Gold cluster

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Gold clusters in cluster chemistry can be either discrete molecules or larger colloidal particles. Both types are described as nanoparticles, with diameters of less than one micrometer. A nanocluster is a collective group made up of a specific number of atoms or molecules held together by some interaction mechanism. [1] Gold nanoclusters have potential applications in optoelectronics [2] and catalysis. [3]

Contents

Bare gold clusters

Bare gold clusters, i.e., clusters without stabilizing ligand shells can be synthesized and studied in vacuum using molecular beam techniques. Their structures have been experimentally studied using, e.g., anion photoelectron spectroscopy, [4] far-infrared spectroscopy, [5] as well as measurements of their ion mobility and electron diffraction studies [6] in conjunction with quantum chemical calculations. The structures of such clusters differ strongly from those of the ligand-stabilized ones, indicating an pivotal influence of the chemical environment on the cluster structure. A notable example is Au20 which forms a perfect tetrahedron in which the Au atom packing closely resembles the atomic arrangement in the fcc bulk structure of metallic gold. [4] [5] Evidence has been presented for the existence of hollow golden cages with the partial formula Aun with n = 16 to 18. [7] These clusters, with diameter of 550 picometres, are generated by laser vaporization and characterized by photoelectron spectroscopy.

Structure of ligand-stabilized Au clusters

Construction of the Au13 icosahedron. Au Build Cluster.png
Construction of the Au13 icosahedron.

Bulk gold exhibits a face-centered cubic (fcc) structure. As gold particle size decreases the fcc structure of gold transforms into a centered-icosahedral structure illustrated by Au13. [1] It can be shown that the fcc structure can be extended by a half unit cell in order to make it look like a cuboctahedral structure. The cuboctahedral structure maintains the cubic-closed pack and symmetry of fcc. This can be thought of as redefining the unit cell into a more complicated cell. Each edge of the cuboctahedron represents a peripheral Au–Au bond. The cuboctahedron has 24 edges while the icosahedron has 30 edges; the transition from cuboctahedron to icosahedron is favored since the increase in bonds contributes to the overall stability of the icosahedron structure. [1]

The centered icosahedral cluster Au13 is the basis of constructing large gold nanoclusters. Au13 is the endpoint of atom-by-atom growth. In other words, starting with one gold atom up to Au12, each successful cluster is created by adding one additional atom. The icosahedral motif is found in many gold clusters through vertex sharing (Au25 and Au36), face-fusion (Au23 and Au29), and interpenetrating biicosahedrons (Au19, Au23, Au26, and Au29). [1] Large gold nanoclusters can essentially be reduced to a series of icosahedrons connecting, overlapping, and/or surrounding each other. The crystallization process of gold nanoclusters involves the formation of surface segments that grow towards the center of the cluster. The cluster assumes an icosahedral structure because of the associated surface energy reduction. [8]

Discrete gold clusters

Well-defined, molecular clusters are known, invariably containing organic ligands on their exteriors. Two examples are [Au6C(P(C6H5)3)6]2+ and [Au9(P(C6H5)3)8]3+. [9] In order to generate naked gold clusters for catalytic applications, the ligands must be removed, which is typically done via a high-temperature (200 °C/392 °F or higher) calcination process, [10] but can also be achieved chemically at low temperatures (below 100 °C/212 °F), e.g. using a peroxide-assisted route. [11]

Colloidal clusters

Gold clusters can be obtained in colloid form. Such colloids often occur with a surface coating of alkanethiols or proteins. Such clusters can be used in immunohistochemical staining. [12] Gold metal nanoparticles (NPs) are characterized by an intense absorption in the visible region, which enhances the utility of these species for the development of completely optical devices. The wavelength of this surface plasmon resonance (SPR) band depends on the size and shape of the nanoparticles as well as their interactions with the surrounding medium. The presence of this band enhances the utility of gold nanoparticle as building blocks for devices for data storage, ultrafast switching, and gas sensors. Whilst plasmonic gold nanoparticles only exhibit electric moments, clusters of such particles can exhibit magnetic moments making them of great interest for use in optical metamaterials [13]

Catalysis

When implanted on a FeOOH surface, gold clusters catalyze oxidation of CO at ambient temperatures. [14] Similarly gold clusters implanted on TiO2 can oxidize CO at temperatures as low as 40K. [15] Catalytic activity correlated with the structure of gold nanoclusters. A strong relationship between energetic and electronic properties with size and structure of gold nanoclusters. [16] [17]

See also

Related Research Articles

<span class="mw-page-title-main">Colloidal gold</span> Suspension of gold nanoparticles in a liquid

Colloidal gold is a sol or colloidal suspension of nanoparticles of gold in a fluid, usually water. The colloid is coloured usually either wine red or blue-purple . Due to their optical, electronic, and molecular-recognition properties, gold nanoparticles are the subject of substantial research, with many potential or promised applications in a wide variety of areas, including electron microscopy, electronics, nanotechnology, materials science, and biomedicine.

<span class="mw-page-title-main">Nanoparticle</span> Particle with size less than 100 nm

A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 100 nm in only two directions. At the lowest range, metal particles smaller than 1 nm are usually called atom clusters instead.

In chemistry, a superatom is any cluster of atoms that seem to exhibit some of the properties of elemental atoms.

Nanomaterial-based catalysts are usually heterogeneous catalysts broken up into metal nanoparticles in order to enhance the catalytic process. Metal nanoparticles have high surface area, which can increase catalytic activity. Nanoparticle catalysts can be easily separated and recycled. They are typically used under mild conditions to prevent decomposition of the nanoparticles.

<span class="mw-page-title-main">Nanochemistry</span> Combination of chemistry and nanoscience

Nanochemistry is an emerging sub-discipline of the chemical and material sciences that deals with the development of new methods for creating nanoscale materials. The term "nanochemistry" was first used by Ozin in 1992 as 'the uses of chemical synthesis to reproducibly afford nanomaterials from the atom "up", contrary to the nanoengineering and nanophysics approach that operates from the bulk "down"'. Nanochemistry focuses on solid-state chemistry that emphasizes synthesis of building blocks that are dependent on size, surface, shape, and defect properties, rather than the actual production of matter. Atomic and molecular properties mainly deal with the degrees of freedom of atoms in the periodic table. However, nanochemistry introduced other degrees of freedom that controls material's behaviors by transformation into solutions. Nanoscale objects exhibit novel material properties, largely as a consequence of their finite small size. Several chemical modifications on nanometer-scaled structures approve size dependent effects.

Magnetic nanoparticles are a class of nanoparticle that can be manipulated using magnetic fields. Such particles commonly consist of two components, a magnetic material, often iron, nickel and cobalt, and a chemical component that has functionality. While nanoparticles are smaller than 1 micrometer in diameter, the larger microbeads are 0.5–500 micrometer in diameter. Magnetic nanoparticle clusters that are composed of a number of individual magnetic nanoparticles are known as magnetic nanobeads with a diameter of 50–200 nanometers. Magnetic nanoparticle clusters are a basis for their further magnetic assembly into magnetic nanochains. The magnetic nanoparticles have been the focus of much research recently because they possess attractive properties which could see potential use in catalysis including nanomaterial-based catalysts, biomedicine and tissue specific targeting, magnetically tunable colloidal photonic crystals, microfluidics, magnetic resonance imaging, magnetic particle imaging, data storage, environmental remediation, nanofluids, optical filters, defect sensor, magnetic cooling and cation sensors.

<span class="mw-page-title-main">Platinum nanoparticle</span>

Platinum nanoparticles are usually in the form of a suspension or colloid of nanoparticles of platinum in a fluid, usually water. A colloid is technically defined as a stable dispersion of particles in a fluid medium.

<span class="mw-page-title-main">Electrocatalyst</span> Catalyst participating in electrochemical reactions

An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst can be heterogeneous such as a platinized electrode. Homogeneous electrocatalysts, which are soluble, assist in transferring electrons between the electrode and reactants, and/or facilitate an intermediate chemical transformation described by an overall half reaction. Major challenges in electrocatalysts focus on fuel cells.

<span class="mw-page-title-main">Silver nanoparticle</span> Ultrafine particles of silver between 1 nm and 100 nm in size

Silver nanoparticles are nanoparticles of silver of between 1 nm and 100 nm in size. While frequently described as being 'silver' some are composed of a large percentage of silver oxide due to their large ratio of surface to bulk silver atoms. Numerous shapes of nanoparticles can be constructed depending on the application at hand. Commonly used silver nanoparticles are spherical, but diamond, octagonal, and thin sheets are also common.

<span class="mw-page-title-main">Iron–nickel clusters</span>

Iron–nickel (Fe–Ni) clusters are metal clusters consisting of iron and nickel, i.e. Fe–Ni structures displaying polyhedral frameworks held together by two or more metal–metal bonds per metal atom, where the metal atoms are located at the vertices of closed, triangulated polyhedra.

Organogold chemistry is the study of compounds containing gold–carbon bonds. They are studied in academic research, but have not received widespread use otherwise. The dominant oxidation states for organogold compounds are I with coordination number 2 and a linear molecular geometry and III with CN = 4 and a square planar molecular geometry.

<span class="mw-page-title-main">Carbon nanotube supported catalyst</span> Novel catalyst using carbon nanotubes as the support instead of the conventional alumina

Carbon nanotube supported catalyst is a novel supported catalyst, using carbon nanotubes as the support instead of the conventional alumina or silicon support. The exceptional physical properties of carbon nanotubes (CNTs) such as large specific surface areas, excellent electron conductivity incorporated with the good chemical inertness, and relatively high oxidation stability makes it a promising support material for heterogeneous catalysis.

<span class="mw-page-title-main">Self-assembly of nanoparticles</span>

Nanoparticles are classified as having at least one of its dimensions in the range of 1-100 nanometers (nm). The small size of nanoparticles allows them to have unique characteristics which may not be possible on the macro-scale. Self-assembly is the spontaneous organization of smaller subunits to form larger, well-organized patterns. For nanoparticles, this spontaneous assembly is a consequence of interactions between the particles aimed at achieving a thermodynamic equilibrium and reducing the system’s free energy. The thermodynamics definition of self-assembly was introduced by Professor Nicholas A. Kotov. He describes self-assembly as a process where components of the system acquire non-random spatial distribution with respect to each other and the boundaries of the system. This definition allows one to account for mass and energy fluxes taking place in the self-assembly processes.

<span class="mw-page-title-main">Thiolate-protected gold cluster</span>

Thiolate-protected gold clusters are a type of ligand-protected metal cluster, synthesized from gold ions and thin layer compounds that play a special role in cluster physics because of their unique stability and electronic properties. They are considered to be stable compounds.

<span class="mw-page-title-main">Icosahedral twins</span> Structure found in atomic clusters and nanoparticles

An icosahedral twin is a nanostructure appearing in atomic clusters and also nanoparticles with some thousands of atoms. These clusters are twenty-faced, with twenty interlinked tetrahedral crystals joined along triangular faces having three-fold symmetry. A related, more common structure has five units similarly arranged with twinning, which were known as "fivelings" in the 19th century, more recently as "decahedral multiply twinned particles", "pentagonal particles" or "star particles". A variety of different methods lead to the icosahedral form at size scales where surface energies are more important than those from the bulk.

<span class="mw-page-title-main">Nanocluster</span> Collection of bound atoms or molecules ≤3 nm in diameter

Nanoclusters are atomically precise, crystalline materials most often existing on the 0-2 nanometer scale. They are often considered kinetically stable intermediates that form during the synthesis of comparatively larger materials such as semiconductor and metallic nanocrystals. The majority of research conducted to study nanoclusters has focused on characterizing their crystal structures and understanding their role in the nucleation and growth mechanisms of larger materials. These nanoclusters can be composed either of a single or of multiple elements, and exhibit interesting electronic, optical, and chemical properties compared to their larger counterparts.

<span class="mw-page-title-main">Irshad Hussain</span> Pakistani Scientist

Irshad Hussain is a Pakistani Scientist in the field of chemistry and among the few pioneers to initiate nanomaterials research in Pakistan.

<span class="mw-page-title-main">Heterogeneous gold catalysis</span>

Heterogeneous gold catalysis refers to the use of elemental gold as a heterogeneous catalyst. As in most heterogeneous catalysis, the metal is typically supported on metal oxide. Furthermore, as seen in other heterogeneous catalysts, activity increases with a decreasing diameter of supported gold clusters. Several industrially relevant processes are also observed such as H2 activation, Water-gas shift reaction, and hydrogenation. No gold-catalyzed reaction has been commercialized.

A bimetallic nanoparticle is a combination of two different metals that exhibit several new and improved properties. Bimetallic nano materials can be in the form of alloys, core-shell, or contact aggregate. Due to their novel properties, they have gained a lot of attention among the scientific and industrial communities. When used as catalysts, they show improved activity as compared to their monometallic counterparts. They are cost-effective, stable alternatives that exhibit high activity and selectivity. Hence a lot of effort has been put into the advancement of these catalysts. The combination or the type of metals present, how they are combined, and their size determines their properties.

<span class="mw-page-title-main">High-entropy-alloy nanoparticles</span>

High-entropy-alloy nanoparticles (HEA-NPs) are nanoparticles having five or more elements alloyed in a single-phase solid solution structure. HEA-NPs possess a wide range of compositional library, distinct alloy mixing structure, and nanoscale size effect, giving them huge potential in catalysis, energy, environmental, and biomedical applications.

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Further reading