work, we demonstrate that the use of bulky thiolate ligands, along with halides, as the surface capping agent promotes the formation of plasmonic multiple-twinned Ag nanoparticles with high surface reactivities. The title nanocluster [Ag141X12(S-Adm)40]3+ (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag71 core protected by a shell of Ag70X12(S-Adm)40. The Ag71 core can be considered as 20 frequency-two Ag10 tetrahedra fused together with a dislocation that resembles multiple-twinning in nanoparticles. The nanocluster…

A unified view of ligand-protected gold clusters as superatom complexes

2008

Synthesis, characterization, and functionalization of self-assembled, ligand-stabilized gold nanoparticles are long-standing issues in the chemistry of nanomaterials. Factors driving the thermodynamic stability of well documented discrete sizes are largely unknown. Herein, we provide a unified view of principles that underlie the stability of particles protected by thiolate (SR) or phosphine and halide (PR 3 , X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au 102 (SR) 44 , Au 39 (PR 3 ) 14 X 6 − , Au 11 (PR 3 ) 7 X 3 , and Au 13 (PR 3 ) 10 X 2 3+ , where X is either a halogen or a thiol…

Ag44(EBT)26(TPP)4Nanoclusters With Tailored Molecular and Electronic Structure

2021

Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge-neutral Ag NC with the formula Ag44 (EBT)26 (TPP)4 (EBT: 2-ethylbenzenethiolate; TPP: triphenylphosphine). The single-crystal X-ray structure reveals that this NC has a hollow metal core of Ag12 @Ag20 and a metal-ligand shell of Ag12 (EBT)26 (TPP)4 . The presence of mixed ligands and long V-shaped metal-ligand …

Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl-Protected Body-Centered Cubic Clus…

2016

The synthesis, structure, substitution chemistry, and optical properties of the gold-centered cubic monocationic cluster [Au@Ag8@Au6(C≡CtBu)12]+ are reported. The metal framework of this cluster can be described as a fragment of a body-centered cubic (bcc) lattice with the silver and gold atoms occupying the vertices and the body center of the cube, respectively. The incorporation of alkali metal atoms gave rise to [MnAg8−nAu7(C≡CtBu)12]+ clusters (n=1 for M=Na, K, Rb, Cs and n=2 for M=K, Rb), with the alkali metal ion(s) presumably occupying the vertex site(s), whereas the incorporation of copper atoms produced [CunAg8Au7−n(C≡CtBu)12]+ clusters (n=1–6), with the Cu atom(s) presumably occup…

A new efficient, highly dispersed, Pd nanoparticulate silica supported catalyst synthesized from an organometallic precursor. Study of the homogeneou…

2018

[EN] A new Pd(0) catalyst supported on silica UVM-7 has been synthesized from the organometallic [Pd-2(mu-(C6H4) Pp(2))(2)(CH3CN)(4)](BF4)(2) precursor, characterized by the high dispersion, activity, and small size of the palladium nanoclusters fixed on the silica surface. The catalyst was tested for the Suzuki-Miyaura (SM) reaction of different 4-substitutedphenyl halides with phenylboronic acid. The kinetic study concurs with most of the catalytic action was carried out by Pd species originated by the partial solubilization of Pd immobilized on mesoporous silica. The Schmidt's analysis of differential selectivity (SADS) in several competitive SM reactions, together the STEM-HAADF and HRT…

ZnO Nanowires catalytic solution growth for piezotronic and bio-applications

2016

Simulations on the mechanism of CNT bundle growth upon smooth and nanostructured Ni as well as θ-Al2O3 catalysts

2011

Abstract In the current study, we have performed ab initio DFT calculations on the gradually growing 2D periodic models of capped single-wall carbon nanotubes (SW CNTs) upon their perpendicular junctions with the Ni(111) substrate, in order to understand the peculiarities of the initial stage of their growth on either smooth or nanostructured catalytic particles. Appearance of the adsorbed carbon atoms upon the substrate follows from the dissociation of CVD hydrocarbon molecules, e.g., CH4: (CH4)ads → (CH)ads+3Hads and (CH)ads → Cads+Hads. (Since the effective growth of CNTs upon Ni nanoparticles occur inside the nanopores of amorphous alumina, we have also simulated analogous surface react…

Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4– Nanoclusters via Ion Pairing

2016

In this work, a facile ion-pairing strategy for asymmetric synthesis of optically active negatively charged chiral metal nanoparticles using chiral ammonium cations is demonstrated. A new thiolated chiral three-concentric-shell cluster, [Ag28Cu12(SR)24]4–, was first synthesized as a racemic mixture and characterized by single-crystal X-ray structure determination. Mass spectrometric measurements revealed relatively strong ion-pairing interactions between the anionic nanocluster and ammonium cations. Inspired by this observation, the as-prepared racemic mixture was separated into enantiomers by employing chiral quaternary ammonium salts as chiral resolution agents. Subsequently, direct asymm…

Dynamic Stabilization of the Ligand-Metal Interface in Atomically Precise Gold Nanoclusters Au68 and Au144 Protected by meta-Mercaptobenzoic Acid

2017

Ligand-stabilized, atomically precise gold nanoclusters with a metal core of a uniform size of just 1–3 nm constitute an interesting class of nanomaterials with versatile possibilities for applications due to their size-dependent properties and modifiable ligand layers. The key to extending the usability of the clusters in applications is to understand the chemical bonding in the ligand layer as a function of cluster size and ligand structure. Previously, it has been shown that monodispersed gold nanoclusters, stabilized by meta-mercaptobenzoic acid (m-MBA or 3-MBA) ligands and with sizes of 68–144 gold atoms, show ambient stability. Here we show that a combination of nuclear magnetic reson…

Selective Acrolein Hydrogenation over Ligand-Protected Gold Clusters : A Venus Flytrap Mechanism

2022

The catalytic partial hydrogenation of α,β-unsaturated aldehydes is an ideal reaction to understand the selectivity between two different functional groups Here the two functional groups are C═C and C═O, and the hydrogenation of C═O is preferentially desired due to the importance of the issuing products, unsaturated alcohols, in fine-chemical industries. Using density functional theory calculations, we investigate the catalytic competency toward this reaction of a Au nanocluster in the presence of protecting ligands that offer higher stability and the possibility for the uniform distribution of size-selected clusters in the catalytic system. meta-Mercaptobenzoic-acid-protected-protected Au …