Modeling Growth of Organized Nanoporous Structures by Anodic Oxidation

• Published in: Langmuir 2012-09, Vol.28 (36), p.13034-13041
• Main Authors: Reis, Fábio D. A. Aarão, Badiali, J. P, di Caprio, Dung
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Chemistry; Colloidal state and disperse state; Condensed Matter; Electrochemistry; Electrodes; Exact sciences and technology; General and physical chemistry; Hydrogen-Ion Concentration; Models, Molecular; Molecular Structure; Nanostructures - chemistry; or physical chemistry; Oxidation-Reduction; Oxides - chemistry; Physics; Porosity; Porous materials; Solutions; Surface physical chemistry; Surface Properties; Theoretical and
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la301840c

Nanostructured porous oxides are produced by anodic dissolution of several metals. A scaling approach is introduced to explain pattern nucleation in an oxide layer, and a related microscopic model shows oxide growth with long nanopores. The scaling approach matches the time of ion transport across the thin oxide layer, which is related to metal corrosion, and the time of diffusion along the oxide/solution (OS) interface, which represents the extension of oxide dissolution. The selected pattern size is of order (dD S/v O)1/2, where d is the oxide thickness, v O is the migration velocity of oxygen ions across the oxide, and D s is the diffusion coefficient of H+ ions along the oxide/solution interface. This result is consistent with available experimental data for those quantities, predicts the increase of pore size with the external voltage, and suggests the independence of pore size with the solution pH. Subsequently, we propose a microscopic model that expresses the main physicochemical processes as a set of characteristic lengths for diffusion and surface relaxation. It shows a randomly perturbed OS interface at short times, its evolution to pore nucleation and to stable growth of very long pores, in agreement with the mechanistic scenario suggested by two experimental groups. The decrease of the size of the walls between the pores with the interface tension is consistent with arguments for formation of titania nanotube arrays instead of nanopores. These models show that pattern nucleation and growth depend on matching a small number of physicochemical parameters, which is probably the reason for the production of nanostructured porous oxides from various materials under suitable electrochemical conditions.