Molecular-scale Insights into Cooperativity Switching of TAB Adsorption on Gold Nanoparticles.

Quantifying adsorption behaviors is crucial for various applications such as catalysis, separation, and sensing, yet it is generally challenging to access in solution. Here, we report a combined experimental and computational study of the adsorption behaviors of alkyl-trimethylammonium bromides (TAB), a class of ligands important for colloidal nanoparticle stabilization and shape control, with various alkyl chain lengths on Au nanoparticles. We use density functional theory (DFT) to calculate TAB binding energies on Au{111} and Au{110} surfaces with standing-up and lying-down configurations, which provides insights into the adsorption affinity and cooperativity differences of TAB on these two facets. We demonstrate the key role of van der Waals interactions in determining the TAB adsorption behavior. These computational results predict and explain the experimental discovery of TAB's adsorption behavior switch from stronger affinity, negative cooperativity to weaker affinity, positive cooperativity when the concentration of TAB increases in solution. We also show that in the standing-up configuration, bilayer adsorption may occur on both facets, which can lead to different differential binding energies and consequently adsorption crossover between the two facets when the ligand concentration increases. Our combined experimental and computational approaches demonstrate a paradigm for gaining molecular-scale insights into adsorbate-surface interactions.