New Operational Modes to Increase Energy Efficiency in Capacitive Deionization Systems.

In order for capacitive deionization (CDI) as a water treatment technology to achieve commercial success, substantial improvements in the operational aspects of the system should be improved in order to efficiently recover the energy stored during the deionization step. In the present work, to increase the energy efficiency of the adsorption-desorption processes, we propose a new operational procedure that utilizes a concentrated brine stream as a washing solution during regeneration. Using this approach, we demonstrate that by replacing the electrolyte during regeneration for a solution with higher conductivity, it is possible to substantially increase round-trip energy efficiency. This procedure was experimentally verified in a flow cell reactor using a pair of carbon electrodes (10(2) cm geometric area) and NaCl solutions having concentrations between 50 and 350 mmol·L(-1). According to experimental data, this new operational mode allows for a better utilization of the three-dimensional structure of the porous material. This increases the energetic efficiency of the global CDI process to above 80% when deionization/regeneration currents ratio are optimized for brackish water treatment.

Plasmon-enhanced photoelectrochemical water splitting with size-controllable gold nanodot arrays.

Size-controllable Au nanodot arrays (50, 63, and 83 nm dot size) with a narrow size distribution (± 5%) were prepared by a direct contact printing method on an indium tin oxide (ITO) substrate. Titania was added to the Au nanodots using TiO(2) sols of 2-3 nm in size. This created a precisely controlled Au nanodot with 110 nm of TiO(2) overcoats. Using these precisely controlled nanodot arrays, the effects of Au nanodot size and TiO(2) overcoats were investigated for photoelectrochemical water splitting using a three-electrode system with a fiber-optic visible light source. From UV-vis measurement, the localized surface plasmon resonance (LSPR) peak energy (ELSPR) increased and the LSPR line width (Γ) decreased with decreasing Au nanodot size. The generated plasmonic enhancement for the photoelectrochemical water splitting reaction increased with decreasing Au particle size. The measured plasmonic enhancement for light on/off experiments was 25 times for the 50 nm Au size and 10 times for the 83 nm Au nanodot size. The activity of each catalyst increased by a factor of 6 when TiO2 was added to the Au nanodots for all the samples. The activity of the catalyst was proportional to the quality factor (defined as Q = E(LSPR)/Γ) of the plasmonic metal nanostructure. The enhanced water splitting performance with the decreased Au nanodot size is probably due to more generated charge carriers (electron/hole pair) by local field enhancement as the quality factor increases.

Exploring the impact of pore size distribution on the performance of carbon electrodes for capacitive deionization.

Capacitive deionization (CDI) removes charged ions from aqueous solutions through entrapment in the electric double layer (EDL) when the porous electrodes are polarized. In this study, three types of activated carbon cloth (ACC) with different pore-size distributions were used to study the effect of pore characteristics on electrosorption during CDI. Removal of seven different monovalent ions was examined for each ACC in batch reactors under 5 different combinations of applied potential and ionic strength. Results show underlying sorption mechanisms in the meso- and micro-pores were different. Electrosorption in the mesopores is influenced by partially-distorted EDL caused by EDL overlapping. Sorption capacity increased with increasing applied potential or ionic strength as overlapping effects were reduced. In contrast, EDL in the microporous regions could be highly distorted resulting in enhanced sorption capacity, which cannot be adequately described using the classic EDL theories. Electrosorption density (i.e., sorption capacity normalized by pore volume) decreased as the mesoporosity-to-microporosity ratio increased. These results are in agreement with those obtained using mathematical modeling by other recent CDI studies. Charge efficiency values were between 20% and 40% and appear to be substantially influenced by Faradaic reactions and ion desorption from the electrode surfaces. These findings suggest that pore-size distribution of electrode materials, especially the meso/microporosity ratio, should be optimized for the removal of targeted ions by CDI and well characterized to conduct more precise CDI modeling.

Optimizing the energy efficiency of capacitive deionization reactors working under real-world conditions.

Capacitive deionization (CDI) is a rapidly emerging desalination technology that promises to deliver clean water while storing energy in the electrical double layer (EDL) near a charged surface in a capacitive format. Whereas most research in this subject area has been devoted to using CDI for removing salts, little attention has been paid to the energy storage aspect of the technology. However, it is energy storage that would allow this technology to compete with other desalination processes if this energy could be stored and reused efficiently. This requires that the operational aspects of CDI be optimized with respect to energy used both during the removal of ions as well as during the regeneration cycle. This translates into the fact that currents applied during deionization (charging the EDL) will be different from those used in regeneration (discharge). This paper provides a mechanistic analysis of CDI in terms of energy consumption and energy efficiencies during the charging and discharging of the system under several scenarios. In a previous study, we proposed an operational buffer mode in which an effective separation of deionization and regeneration steps would allow one to better define the energy balance of this CDI process. This paper reports on using this concept, for optimizing energy efficiency, as well as to improve upon the electro-adsorption of ions and system lifetime. Results obtained indicate that real-world operational modes of running CDI systems promote the development of new and unexpected behavior not previously found, mainly associated with the inhomogeneous distribution of ions across the structure of the electrodes.

Evaluating the electrochemical capacitance of surface-charged nanoparticle oxide coatings.

While transition metal oxides have been thoroughly investigated as coatings for electrochemical capacitors due to their pseudocapacitance, little work has been done investigating other oxide coatings. There exists a whole class of nanoporous oxides typically synthesized by sol-gel chemistry techniques that have very high differential capacitance. This high differential capacitance has been attributed to the surface potential of these materials and the close approach of counterions near the surface of these oxides. This study focuses on investigating the electrochemical capacitance of non-transition metal oxide nanoparticle coatings when deposited on supporting electrodes. Here, we show that, by adding coatings of SiO(2), AlOOH, TiO(2), and ZrO(2) nanoparticles to graphite support electrodes, we can increase the electrochemical capacitance. We also show that the measured electrochemical capacitance of these oxide-coated electrodes directly relates to the electrophoretic mobility of these materials with the lowest values in capacitance occurring at or near the respective isoelectric pH (pH(IEP)) of each oxide.

Assessment of by-products of chlorination and photoelectrocatalytic chlorination of an azo dye.

The present work describes a more efficient methodology for the chlorination of water containing disperse dyes, where the chlorinated byproducts identified by mass spectra are compared. For this investigation, we tested the degradation of CI Disperse Blue 291 dye, 2-[(2-Bromo-4,6-dinitrophenyl)azo]-5-(diethylamino)-4-methoxyacetanilide) a commercial azo dye with mutagenic properties. The present work evaluates the photoelectrocatalytic efficiency of removing the CI Disperse Blue 291 dye from a wastewater of the textile industry. We employed NaCl as a supporting electrolyte. It should be noted that photoelectrocatalytic techniques are non-conventional method of generating chlorine radicals. The by-products formed in this process were analyzed using spectrophotometry, liquid chromatography, dissolved organic carbon, mass spectral analysis and mutagenicity assays. The process efficiency was compared with the conventional chlorination process adopted during sewage and effluents treatment processes. This conventional chlorination process is less efficient in removing color, total organic carbon than the photoelectrochemistry technique. Furthermore, we shall demonstrate that the mutagenicity of the generated by-products obtained using photoelectrocatalysis is completely different from that obtained by the conventional oxidation of chloride ions in the drinking water treatment process.

Interface engineering by piezoelectric potential in ZnO-based photoelectrochemical anode.

Through a process of photoelectrochemical (PEC) water splitting, we demonstrated an effective strategy for engineering the barrier height of a heterogeneous semiconductor interface by piezoelectric polarization, known as the piezotronic effect. A consistent enhancement or reduction of photocurrent was observed when tensile or compressive strains were applied to the ZnO anode, respectively. The photocurrent variation is attributed to a changed barrier height at the ZnO/ITO interface, which is a result of the remnant piezoelectric potential across the interface due to a nonideal free charge distribution in the ITO electrode. In our system, ∼1.5 mV barrier height change per 0.1% applied strain was identified, and 0.21% tensile strain yielded a ∼10% improvement of the maximum PEC efficiency. The remnant piezopotential is dictated by the screening length of the materials in contact with piezoelectric component. The difference between this time-independent remnant piezopotential effect and time-dependent piezoelectric effect is also studied in details.

Three-dimensional high-density hierarchical nanowire architecture for high-performance photoelectrochemical electrodes.

Three-dimensional (3D) nanowire (NW) networks are promising for designing high-performance photoelectrochemical (PEC) electrodes owing to their long optical path for efficient light absorption, high-quality one-dimensional conducting channels for rapid electron-hole separation and charge transportation, as well as high surface areas for fast interfacial charge transfer and electrochemical reactions. By growing titanium dioxide (TiO(2)) nanorods (NRs) uniformly on dense Si NW array backbones, we demonstrated a novel three-dimensional high-density heterogeneous NW architecture that could enhance photoelectrochemical efficiency. A 3D NW architecture consisting of 20 µm long wet-etched Si NWs and dense TiO(2) NRs yielded a photoelectrochemical efficiency of 2.1%, which is three times higher than that of TiO(2) film-Si NWs having a core-shell structure. This result suggests that the 3D NW architecture is superior to straight NW arrays for PEC electrode design. The efficiency could be further improved by optimizing the number of overcoating cycles and the length/density of NW backbones. By implementing these 3D NW networks into electrode design, one may be able to advantageously impact PEC and photovoltaic device performance.

Photoelectrocatalytic removal of bromate using Ti/TiO2 coated as a photocathode.

These studies represent the rare use of a TiO2 material as a photocathode and the first application of photoelectrocatalysis for BrO3- removal. Photoelectrocatalytic reduction of BrO3- to Br- can reach 70% at neutral pH under an applied potential of -0.20 V versus SCE (saturated calomel electrode) after 75 min on the irradiated nanoporous thin-film TiO2-coated working electrode, which presented a flat band potential of -0.0274 V versus SCE. Regardless of the potential applied in these experiments, no BrO3- removal was observed in the counter electrode compartment or during electrolysis or photocatalysis, confirming that reduction of BrO3- to Br requires the combination of a negative potential (ideally near -0.20 V) and ultraviolet irradiation of the Ti/TiO2 electrode. The process was selective for BrO3- removal in that this process did not significantly reduce levels of Ca2+ and Mg2+ in drinking waters.

Involvement of reactive oxygen species in the electrochemical inhibition of barnacle (Amphibalanus amphitrite) settlement.

The role of reactive oxygen species (ROS) in electrochemical biofouling inhibition was investigated using a series of abiotic tests and settlement experiments with larvae of the barnacle Amphibalanus amphitrite, a cosmopolitan fouler. Larval settlement, a measure of biofouling potential, was reduced from 43% +/- 14% to 5% +/- 6% upon the application of pulsed electric signals. The application of ROS scavengers such as glutathione and catalase counteracted the inhibitory effects of the electric signals, allowing settlement, and thus indicating that ROS are antifouling agents. Based on the experimental evidence, the proposed mechanism for ROS-based fouling prevention with interdigitated electrodes involved the electrochemical generation of hydrogen peroxide by oxygen reduction, and its likely reduction to hydroxyl radicals. Either hydroxyl radicals or products of hydroxyl radical reactions appeared to be the main deterrents of larval settlement.

Simultaneous removal of chromium and leather dye from simulated tannery effluent by photoelectrochemistry.

The feasibility of the photobleaching of a leather acid dye, acid red 151, simultaneously to degradation of anionic surfactant, Tamol, and reduction of Cr(VI) to the less toxic Cr(III) was investigated by photoelectrocatalytic oxidation. The best experimental conditions were found to be pH 2.0 and 0.1 mol L(-1) sodium sulfate when the nanoporous Ti/TiO2 photo anode was biased at +1.0 V and submitted to UV-irradiation. The photoelectrocatalytic oxidation promotes 100% discoloration, reducing around 98-100% of Cr(VI) and achieving an abatement of 95% of the original total organic carbon. The effect of pH, the applied potential, the Cr(VI) concentration and the complexation reaction between Cr(VI) and acid red dye were evaluated as to their effect on the kinetics of the reaction.

Inhibition of barnacle (Amphibalanus amphitrite) cyprid settlement by means of localized, pulsed electric fields.

The increasing needs for environmental friendly antifouling coatings have led to investigation of new alternatives for replacing copper and TBT-based paints. In this study, results are presented from larval settlement assays of the barnacle Amphibalanus (= Balanus) amphitrite on planar, interdigitated electrodes (IDE), having 8 or 25 mum of inter-electrode spacing, upon the application of pulsed electric fields (PEF). Using pulses of 100 ms in duration, 200 Hz in frequency and 10 V in pulse amplitude, barnacle settlement below 5% was observed, while similar IDE surfaces without pulse application had an average of 40% settlement. The spacing between the electrodes did not affect cyprid settlement. Assays with lower PEF amplitudes did not show significant settlement inhibition. On the basis of the settlement assays, the calculated minimum energy requirement to inhibit barnacle settlement is 2.8 W h m(-2).

Measuring the mass of thin films and adsorbates using magnetoelastic techniques.

Magnetoelastic sensor techniques have the unique characteristics of being able to wirelessly detect resonant frequency shifts of a magnetoelastic foil in response to differences in the foil mass. However, the mathematical expression that links the resonant frequency shift with the change in the mass of the magnetoelastic foil is rarely reported. Furthermore, this relationship is not easy to ascertain due to potential changes in the Young's modulus of the sensor upon a change in mass loading. In this paper, we have shown that adsorption of water vapor from the gas phase by magnetoelastic ribbons coated with a two layer porous thin film (SiO2/Pt-TiO2) induces large changes in the effective Young's modulus of the sensor. We also demonstrated that the change in Young's modulus upon mass loading can be eliminated from the relationship between mass loading and shifts in resonant frequency by using a technique that we refer to as the two different length sensor method (TDLS). This methodology permits the conversion of the magnetoelastic sensor into a microbalance. From data presented in this paper, we illustrate that the sensitivity for the same sensor can range between 214 Hz/mg for mass loadings of Au to 438 kHz/mg for acetone. In the case of water adsorption, frequency shifts varies from 20.0 kHz/mg when Deltam

Redox equilibria of iron oxides in aqueous-based magnetite dispersions: effect of pH and redox potential.

The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.

Effects of localised, low-voltage pulsed electric fields on the development and inhibition of Pseudomonas aeruginosa biofilms.

This work describes the use of low-voltage (0.5 - 5 V) pulsed electric fields to prevent Pseudomonas aeruginosa biofilm development. Interdigitated electrodes (IDEs) with 29-mum spacing between 22-mum-wide electrodes, were used as a platform where the effect of localised, high-strength electric fields could be tested. Alternating current, square-wave pulses were applied to the IDEs in 1 sec intervals. A two-level, three-variable factorial design experiment was used to detect the effects of applied voltage, frequency, and pulse duty ratio (i.e. percentage of pulsing time over one cycle) on the inhibition of biofilm formation. The observations indicated that a pulse configuration of 1% duty ratio, 5 V, and 200 Hz frequency reduced the area of the electrodes covered by biofilm by 50%. In general, the application of low-duty ratio pulses had a positive effect on preventing biofouling. Comparatively, frequency and applied voltage were observed to have less influence on biofouling.

FTIR spectroscopy of alcohol and formate interactions with mesoporous TiO2 surfaces.

The effects of pH and ultraviolet (UV) light with ligated formic acid on mesoporous TiO2 were characterized by transmission Fourier transform infrared (FTIR) spectroscopy and compared with adsorbed formate complexes. Surface-modified anatase thin films were prepared from acidic aqueous nanoparticulate anatase suspensions diluted with methanol and ethanol. Bands assigned to carboxylic acid groups displayed unique bonding character in the ligated formic acid on the anatase surface. For increased proton concentrations in the films, separation in -COO stretching bands (delta nu) for formic acid increased (increase in frequency for nuC=O and decrease in frequency for nuC-O). With UV exposure, surface-bound organics were rapidly removed by photocatalytic oxidation at 40 degrees C and 40% relative humidity (RH). In addition, the delta nu of the formic acid bands decreased as organics were mineralized to carbonates and CO2 with UV light. Aqueous formic acid adsorption experiments showed a distinctly different bonding environment lacking carbonate, and the delta nu for the carboxylic groups indicated a bridging bidentate coordination. The delta nu of the bands increased with increasing proton concentration, with both bands shifting to higher wavenumbers. The shifts may be ascribed to the influence of protonation on surface charge and the effect of that charge on the electronegativity of carboxylate groups bound to the surface. As alcohols are used in the mesoporous TiO2 solar cell preparation, implications of these surface modifications to dye-sensitized photovoltaics are discussed.

Bromate formation on the non-porous TiO2 photoanode in the photoelectrocatalytic system.

The increasing use of ozone in water disinfection processes has been the focus of considerable concern in regards to inorganic disinfection by product formation of bromate in waters containing bromide. Due to the public health risk caused by the presence of bromate as a suspected carcinogen, attention had been addressed to the conditions under which bromate is formed. In this study, photoanodic bromine generation and bromate (BrO(3)(-)) formation were investigated using a TiO(2) electrode in a photoelectrocatalytic (PEC) treatment process. The separation of anodic and cathodic reactions in the PEC system resulted in a pH decrease from 9.3 to 3.0 in the photoanode compartment and an increase to 11.0 in the cathode compartment. Under a photo-illumination intensity of 5.7 m W cm(-2) UV, a biasing potential of +1.0V vs SCE, a pH of 6.0 and at a NaBr concentration of 1.0 x 10(-2) M, active bromine formation increased over time with 2.4 x 10(-6) M min(-6) rate and reached a steady-state concentration of 1.44 x 10(-4) M in 60 min. Bromate formation was detected after a lag-period of 15 min and exhibited a continuous increasing trend with respect to irradiation time. No bromate formation was observed below pH 6.5 whereas an increasing bromate concentrations and pH up to pH=8.5 were noted.

Photoelectrocatalytic production of active chlorine on nanocrystalline titanium dioxide thin-film electrodes.

The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L(-1) of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L(-1) NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photo electrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes.

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH>7.

Characterization of gas-phase adsorption on metal oxide thin films using a magnetoelastic resonance microbalance.

In this study, a magnetoelastic resonance microbalance (MERM) was used to directly measure the gas-phase adsorption behavior of water vapor, isopropyl alcohol, and acetone on a sol-gel-derived titanium dioxide sensor coating. The nature of the MERM platform enables chemical measurements in situations in which wires or physical connections are undesired (or not possible) or in which sensor cost is a major issue. The underlying MERM technique (with an uncoated sensor) showed excellent day-to-day stability, a linear calibration over a 1 kHz change in frequency (or a 1.5-mg change in mass), and the ability to detect a mass change of 15 microg without any efforts at sensitivity optimization. The titanium dioxide coated sensor yielded excellent response to each of the analytes; however, the response did not follow a simple linear calibration function. A more complex calibration model or utilization of the coated sensor in a limited concentration range would be required for quantitative analysis. The process of applying the metal oxide coatings onto the magnetic substrate altered the structure of the thin film layer, resulting in a relatively loose packing of the porous primary titanium dioxide particles to create an open overall honeycomb structure, thereby affecting the adsorption behavior at high relative concentration.