Reactive Transport Mechanism for Organic Oxidation during Electrochemical Filtration: Mass-Transfer, Physical Adsorption, and Electron-Transfer

Abstract

An electrochemical carbon nanotube (CNT) filter has been reported to be effective for the adsorptive removal and oxidation of aqueous organic compounds. Here, we complete a detailed investigation of the aqueous dye oxidation reactive transport mechanism during electrochemical filtration. Similar to batch electrolysis, mass transfer, physical adsorption, and electron transfer are found to be three primary steps in the overall electrochemical filtration organic oxidation mechanism. Mass transfer was quantitatively examined by chronoamperometry and normal pulse voltammetry and determined to be increased 6-fold during electrochemical filtration as compared to batch electrochemistry. Convection-enhanced mass transfer to the electrode surface is determined to be the primary factor for increased current density and organic oxidation during electrochemical filtration. Physical adsorption of the organics onto the CNTs was evaluated using temperature-dependent batch adsorption and electrochemical filtration experiments. The electrochemical filtration kinetics were observed to have a minor negative temperature-dependence. Electron transfer was examined by challenging the electrochemical filter with a range of increasing dye concentrations until the mass transfer and adsorption processes were saturated. Upon surface site saturation, the electron transfer rates were determined to be 8.5 × 10 15, 6.3 × 10 16, and 1.3 × 10 17 e – s –1 m –2 at anode potentials of 0.35, 0.77, and 1.50 V, respectively. The electron transfer mechanism was also investigated and direct electron transfer was determined to be the dominant methyl orange oxidation mechanism at all evaluated anode potentials with an increasing contribution from indirect oxidation processes at potentials ≥1.0 V. The anode potential dependent maximum electron transfer rate is also observed to be affected by the polarity of the organic charge indicating electromigration is also active. In summary, electrochemical filtration is advantageous as compared to batch electrolysis due to the liquid flow through the electrode resulting in convection-enhanced transfer of the target molecule to the electrode surface.