Kangwoo Cho

Effects of Anodic Potential and Chloride Ion on Overall Reactivity in Electrochemical Reactors Designed for Solar-Powered Wastewater Treatment

We have investigated electrochemical treatment of real domestic wastewater coupled with simultaneous production of molecular H2 as useful byproduct. The electrolysis cells employ multilayer semiconductor anodes with electroactive bismuth-doped TiO2 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·, Cl2(-)·) 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 H2 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.

Urea Degradation by Electrochemically Generated Reactive Chlorine Species: Products and Reaction Pathways

This study investigated the transformation of urea by electrochemically generated reactive chlorine species (RCS). Solutions of urea with chloride ions were electrolyzed using a bismuth doped TiO2 (BiOx/TiO2) anode coupled with a stainless steel cathode at applied anodic potentials (Ea) of either +2.2 V or +3.0 V versus the normal hydrogen electrode. In NaCl solution, the current efficiency of RCS generation was near 30% at both potentials. In divided cell experiments, the pseudo-first-order rate of total nitrogen decay was an order of magnitude higher at Ea of +3.0 V than at +2.2 V, presumably because dichlorine radical (Cl2(-)·) ions facilitate the urea transformation primary driven by free chlorine. Quadrupole mass spectrometer analysis of the reactor headspace revealed that N2 and CO2 are the primary gaseous products of the oxidation of urea, whose urea-N was completely transformed into N2 (91%) and NO3(-) (9%). The higher reaction selectivity with respect to N2 production can be ascribed to a low operational ratio of free available chlorine to N. The mass-balance analysis recovered urea-C as CO2 at 77%, while CO generation most likely accounts for the residual carbon. In light of these results, we propose a reaction mechanism involving chloramines and chloramides as reaction intermediates, where the initial chlorination is the rate-determining step in the overall sequence of reactions.

Photoelectrochemical Degradation of Organic Compounds Coupled with Molecular Hydrogen Generation Using Electrochromic TiO2 Nanotube Arrays

Vertically aligned TiO2 nanotube arrays (TNTs) were prepared by electrochemical anodization, and then cathodically polarized with dark blue coloration for the dual-functional photoelectrochemical water treatment of organic substrates degradation and accompanying H2 generation. The resulting Blue-TNTs (inner diameter: ∼40 nm; length: ∼9 μm) showed negligible shift in X-ray diffraction pattern compared with the intact TNTs, but the X-ray photoelectron spectra indicated a partial reduction of Ti4+ to Ti3+ on the surface. The electrochemical analyses of Blue-TNTs revealed a marked enhancement in donor density and electrical conductivity by orders of magnitude. Degradations of test organic substrates on Blue-TNTs were compared with the intact TNTs in electrochemical (EC), photocatalytic (PC), and photoelectrochemical (PEC) conditions (potential bias: 1.64 VNHE; λ > 320 nm). The degradation of 4-chlorophenol was greatly enhanced on Blue-TNTs particularly in PEC condition, whereas the PC activities of the Blue- and intact TNTs were similar. The potential bias of 1.64 VNHE did not induce any noticeable activity in EC condition. Similar trends were observed for the degradation of humic acid and fulvic acid, where main working oxidants were found to be the surface hydroxyl radical as confirmed by hydroxyl radical probe and scavenger tests. H2 generation coupled with the organic degradation was observed only in PEC condition, where the H2 generation rate with Blue-TNTs was more than doubled from that of intact TNTs. Such superior PEC activity was not observed when a common TiO2 nanoparticle film was used as a photoanode. The enhanced electric conductivity of Blue-TNTs coupled with a proper band bending in PEC configuration seemed to induce a highly synergic enhancement.

Sequential Combination of Electro-Fenton and Electrochemical Chlorination Processes for the Treatment of Anaerobically-Digested Food Wastewater

A two-stage sequential electro-Fenton (E-Fenton) oxidation followed by electrochemical chlorination (EC) was demonstrated to concomitantly treat high concentrations of organic carbon and ammonium nitrogen (NH4+-N) in real anaerobically digested food wastewater (ADFW). The anodic Fenton process caused the rapid mineralization of phenol as a model substrate through the production of hydroxyl radical as the main oxidant. The electrochemical oxidation of NH4+ by a dimensionally stable anode (DSA) resulted in temporal concentration profiles of combined and free chlorine species that were analogous to those during the conventional breakpoint chlorination of NH4+. Together with the minimal production of nitrate, this confirmed that the conversion of NH4+ to nitrogen gas was electrochemically achievable. The monitoring of treatment performance with varying key parameters (e.g., current density, H2O2 feeding rate, pH, NaCl loading, and DSA type) led to the optimization of two component systems. The comparative evaluation of two sequentially combined systems (i.e., the E-Fenton-EC system versus the EC-E-Fenton system) using the mixture of phenol and NH4+ under the predetermined optimal conditions suggested the superiority of the E-Fenton-EC system in terms of treatment efficiency and energy consumption. Finally, the sequential E-Fenton-EC process effectively mineralized organic carbon and decomposed NH4+-N in the real ADFW without external supply of NaCl.

Nitrite ion mitigates the formation of N-nitrosodimethylamine (NDMA) during chloramination of ranitidine

Ranitidine (RNT) has been an important tertiary amine precursor of N-nitrosodimethylamine (NDMA) in chlorine-based water treatment, due to reaction with monochloramine (NH2Cl) with exceptionally high molar yields up to 90%. This study examined the effects of nitrite ions (NO2-) on the kinetics of NDMA formation during the chloramination of RNT under variable concentrations of dissolved oxygen (DO, 0.7-7.5mg/L), RNT (5-30μM), NH2Cl (5-20mM), NO2- or NO3- (0-2mM) and pH (5.6-8.6). In the absence of the NO2-, the ultimate molar yield of NDMA after 6h of reaction was primarily influenced by [DO] and pH, while marginally affected by initial [RNT] and [NH2Cl]. A kinetic model, prepared in accordance with the reaction sequence of NDMA formation, suggested that the rate determining step was accelerated with increasing [NH2Cl]0, [DO], and pH. A Kinetic study together with ultra-performance liquid chromatography-quadrupole-time of flight mass spectrometer (UPLC-Q-TOF MS) and gas chromatography (GC)/TOF MS analyses in parallel demonstrated that the nitrite ion inhibited the nucleophilic substitution of the terminal amine on NH2Cl, and reduced the pseudo-steady state concentration of N-peroxyl radicals, significantly decreasing the ultimate yields of NDMA.