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The energetics of electrons at the surface of a nanostructured semiconductor in contact with an electrolyte are analyzed in this paper. The solvation of electrons produces a gap in the density of states, which separates the occupied states from empty states by solvation energy. The dynamic effects of the solvation, with respect to the relaxation time of the electrolyte, are discussed. A calculation by random-walk numerical simulation of the diffusion coefficient of electrons moving in the surface of nanoparticles shows the reduction of the rate of transport by the polarization effect.