pH-controlled desorption of silver nanoparticles from monolayers deposited on PAH-covered mica

Although the release of silver nanoparticles from various surfaces and coatings plays an important role in many practical applications, the mechanisms of these processes are not fully understood. Therefore, in this work, the charge-stabilized silver particles of well-defined surface properties, with average sizes of 15, 28, and 54 nm, were used to quantitatively study this problem. The silver nanoparticles were obtained by the chemical reduction method using trisodium citrate as the stabilizing agent. Their size distributions and stabilities were determined using dynamic light scattering and transmission electron microscopy. The electrophoretic mobility and zeta potential of nanoparticles were determined for controlled ionic strength as a function of pH. The monolayers were produced on poly(allylamine hydrochloride)-modified mica under diffusion-controlled conditions. The coverage was determined by a direct enumeration of deposited nanoparticles using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Using these well-defined monolayers, the kinetics of the release of nanoparticles was studied under controlled ionic strength and various pH values. The direct AFM and SEM measurements of the monolayer coverage, as a function of desorption time, allowed one to determine the kinetics of the release process. The equilibrium adsorption constant and the binding energy of particles were also determined using the random sequential adsorption model. The experimental results indicated that the release rate of particles is the fastest at lower pH values and for smaller particle sizes. This is confirmed by the binding energy values that at pH 3.5 varied between −15.9 and −18.1 kT for particles of the sizes 15 and 54 nm, respectively. These results were quantitatively interpreted in terms of the ion-pair concept where it was assumed that the binding energy between nanoparticles and the substrate was controlled by electrostatic interactions. Based on the conducted studies, one can conclude that the rate of nanoparticle release can be tuned by changing the pH values.