Controlling ultrasmall gold nanoparticles with atomic precision

Gold nanoparticles are probably the nanoparticles that have been best studied for the longest time due to their stability, physicochemical properties and applications. Controlling gold nanoparticles with atomic precision is of significance for subsequent research on their structures, properties and applications, which is a dream that has been pursued for many years since ruby gold was first obtained by Faraday in 1857. Fortunately, this dream has recently been partially realized for some ultrasmall gold nanoparticles (nanoclusters). However, rationally designing and synthesizing gold nanoparticles with atomic precision are still distant goals, and this challenge might rely primarily on rich atomically precise gold nanoparticle libraries and the in-depth understanding of metal nanoparticle chemistry. Herein, we review general synthesis strategies and some facile synthesis methods, with an emphasis on the controlling parameters determined from well-documented results, which might have important implications for future nanoparticle synthesis with atomic precision and facilitate related research and applications.

The synthesis strategy, methods and parameters for atomically precise gold nanoclusters were reviewed, and future outlook was also proposed.     

Facile synthesis of gold nanoparticles with narrow size distribution by using AuCl or AuBr as the precursor

Gold(I) halides, including AuCl and AuBr, were employed for the first time as precursors in the synthesis of Au nanoparticles. The synthesis was accomplished by dissolving Au(I) halides in chloroform in the presence of alkylamines, followed by decomposition at 60 degrees C. The relative low stability of the Au(I) halides and there derivatives eliminated the need for a reducing agent, which is usually required for Au(III)-based precursors to generate Au nanoparticles. Controlled growth of Au nanoparticles with a narrow size distribution was achieved when AuCl and oleylamine were used for the synthesis. FTIR and mass spectra revealed that a complex, [AuCl(oleylamine)], was formed through coordination between oleylamine and AuCl. Thermolysis of the complex in chloroform led to the formation of dioleylamine and Au nanoparticles. When oleylamine was replaced with octadecylamine, much larger nanoparticles were obtained due to the lower stability of [AuCl(octadecylamine)] complex relative to [AuCl(oleylamine)]. Au nanoparticles can also be prepared from AuBr through thermolysis of the [AuBr(oleylamine)] complex. Due to the oxidative etching effect caused by Br(-), the nanoparticles obtained from AuBr exhibited an aspect ratio of 1.28, in contrast to 1.0 for the particles made from AuCl. Compared to the existing methods for preparing Au nanoparticles through the reduction of Au(III) compounds, this new approach based on Au(I) halides offers great flexibility in terms of size control.     

Rapid purification and size separation of gold nanoparticles via diafiltration

Purification and size-based separation of nanoparticles remain significant challenges in the preparation of well-defined materials for fundamental studies and applications. Diafiltration shows considerable potential for the efficient and convenient purification and size separation of water-soluble nanoparticles, allowing for the removal of small-molecule impurities and for the isolation of small nanoparticles from larger nanostructures in a single process. Herein, we report studies aimed at assessing the suitability of diafiltration for (i) the purification of water-soluble thiol-stabilized 3-nm gold nanoparticles, (ii) the separation of a bimodal distribution of nanoparticles into the corresponding fractions, and (iii) the separation of a polydisperse sample into fractions of differing mean core diameter. NMR, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) measurements demonstrate that diafiltration produces nanoparticles with a much higher degree of purity than is possible by dialysis or a combination of solvent washes, chromatography, and ultracentrifugation. UV-visible spectroscopic and transmission electron microscopic (TEM) analyses show that diafiltration offers the ability to separate nanoparticles of disparate core size. These results demonstrate the applicability of diafiltration for the rapid and green preparation of high-purity gold nanoparticle samples and the size separation of heterogeneous nanoparticle samples. They also suggest the development of novel diafiltration membranes specifically suited to high-resolution nanoparticle size separation.     

Shape-controlled synthesis of highly monodisperse and small size gold nanoparticles

We describe here that fine control of nanoparticle shape and size can be achieved by systematic varia-tion of experimental parameters in the seeded growth procedure in aqueous solution. Cubic and spherical gold nanoparticles are obtained respectively. In particularly, the Au cubes are highly mono-disperse in 33±2 nm diameter. The experimental methods involve the preparation of Au seed particles and the subsequent addition of an appropriate quantity of Au seed solution to the aqueous growth solutions containing desired quantities of CTAB and ascorbic acid (AA). Here, AA is a weak reducing agent and CTAB is not only a stable agent for nanoparticles but also an inductive agent for leading increase in the face of nanoparticle. Ultraviolet visible spectroscopy (UV-vis), X-ray diffraction (XRD), transmission electron microscopy (TEM) are used to characterize the nanoparticles. The results show that the different size gold nanoparticles displayed high size homogenous distribution and formed mono-membrane at the air/solid interface.     

The properties of silica nanoparticles with high monodispersity synthesized in the microreactor system

A new combined micromixer/microreactor/batch reactor system for the synthesis of monodisperse silica particles was demonstrated, which showed superiorities over the batch reactor. The silica nanoparticles with different sizes (ranging from 20 nm to 2 μm) and size distributions could be controllably synthesized by varying the reaction temperature and reaction time. The narrowest size distribution of the silica particles was synthesized at 60 °C. The transmission electron microscopy characterization showed that the sphericities of silica particles got better as the particle size increased. Thermal gravimetry–differential thermal analysis and Fourier transform infrared characterization indicated that the amount of ethoxy groups of silica particles decreased and the hydroxyl groups increased with the reaction time increasing. And the hydroxyl groups in silica particles increased with the reaction temperature rising.     

Controllable synthesis of water-soluble gold nanoparticles and their applications in electrocatalysis and surface-enhanced Raman scattering

We report a facile method to synthesize water-soluble gold nanoparticles (AuNPs) using a biosurfactant sodium cholate as reducing reagents and protective groups in aqueous solution at ambient temperature. The diameters (13-70 nm) of uniform AuNPs can be readily adjusted by changing the initial molar ratio of sodium cholate to chloroauric acid (HAuCl(4)). Also, the alkaline condition of preparative solution is found to affect the size of as-synthesized AuNPs. This synthetic approach is one-step and "green". The obtained AuNPs exhibit a good electrocatalytic activity toward methanol oxidation. Meanwhile, the AuNPs thin films can serve as an efficient substrate for surface-enhanced Raman scattering (SERS). Furthermore, platinum nanoparticles (PtNPs) are also prepared by reducing sodium tetrachloro platinate hydrate with sodium cholate.     

Fine-tuning size of gold nanoparticles by cooling during reverse micelle synthesis

By lowering the reaction temperature during metal ion reduction in a reverse micelle system, gold nanoparticle size can be subtly tuned from 6.6 to 2.2 nm in diameter. Under these reaction conditions, the water-to-surfactant ratio (W value) also plays an important role in controlling the particle size, enabling a wide range of products obtainable via a simple, quick, reproducible synthesis. Particle sizes were measured by HRTEM, and size trends were supported by UV-vis spectroscopy.     

Facile polyol synthesis of ultrasmall water-soluble cobalt ferrite nanoparticles

A facile protocol to prepare ultrasmall citrate-coated cobalt ferrite NPs was proposed from the comparison between one-step and two-step chemical routes based on the polyol method. Infrared spectroscopy, thermogravimetry and zeta potential data indicated different coordinations of citrate groups affecting the NP colloidal stability. The magnetic core size and saturation magnetization were also affected. The surface-modified NPs prepared by the one-step route presented superior colloidal stability, low core (2.9 nm) and hydrodynamic (4.8 nm) sizes, high magnetization (45 emu/g), and can be considered suitable platforms to produce nanoparticle-biomolecule conjugates.     

Morphology-selective synthesis of polyhedral gold nanoparticles: what factors control the size and morphology of gold nanoparticles in a wet-chemical process

Polyhedral gold nanoparticles below 100 nm in size were fabricated by continuously delivered HAuCl(4) and PVP starting solutions into l-ascorbic acid aqueous solution in the presence of gold seeds, and under addition of sodium hydroxide (NaOH). By continuously delivered PVP and HAuCl(4) starting solutions in the presence of gold seed, the size and shape of polyhedral gold were achieved in relatively good uniformity (particle size distribution=65-95 nm). Morphological evolution was also attempted using different growth rates of crystal facets with increasing reaction temperature, and selective adsorption of PVP.     

Polymer-stabilized gold nanoparticles with high grafting densities

A series of polymer-coated Au nanoparticles have been prepared using the "grafting-to" approach. Thiol-terminated polystyrene and poly(ethylene oxide) ligands are found to form dense brushes on the faceted gold nanoparticle surfaces. Depending on the polymer, the ligand grafting densities on the gold nanoparticles are 1.2- to 23.5-fold greater than those available via self-assembled monolayer formation of the corresponding two-dimensional gold surfaces.     

Expeditious synthesis of water-soluble, monolayer-protected gold nanoparticles of controlled size and monolayer composition

A protocol is reported for the preparation of water-soluble, thiol-protected Au nanoparticles (Au-MPC) where dioctylamine is used as a stabilizing agent when the gold cluster is formed using the two-phase Brust and Schiffrin procedure. The amount of amine controls the size of the nanoparticles in the 1.9-8.9 nm diameter range. The final stabilization of the gold clusters by addition of functionalized thiols is performed under very mild conditions compatible with most biomolecules. The procedure is suitable for a wide variety of functional groups present in the thiol and allows one to use thiol mixtures with a precise control of their composition in the monolayer. As a proof of principle, examples of nanoparticles protected with thiols comprising functional groups ranging from polyethers, saccharides, polyamines and ammonium ions are reported.     

Controllable synthesis of MnS nanocrystals from a single-source precursor

A facile single-source precursor method has been applied for the selective synthesis of MnS nanocrystals (NCs) with well-defined shapes and crystal structures such as hexapod, octahedral, hexagonal shaped α-MnS NCs, and pencil-shaped γ-MnS NCs. The effects of the composition of precursor, reaction temperature, and the heating rate on the morphologies, and crystal structures of MnS NCs were systematically studied for the first time.     

One-phase synthesis of gold nanoparticles with varied solubility

We developed a straightforward synthesis of gold nanoparticles with diameters in the range 2.1-7.0 nm which display solubility in both aqueous and nonpolar (toluene, chloroform) media. This versatile solubility of the nanoparticles is achieved by the use of a thiolated PEG capping agent. Their plasmon resonance band is virtually unaltered in different media.     

Seed free high yield gold nanorods synthesis from single precursor gold(I) dithiophosphate complex

In this work, we demonstrate a simple, one pot and seed free synthetic route for the formation of gold nanorods (Au NRs) via thermal decomposition of gold(I) dithiophosphate {[Au₂{S₂P(OⁱPr)₂}₂]_n,} 1 complex as a molecular precursor in presence of 4′‐amino‐biphenyl‐4‐carboxylic molecule. Here [Au₂{S₂P(OⁱPr)₂}₂]_n, complex functioned as gold (Au) source and 4′‐amino‐biphenyl‐4‐carboxylic molecule stabilized gold (Au) nanorods (NRs) through the unidirectional coating of Au surface during its growth in the reaction medium.     

Surfactant-free synthesis and functionalization of gold nanoparticles

A new, facile and generally applicable synthesis of functionalized gold nanoparticles is presented. It is based on the surfactant-free generation of weakly stabilized nanoparticles by the reduction of HAuCl4 with sodium naphthalenide in diglyme. These nanoparticles were found to lack long-term stability. However, stabilization in both unpolar and polar solvents could straightforwardly be achieved by subsequent addition of various capping ligands. The resulting ligand-capped gold nanoparticles were investigated by TEM microscopy, UV-vis, and FT-IR spectroscopy. Particle core size can be tuned by the amount of reduction agent. The strict separation of the reduction step and the functionalization step in this one-pot synthesis offers an easy and fast access to highly functionalized gold nanoparticles.     

Photochemical synthesis and self-assembly of gold nanoparticles

Colloidal gold was prepared by UV light irradiation of the mixture of HAuCl₄ aqueous solution and poly(vinyl pyrrolidone) (PVP) ethanol solution in the presence of silver ions. The resulting sheet-like nanoparticles were found to self-assemble into nanoflowers by a centrifuging process. The results of control experiments reflected that only suitable size sheet-like nanoparticles could assemble into the flower-like structures. The presence of Ag ions and PVP are essential for the formation process of nanoflowers. They perform their function by serving as structure-directing agents to produce the sheet-like particles. The appearance of the flower-like assemblages is attributed to the combination of Van der Waals force and the anisotropic hydrophobic attraction between the nanoparticles. The flower-like assemblages films can be used as surface-enhanced Raman spectroscopy (SERS) substrates with 4-aminothiophenol (4-ATP) molecule as a test probe.     

聚甲基丙烯酸钠辅助的金纳米颗粒的绿色制备

利用聚甲基丙烯酸钠的弱还原性和螯合作用,建立了一种水溶性金纳米颗粒合成的新方法.借助紫外可见分光光度计和透射电子显微镜对金纳米颗粒进行了表征,初步讨论了反应物浓度以及反应温度对产物的影响.     

One-step synthesis of FePt nanoparticles with tunable size

A one-step synthesis of FePt nanoparticles is reported. The size, composition, and shape of the particles are controlled by varying the synthetic parameters such as molar ratio of stabilizers to metal precursor, addition sequence of the stabilizers and metal precursors, heating rate, heating temperature, and heating duration. An assembly of large (6 nm or greater) FePt nanoparticles, especially oxide-coated FePt nanoparticles, can sustain higher temperature (up to 650 degrees C) annealing without noticeable particle sintering. Room temperature coercivity of an assembly containing discrete FePt dots can reach as high as 1.3 T, a value that is suitable for hard magnetic applications.