Abstract
When a metallic nanoparticle (NP) comes in close contact with an electrode, its Fermi level equilibrates with that of the electrode if their separation is less than the cut-off distance for electron tunnelling. In the absence of chemical reactions in solution, the charge on the metallic nanoparticle is constant outside this range before or after the collision. However, the double layer capacitances of both the electrode and the NP are influenced by each other, varying as the function of distance. Because the charge on the nanoparticle is constant, the outer potential of the metallic NP and hence its Fermi level varies as the capacitance changes. This effect is more pronounced for small particles (<10 nm) in diluted supporting electrolyte solutions, especially if the metallic nanoparticle and the electrode have different potentials of zero charge. Nanoparticles were found to be more electrochemically active in the vicinity of the electrode. For example, the outer potential of a positively-polarized 2 nm radius NP was predicted to decrease by 35 mV or 100 mV (depending on the electrostatic model used to describe the electric double layer), when the NP moved from an electrode at 1 V (vs. its pzc) to the bulk. The force between the equilibrated NP and the electrode is always repulsive when they have the same pzc. Otherwise there can be an attraction even when the NP and the electrode carry charges of the same sign, due to the redistibution of surface charge density at both the NP and electrode surface.