Adsorption Kinetics of Alkane-thiol Capped Gold Nanoparticles at Liquid-Liquid Interfaces.

Abstract

The pendant drop technique was used to characterize the adsorption behavior of n-dodecane-1-thiol and n-hexane-1-thiol capped gold nanoparticles at the hexane-water interface. The adsorption process was studied by analyzing the dynamic interfacial tension versus nanoparticle concentration, both at early times and at later stages (i.e., immediately after the interface between the fluids is made and once equilibrium has been established). Following free diffusion of nanoparticles from the bulk hexane phase, adsorption leads to ordering and rearrangement of the nanoparticles at the interface and formation of a dense layer. With increasing interfacial coverage, the diffusion-controlled adsorption for the nanoparticles at the interface was found to change to an interaction-controlled assembly and the presence of an adsorption barrier was experimentally verified. At the same bulk concentration, different sizes of n-dodecane-1-thiol nanoparticles showed different absorption behavior at the interface, in agreement with the findings of Kutuzov et al. [1]. The experiments additionally demonstrated the important role played by the capping agent. At the same concentration, gold nanoparticles stabilized by n-hexane-1-thiol exhibited greater surface activity than gold nanoparticles of the same size stabilized by n-dodecane-1-thiol. 1.6 nm, 2.8 nm, and 4.4 nm nanoparticles capped with n-dodecane-1-thiol, and 2.9 nm, and 4.3 nm particles capped with n-hexane-1-thiol were used in this study. The physical size of the gold nanoparticles was determined by TEM image analysis. The pendant drop technique was also used to study the adsorption properties of mixtures of gold nanoparticles at the hexane-water interface; and also investigate the effects of different factors (i.e., temperature, pH or ionic strength) on interfacial tension (IFT). The interfacial properties of mixtures of these nanoparticles, having different sizes and capping agents, were then studied. No interaction was found between the unmixed studied nanoparticles. Using the theory of non-ideal interactions for binary mixtures, the interaction parameters for mixtures of nanoparticles at the interface were determined. The results indicate that nanoparticle concentration of the mixtures has a profound effect on the interfacial nanoparticle composition. A repulsive interaction between nanoparticles of different size and cap was found in the mixtures at the interface layer. The interfacial tension for mixtures was found to be higher than the interfacial tension for non-mixed nanoparticle suspensions. The nanoparticle composition at the interface was found to differ from the composition of nanoparticles in the bulk liquid phase. The activity of unmixed nanoparticles proved to be a poor predictor of the activity of mixtures. It was observed that the most active nanoparticles concentrated at the interface. The effects of temperature, pH and ionic strength concentration on the equilibrium and dynamic IFT of 4.4 nm gold nanoparticles capped with n-dodecane-1-thiol at the hydrocarbon-water interface was studied. The pendant drop technique was also used to study the adsorption properties of these nanoparticles at the hexane-water and nonane-water interface. The addition of NaCl was found to cause a decrease of the equilibrium and dynamic IFT greater than that, which accompanies the adsorption of nanoparticles at the interface in the absence of NaCl. Although IFT values for acidic and neutral conditions were found to be similar, a noticeable decrease in the IFT was found for more basic conditions. Increasing the temperature of the system was found to cause an increase in both dynamic and equilibrium IFT values. The adsorption of functionalized gold nanoparticles at liquid-liquid interfaces is a promising method for self-assembly and the creation of useful nanostructures. These findings contribute to the design of useful supra-colloidal structures by the self-assembly of alkane-thiol capped gold nanoparticles at liquid-liquid interfaces.