We have investigated electrochemical treatment of real domestic wastewater coupled with simultaneous production of molecular H 2 as useful byproduct. The electrolysis cells employ multilayer semiconductor anodes with electroactive bismuth-doped TiO 2 functionalities and stainless steel cathodes. DC-powered laboratory-scale electrolysis experiments were performed under static anodic potentials (+2.2 or +3.0 V NHE) using domestic wastewater samples, with added chloride ion in variable concentrations. Greater than 95% reductions in chemical oxygen demand (COD) and ammonium ion were achieved within 6 h. In addition, we experimentally determined a decreasing overall reactivity of reactive chlorine species toward COD with an increasing chloride ion concentration under chlorine radicals (Cl•, Cl 2 − •) generation at +3.0 V NHE. The current efficiency for COD removal was 12% with the lowest specific energy consumption of 96 kWh kgCOD −1 at the cell voltage of near 4 V in 50 mM chloride. The current efficiency and energy efficiency for H 2 generation were calculated to range from 34 to 84% and 14 to 26%, respectively. The hydrogen comprised 35 to 60% by volume of evolved gases. The efficacy of our electrolysis cell was further demonstrated by a 20 L prototype reactor totally powered by a photovoltaic (PV) panel, which was shown to eliminate COD and total coliform bacteria in less than 4 h of treatment.

We have developed a wastewater treatment system that incorporates an electrolysis cell for on-site wastewater treatment coupled with molecular hydrogen production for use in a hydrogen fuel cell.Herein, we report on the efficacy of a laboratory-scale wastewater electrolysis cell (WEC) using real human waste for the first time with semiconductor electrode utilizing a mixed particle coating of bismuth oxide doped titanium dioxide (BiO x /TiO 2 ). A comprehensive environmental analysis has been coupled together with a robust kinetic model under the chemical reaction limited regime to investigate the role of various redox reactions mediated by chloride present in human waste. The oxidative elimination of the chemical oxygen demand (COD) and ammonium ion can be modelled using empirical, pseudo-first-order rate constants and current efficiencies (CE). In combination with an anaerobic pre-treatment step, human waste containing high-levels of COD, protein, and color are eliminated within 6 hours of batch treatment in the WEC. The reactor effluent has a residual inorganic total nitrogen (TN) concentration of $40 mM. The CE and specific energy consumption were 8.5% and 200 kWh per kgCOD for the COD removal, 11% and 260 for kWh per kgTN for the TN conversion. The CE and energy efficiencies (EE) for hydrogen production were calculated to be 90% and 25%, respectively.

The production of hydrogen accompanied by the simultaneous oxidation of arsenite (As(III)) was achieved using an electrochemical system that employed a BiO x –TiO2 semiconductor anode and a stainless steel (SS) cathode in the presence of sodium chloride (NaCl) electrolyte. The production of H2 was enhanced by the addition of As(III) during the course of water electrolysis. The synergistic effect of As(III) on H2 production can be explained in terms of (1) the scavenging of reactive chlorine species (RCS), which inhibit the production of H2 by competing with water molecules (or protons) for the electrons on the cathode, by As(III) and (2) the generation of protons, which are more favorably reduced on the cathode than water molecules, through the oxidation of As(III). The addition of 1.0 mM As(III) to the electrolyte at a constant cell voltage (E cell) of 3.0 V enhanced the production of H2 by 12% even though the cell current (I cell) was reduced by 5%. The net effect results in an increase in the energy efficiency (EE) for H2 production (ΔEE) by 17.5%. Furthermore, the value ΔEE, which depended on As(III) concentration, also depended on the applied E cell. For example, the ΔEE increased with increasing As(III) concentration in the micromolar range but decreased as a function of E cell. This is attributed to the fact that the reactions between RCS and As(III) are influenced by both RCS concentration depending on E cell and As(III) concentration in the solution. On the other hand, the ΔEE decreased with increasing As(III) concentration in the millimolar range due to the adsorption of As(V) generated from the oxidation of As(III) on the semiconductor anode. In comparison to the electrochemical oxidation of certain organic compounds (e.g., phenol, 4-chlorophenol, 2-chlorophenol, salicylic acid, catechol, maleic acid, oxalate, and urea), the ΔEE obtained during As(III) oxidation (17.5%) was higher than that observed during the oxidation of the above organic compounds (ΔEE = 3.0–15.3%) with the exception of phenol at 22.1%. The synergistic effect of As(III) on H2 production shows that an energetic byproduct can be produced during the remediation of a significant inorganic pollutant.