Electrochimica Acta, Vol.54, No.12, 3285-3297, 2009
Isolation and dispersion of reduced metal particles using the surface dipole moment of F-terminated diamond electrodes
Cu particles that have been reductively generated at the oxidized surface of a boron-doped diamond electrode (O-BDD) can be removed from the electrode's surface by the repulsive electrostatic force of the surface dipole moment during a potential cycle of a solution of Cu2+ ions. The objective of this study was to isolate various metal particles other than Cu by use of a fluorine-terminated BDD surface (F-BDD) with a stronger surface dipole moment than O-BDD, and to clarify the mechanism of the metal particles' separation from the electrode. During the potential cycle treatment of Cu2+ ions using F-BDD, the reionization of the reduced Cu could be suppressed in the presence of dissolved oxygen, and the Cu particles were separated from the electrode surface as CuO. A similar result was seen with O-BDD. The degree of separation of the Cu particles could be drastically enhanced by raising the upper potential limit in the potential cycle from +0.2 to +0.8V. By setting the upper potential to a potential greater than the metal-metal oxide equilibrium line in the potential-pH equilibrium diagram of the Cu-water system (Pourbaix Diagram), oxidation of the reduced metal surface by reaction with dissolved oxygen could be accelerated and the surface of metal particles could be insulated. The Cu particles were forced from the BDD surface by the electrostatic repulsion from the surface dipole moment of F-BDD. Also, it turned out that the physical adsorption of chloride ions (Cl-) on the electrode surface intensified the electrostatic repulsive force between the F- or O-BDD surface and the metal particles, and thus increased the degree of the metal particles' separation. For Zn with a metal-metal oxide equilibrium potential of approximately -0.8V at pH 7, complete separation of the Zn particles was achieved with F-BDD by setting the upper potential limit to +0.8V (vs. Ag/AgCl), decreasing the Zn2+ concentration (1/10 that of Cu2+) and optimizing the sweep rate to minimize the Zn particle diameter. This result was hard to achieve with O-BDD. The separation of metal particles other than Cu was achieved with F-BDD because of its stronger surface dipole moment. However, with noble type metals (such as Pt and Ni) that have metal-metal oxide equilibrium potentials higher than the upper potential limit for potential cycling with F-BDD (+0.8V), the surfaces of the reduced metal particles were not insulated and metal particles were deposited on the BDD surface. In order to isolate metal particles from the electrode, it was necessary to apply a maximum potential over that of the metal-metal oxide equilibrium line in the Pourbaix Diagram during the potential cycle. (C) 2009 Elsevier Ltd. All rights reserved.
Keywords:F-terminated BDD;Metal nano-particle;Isolation of metal particle;Surface dipole moment;Wastewater treatment