Microemulsion Synthesis of Nanoparticles

U ovom pregledu prikazane su mikroemulzijske tehnike za sintezu metalnih, metal-oksidnih, sulfidnih i polimernih nanočestica. Sinteza se izvodi u mikroemulzijama voda-u-ulju, miješanjem dviju mikroemulzija, od kojih jedna sadrži kationski prekursor, a druga precipitacijski medij ili redukcijsko sredstvo. Nanočestice metala dobivaju se redukcijom metalnog kationa s jakim redukcijskim sredstvima uz oslobađanje vodika prikladnim redukcijskim sredstvom. Na sličan način mogu se pripraviti i nanočestice legura od soli različitih metala pod uvjetom da se metali međusobno miješaju. Mikroemulzijska tehnika veoma je pogodna i za nanošenje nanočestica na različite podloge. Na taj način mogu se dobiti visokoaktivni katalizatori od nanočestica Pt, Pd, Rh i drugih plemenitih metala. Metalni oksidi i hidroksidi pripravljaju se hidrolizom ili taloženjem u vodenoj jezgri mikroemulzije. Da se spriječi oksidacija nanočestica, osobito Fe, čestice se prevlače inertnim metalima, oksidima, različitim polimerima i dr. Prevlačenjem se može postići dodatna funkcionalnost; npr. prevlačenje zlatom omogućava naknadnu funkcionalizaciju organskim spojevima koji sadrže sumpor, zahvaljujući jakoj tiolnoj vezi Au–S. Polimerne prevlake smanjuju toksičnost nanočestica i povećavaju biokompatibilnost, a funkcionalne skupine na površini omogućavaju razne primjene u biomedicini. Reakcije polimerizacije ili umrežavanja mogu se inicirati u vodenim jezgrama mikroagregata kemijskim sredstvima ili npr. UV ili ionizirajućim zračenjem. Prednosti mikroemulzijske polimerizacije su velika brzina, jednolična veličina čestica, stabilnost te visoki stupanj polimerizacije. Nanočestice magnetita pobuđuju velik interes zbog primjene u biomedicini. Magnetit je biokompatibilni materijal, a može se pripremiti u obliku dobro dispergiranih nanočestica manjih od 4 nm, koje imunosni sustav ne prepoznaje. Prikazana je vlastita metoda mikroemulzijske sinteze nanočestica magnetita potpomognuta γ-zračenjem.
Nanoparticles and nanomaterials have wide applications in electronics, physics, material design, being also utilized as sensors, catalysts, and more and more in biomedicine. Microemulsions are an exceptionally suitable medium for the synthesis of nanoparticles due to their thermodynamical stability, great solubility of both polar and nonpolar components, as well as their ability to control the size, dispersity and shape of the particles. This review presents microemulsion techniques for the synthesis of inorganic nanoparticles. It takes place in water-in-oil microemulsions by mixing one microemulsion with a cationic precursor, and the other with a precipitating or reducing agent, or by direct addition of reducing agents or gas (O2, NH3 ili CO2 ) into microemul sion (Fig. 1). Metal nanoparticles are used as catalysts, sensors, ferrofluids etc. They are produced by reducing the metal cation with a suitable reducing agent. In a similar way, one can prepare nanoparticles of alloys from the metal salts, provided that the metals are mutually soluble. The microemulsion technique is also suitable for depositing nanoparticles onto various surfaces. Highly active catalysts made from nanoparticles of Pt, Pd, Rh and other noble metals may be obtained in this way. Metal oxides and hydroxides may be prepared by hydrolysis or precipitation in the water core of microemulsion. Precipitation can be initiated by adding the base or precipitating agent into the microemulsion with water solution of metal ions. Similarly, nanoparticles may be prepared of sulphides, halogenides, cyanides, carbonates, sulphates and other insoluble metal salts. To prevent oxidation of nanoparticles, especially Fe, the particles are coated with inert metals, oxides, various polymers etc. Coating may provide additional functionality; e.g. coating with gold allows subsequent functionalization with organic compounds containing sulphur, due to the strong Au–S bond. Polymer coatings decrease toxicity of the nanoparticles and increase their biocompatibility, and the functional groups on the surface enable specific applications in biomedicine. Microemulsion synthesis is convenient both for organic and polymer particles. Polymerization or crosslinking reactions may be initiated in the water core of microaggregates by using chemicals, UV or ionizing radiation (Fig. 3). Microemulsion polymerization is advantageous due to fast reactions, uniform particle size, great stability and high polymerization degree. Magnetite nanoparticles induce great interest due to biomedical applications. Magnetite is a biocompatible material that may be prepared in the form of well-dispersed nanoparticles smaller than 4 nm, which are not recognized by the immune system. The authors’ own approach for the synthesis of magnetite nanoparticles using γ-irradiation assisted microemulsion technique is described (Figs. 5–10).