Preparation of gold nanoparticles by photolysis and radiolysis in alcohol solutions of functional hyperbranched polyorganosiloxane/H[AuCl4]: Effect of irradiation mode on nanoparticle size and formation mechanism

Ethanol solutions of functional hyperbranched polyorganosiloxanes (0.2 vol%) with a molar ratio of NH₂(CH₂)₂NH-/H[AuCl₄]x3H₂O of 8/1 were used as precursors for nanocomposite preparation using UV photolysis and X-ray radiolysis. It was shown that various irradiation modes provide the synthesis of gold nanoparticles (AuNPs) with tunable sizes and narrow size distributions. It was established that size distributions of AuNPs depend on the excitation wavelength. AuNPs with an average size of 3.5 nm were obtained by the direct excitation of gold ions using UV light with λ_max = 365 nm. Meanwhile, the action of a higher energy light (λ = 254 nm) on the metal polymer complexes resulted in formation of ultra-small nanoparticles with an average size of 1.5 nm, presumably due to the increased efficiency of their nucleation process. In the case of radiolysis with X-rays, reduction of Au³⁺ ions occurs due to reactions with radicals produced from ethanol and leads to the formation of AuNPs of 2–3 nm. Thus, the size distribution of the prepared AuNPs may be controlled by the irradiation mode, which critically affects nanomaterial properties. Additionally nanoparticles obtained by photochemical or radiation-chemical methods are free of chemical impurities, which is important for the development of functional materials.