Known since ancient times, the synthesis of colloidal gold was originally used as a method of staining glass. Modern scientific evaluation of colloidal gold did not begin until Michael Faraday's work of the 1850s. A so-called Elixir of Life, a potion made from gold, was discussed, if not actually manufactured, in ancient times. Colloidal gold has been used since Ancient Roman times to colour glass intense shades of yellow, red, or mauve, depending on the concentration of gold, and in Hindu Chemistry, for various potions. In the 16th century, the alchemist Paracelsus claimed to have created a potion called Aurum Potabile (Latin: potable gold). In the 17th century the glass-colouring process was refined by Andreus Cassius and Johann Kunckel. In 1842, John Herschel invented a photographic process called Chrysotype (from the Greek word for gold) that used colloidal gold to record images on paper. Paracelsus' work is known to have inspired Michael Faraday to prepare the first pure sample of colloidal gold, which he called 'activated gold', in 1857. He used phosphorus to reduce a solution of gold chloride.
For a long time the composition of the Cassius ruby-gold was unclear. Several chemists suspected it to be a gold tin compound, due to its preparation. Faraday was the first to recognize that the color was due to the minute size of the gold particles. In 1898 Richard Adolf Zsigmondy prepared the first colloidal gold in diluted solution. Apart from Zsigmondy, Theodor Svedberg, who invented ultracentrifugation, and Gustav Mie, who provided the theory for scattering and absorption by spherical particles, were also interested in understanding synthesis and properties of colloidal gold.
Generally, gold nanoparticles are produced in a liquid ("liquid chemical methods") by reduction of chloroauric acid (H[AuCl4]), although more advanced and precise methods do exist. After dissolving H[AuCl4], the solution is rapidly stirred while a reducing agent is added. This causes Au3+ ions to be reduced to neutral gold atoms. As more and more of these gold atoms form, the solution becomes supersaturated, and gold gradually starts to precipitate in the form of sub-nanometer particles. The rest of the gold atoms that form stick to the existing particles, and, if the solution is stirred vigorously enough, the particles will be fairly uniform in size.
To prevent the particles from aggregating, some sort of stabilizing agent that sticks to the nanoparticle surface is usually added. They can be functionalized with various organic ligands to create organic-inorganic hybrids with advanced functionality. It can also be synthesised by laser ablation.
The method pioneered by J. Turkevich et al. in 1951  and refined by G. Frens in 1970s, is the simplest one available. Generally, it is used to produce modestly monodisperse spherical gold nanoparticles suspended in water of around 10–20 nm in diameter. Larger particles can be produced, but this comes at the cost of monodispersity and shape. It involves the reaction of small amounts of hot chlorauric acid with small amounts of sodium citrate solution. The colloidal gold will form because the citrate ions act as both a reducing agent, and a capping agent.
Recently, the evolution of the spherical gold nanoparticles in the Turkevich reaction has been elucidated. Interestingly, extensive networks of gold nanowires are formed as a transient intermediate. These gold nanowires are responsible for the dark appearance of the reaction solution before it turns ruby-red.
To produce larger particles, less sodium citrate should be added (possibly down to 0.05%, after which there simply would not be enough to reduce all the gold). The reduction in the amount of sodium citrate will reduce the amount of the citrate ions available for stabilizing the particles, and this will cause the small particles to aggregate into bigger ones (until the total surface area of all particles becomes small enough to be covered by the existing citrate ions).
This method was discovered by Brust and Schiffrin in early 1990s, and can be used to produce gold nanoparticles in organic liquids that are normally not miscible with water (like toluene). It involves the reaction of a chlorauric acid solution with tetraoctylammonium bromide (TOAB) solution in toluene and sodium borohydride as an anti-coagulant and a reducing agent, respectively.
Here, the gold nanoparticles will be around 5–6 nm. NaBH4 is the reducing agent, and TOAB is both the phase transfer catalyst and the stabilizing agent.
It is important to note that TOAB does not bind to the gold nanoparticles particularly strongly, so the solution will aggregate gradually over the course of approximately two weeks. To prevent this, one can add a stronger binding agent, like a thiol (in particular, alkanethiols), which will bind to gold, producing a near-permanent solution. Alkanethiol protected gold nanoparticles can be precipitated and then redissolved. Some of the phase transfer agent may remain bound to the purified nanoparticles, this may affect physical properties such as solubility. In order to remove as much of this agent as possible the nanoparticles must be further purified by soxhlet extraction.
This approach, discovered by Perrault and Chan in 2009, uses hydroquinone to reduce HAuCl4 in an aqueous solution that contains gold nanoparticle seeds. This seed-based method of synthesis is similar to that used in photographic film development, in which silver grains within the film grow through addition of reduced silver onto their surface. Similarly, gold nanoparticles can act in conjunction with hydroquinone to catalyze reduction of ionic gold onto their surface. The presence of a stabilizer such as citrate results in controlled particle growth. Typically, the nanoparticle seeds are produced using the citrate method. The hydroquinone method complements that of Frens, as it extends the range of monodispersed spherical particle sizes that can be produced. Whereas the Frens method is ideal for particles of 12-20 nm, the hydroquinone method can produce particles of at least 30-250 nm.
Another method for the experimental generation of gold particles is by sonolysis. In one such process based on ultrasound, the reaction of an aqueous solution of HAuCl4 with glucose, the reducing agents are hydroxyl radicals and sugar pyrolysis radicals (forming at the interfacial region between the collapsing cavities and the bulk water) and the morphology obtained is that of nanoribbons with width 30 -50 nm and length of several micrometers. These ribbons are very flexible and can bend with angles larger than 90°. When glucose is replaced by cyclodextrin (a glucose oligomer) only spherical gold particles are obtained suggesting that glucose is essential in directing the morphology towards a ribbon.
Block Copolymer-mediated Method
An economical, environmentally benign and fast synthesis methodology for gold nanoparticles using block copolymer has been developed by Sakai et al. . In this synthesis methodology, block copolymer plays the dual role of a reducing agent as well as a stabilizing agent. The formation of gold nanoparticles comprises three main steps: reduction of gold salt ion by block copolymers in the solution and formation of gold clusters, adsorption of block copolymers on gold clusters and further reduction of gold salt ions on the surfaces of these gold clusters for the growth of gold particles in steps, and finally its stabilization by block copolymers. But this method usually has a limited yield (nanoparticle concentration) which does not increase with the increase in the gold salt concentration. Recently, Ray et al. demonstrated that the presence of an additional reductant (trisodium citrate) in 1:1 molar ratio with gold salt enhances the yield by manyfold .
Last edited by Mustafa Umut Sarac; 11-09-2012 at 06:07 PM. Click to view previous post history.