Photochemical Synthesis of Noble Metal Nanoparticles: Influence of Metal Salt Concentration on Size and Distribution

This paper explores the photochemical synthesis of noble metal nanoparticles, specifically gold (Au) and silver (Ag) nanoparticles, using a one-component photoinitiator system. The synthesis process involves visible light irradiation at a wavelength of 419 nm and an intensity of 250 mW/cm². The radical-generating capabilities of the photoinitiators were evaluated using electron spin resonance (ESR) spectroscopy. The main objective of this study was to investigate how the concentration of metal salts influences the size and distribution of the nanoparticles. Proposed mechanisms for the photochemical formation of nanoparticles through photoinitiated radicals were validated using cyclic voltammetry. The results showed that the concentration of AgNO₃ significantly impacted the size of silver nanoparticles, with diameters ranging from 1 to 5 nm at 1 wt% and 3 wt% concentrations, while increasing the concentration to 5 wt% led to an increase in the diameter of silver nanoparticles to 16 nm. When HAuCl₄ was used instead of AgNO₃, it was found that the average diameters of gold nanoparticles synthesized using both photoinitiators at different concentrations ranged between 1 and 4 nm. The findings suggest that variations in HAuCl₄ concentration have minimal impact on the size of gold nanoparticles. The photoproduction of AuNPs was shown to be thermodynamically favorable, with the reduction of HAuCl₄ to Au⁰ having ∆G values of approximately -3.51 and -2.96 eV for photoinitiators A and B, respectively. Furthermore, the photoreduction of Ag⁺¹ to Ag⁰ was demonstrated to be thermodynamically feasible, with ∆G values of approximately -3.459 and -2.91 eV for photoinitiators A and B, respectively, confirming the effectiveness of the new photoinitiators on the production of nanoparticles. The synthesis of nanoparticles was monitored using UV-vis absorption spectroscopy, and their sizes were determined through particle size analysis of transmission electron microscopy (TEM) images.