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This research focused on improving mineralization rates during the advanced electrochemical oxidation treatment of agricultural water contaminants. For the first time, bismuth-doped tin oxide (BDTO) catalysts were deposited on Magnéli phase (Ti n O 2 n-1 , n = 4-6) reactive electrochemical membranes (REMs). Terephthalic acid (TA) was used as a OH • probe, whereas atrazine (ATZ) and clothianidin (CDN) were chosen as model agricultural water contaminants. The BDTO-deposited REMs (REM/BDTO) showed higher compound removal than the REM, due to enhanced OH • production. At 3.5 V/SHE, complete mineralization of TA, ATZ, and CDN was achieved for the REM/BDTO upon a single pass in the reactor (residence time ∼3.6 s). Energy consumption for REM/BDTO was as much as 31-fold lower than the REM, with minimal values per log removal of <0.53 kWh m -3 for TA (3.5 V/SHE), <0.42 kWh m -3 for ATZ (3.0 V/SHE), and 0.83 kWh m -3 for CDN (3.0 V/SHE). Density functional theory simulations provided potential dependent activation energy profiles for ATZ, CDN, and various oxidation products. Efficient mass transfer and a reaction mechanism involving direct electron transfer and reaction with OH • were responsible for the rapid and complete mineralization of ATZ and CDN at very short residence times.

This research focused on synthesis, characterization, and application of point-of-use catalytic reactive electrochemical membranes (REMs) for electrocatalytic NO 3 - reduction. Deposition of Pd-Cu and Pd-In catalysts to the REMs produced catalytic REMs (i.e., Pd-Cu/REM and Pd-In/REM) that were active for NO 3 - reduction. Optimal performance was achieved with a Pd-Cu/REM and upstream counter electrode, which reduced NO 3 - from 1.0 mM to below the EPAs regulatory MCL (700 μM) in a single pass through the REM (residence time ∼2 s), obtaining product selectivity of <2% toward NO 2 - /NH 3 . Nitrate reduction was not affected by dissolved oxygen and carbonate species and only slightly decreased in a surface water sample due to Ca 2+ and Mg 2+ scaling. Energy consumption to treat surface water was 1.1 to 1.3 kWh mol -1 for 1 mM NO 3 - concentrations, and decreased to 0.19 and 0.12 kWh mol -1 for 10 and 100 mM NaNO 3 solutions, respectively. Electrocatalytic reduction kinetics were shown to be an order of magnitude higher than catalytic NO 3 - reduction kinetics. Conversion of up to 67% of NO 3 - , with low NO 2 - (0.7-11 μM) and NH 3 formation (<10 μM), and low energy consumption obtained in this study suggest that Pd-Cu/REMs are a promising technology for distributed water treatment.

This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO 4 - formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO 4 - formation decreased from rates of 0.45 ± 0.03 mmol m -2 min -1 during 1 mM NaClO 3 oxidation and 0.28 ± 0.01 mmol m -2 min -1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (<0.12 μmoles m -2 min -1 ) for the BDD electrode functionalized by a 1H,1H,2H,2H-perfluorodecyltrichlorosilane SAM. These decreases in rates corresponded to 99.94 and 99.85% decreases in selectivity for ClO 4 - formation during the electrolysis of 10 mM NaCl and 1 mM NaClO 3 electrolytes, respectively. By contrast, the oxidation rates of phenol were reduced by only 16.3% in the NaCl electrolyte and 61% in a nonreactive 0.1 M KH 2 PO 4 electrolyte. Cyclic voltammetry with Fe(CN) 6 3-/4- and Fe 3+/2+ redox couples indicated that the long fluorinated chains created a blocking layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH • production. Perchlorate formation rates were below the detection limit (<0.12 μmoles m -2 min -1 ) for up to 10 consecutive NaClO 3 oxidation experiments.

This study focuses on the development of electrochemical sensors for the detection of Ciprofloxacin (CFX) in natural waters and wastewater effluents. The sensors are prepared by depositing a layer of multiwalled carbon nanotubes (MWCNTs) dispersed in a porous Nafion film on to a boron-doped diamond (BDD) electrode substrate. The porous-Nafion-MWCNT/BDD electrode enhanced detection of CFX due to selective adsorption, which was accomplished by a combination of electrostatic attraction at -SO3(-) sites in the porous Nafion film and the formation of charge assisted hydrogen bonding between CFX and -COOH MWCNT surface functional groups. By contrast, the bare BDD electrode did not show any activity for CFX oxidation. The sensors were selective for CFX detection in the presence of other antibiotics (i.e., amoxicillin) and other nontarget water constituents (i.e., Cl(-), Ca(2+), humic acid, sodium dodecylbenzenesulfonate, salicylic acid, 4-aminobenzoic acid, and 4-hydroxybenzoic acid). A limit of detection of 5 nM (S/N = 5.04 ± 0.26) in a 0.1 M KH2PO4 supporting electrolyte (pH = 4.5) was obtained using differential pulse voltammetry. The linear dynamic ranges with respect to CFX concentration were 0.005-0.05 μM and 0.05-10 μM, and the sensitivities were 41 ± 5.2 μA μM(-1) and 2.1 ± 0.22 μA μM(-1), respectively. Sensor fouling was observed at high concentrations of some organic compounds such as 1 mM 4-aminobenzoic acid and 4-hydroxybenzoic acid. However, a short cathodic treatment fully restores sensor response. The results indicate that these sensors have application in detecting CFX in natural waters and wastewater effluents.