Electrochemical Investigations of 4-Methoxypyridine Adsorption on Au(111) Predict Its Suitability for Stabilizing Au Nanoparticles

A thermodynamic analysis of the adsorption of 4-methoxypyridine (MOP) on Au(111) surfaces is presented in an effort to determine its propensity to stabilize metal nanoparticles. The adsorption of MOP is compared and contrasted to the adsorption of 4-dimethylaminopyridine (DMAP), the latter of which is well-known to form stable Au nanoparticles. Electrochemical studies show that MOP, like most pyridine derivatives, can exhibit two different adsorption states. The electrical state of the metal, the pH of the solution, and the surface crystallography determine whether MOP adopts a low-coverage, π-bonded orientation or a high-coverage, σ-type orientation. A modified Langmuir adsorption isotherm is used to extract free energies of adsorption which are roughly 10% stronger for DMAP compared to MOP at equivalent conditions when expressed on a rational basis. The higher adsorption strength is attributed to DMAP's greater Lewis basicity. Qualitatively, MOP and DMAP adsorption are found to be completely analogous, implying that MOP-protected gold particles should be stable under conditions that favor the high-coverage adsorption state. Using a previously reported, single-phase synthesis, this is shown to be the case.