Tailored Metal-Organic Frameworks for Water Purification: Perfluorinated Fe-MOFs for Enhanced Heterogeneous Catalytic Ozonation.

An industrially viable catalyst for heterogeneous catalytic ozonation (HCO) in water purification requires the characteristics of good dispersion of active species on its surface, efficient electron transfer for ozone decay, and maximum active species utilization. While metal-organic frameworks (MOFs) represent an attractive platform for HCO, the metal nodes in the unmodified MOFs exhibit low catalytic activity. Herein, we present a perfluorinated Fe-MOF catalyst by substituting H atoms on the metalated ligands with F atoms (termed 4F-MIL-88B) to induce structure evolution. The Lewis acidity of 4F-MIL-88B was enhanced via the formation of Fe nodes, tailoring the electron distribution on the catalyst surface. As a result of catalyst modification, the rate constant for degradation of the target compounds examined increased by ∼700% compared with that observed for the unmodified catalyst. Experimental evidence and theoretical calculations showed that the modulated polarity and the enhanced electron transfer between the catalyst and ozone molecules contributed to the adsorption and transformation of O3 to •OH on the catalyst surface. Overall, the results of this study highlight the significance of tailoring the metalated ligands to develop highly efficient and stable MOF catalysts for HCO and provide an in-depth mechanistic understanding of their structure-function evolution, which is expected to facilitate the applications of nanomaterial-based processes in water purification.

Ion-Selective Metathesis Design of Flow-Electrode Capacitive Deionization for Energy-Saving and Anti-Scaling Softening of Brackish Water.

While flow-electrode capacitive deionization (FCDI) is recognized as an attractive desalination technology, its practical implementation has been hindered by the ease of scaling and energy-intensive nature of the single-cell FCDI system, particularly when treating brackish water with elevated levels of naturally coexisting SO42- and Ca2+. To overcome these obstacles, we propose and design an innovative ion-selective metathesis FCDI (ISM-FCDI) system, consisting of a two-stage tailored cell design. Results indicate that the specific energy consumption per unit volume of water for the ISM-FCDI is lower (by up to ∼50%) than that of a conventional single-stage FCDI due to the parallel circuit structure of the ISM-FCDI. Additionally, the ISM-FCDI benefits from a conspicuous disparity in the selective removal of ions at each stage. The separate storage of Ca2+ and SO42- by the metathesis process in the ISM-FCDI (46.25% Ca2+, 14.25% SO42- in electrode 1 and 4.75% Ca2+, 35.25% SO42- in electrode 2) can effectively prevent scaling. Furthermore, configuration-performance analysis on the ion-selective migration suggests that the properties of the ion exchange membrane, rather than the carbon species, govern the selectivity of ion removal. This work introduces system-level enhancements aimed at enhancing energy conservation and scaling prevention, providing critical optimization of the FCDI for brackish water softening.

New Insights into the Role of Humic Acid in Permanganate Oxidation of Diclofenac: A Novel Electron Transfer Mechanism.

Humic acid (HA) ubiquitously existing in aquatic environments has been reported to significantly impact permanganate (KMnO4) decontamination processes. However, the underlying mechanism of the KMnO4/HA system remained elusive. In this study, an enhancing effect of HA on the KMnO4 oxidation of diclofenac (DCF) was observed over a wide solution pH range of 5-9. Surprisingly, the mechanism of HA-induced enhancement varied with solution pH. Quenching and chemical probing experiments revealed that manganese intermediates (Mn(III)-HA and MnO2) were responsible for the enhancement under acidic conditions but not under neutral and alkaline conditions. By combining KMnO4 decomposition, galvanic oxidation process experiments, electrochemical tests, and FTIR and XPS analysis, it was interestingly found that HA could effectively mediate the electron transfer from DCF to KMnO4 in neutral and alkaline solutions, which was reported for the first time. The formation of an organic-catalyst complex (i.e., HA-DCF) with lower reduction potential than the parent DCF was proposed to be responsible for the accelerated electron transfer from DCF to KMnO4. This electron transfer likely occurred within the complex molecule formed through the interaction between HA-DCF and KMnO4 (i.e., HA-DCF-KMnO4). These results will help us gain a more comprehensive understanding of the role of HA in the KMnO4 oxidation processes.

Shifting Emphasis from Electro- to Catalytically Active Sites: Effects of Pore Size of Flow-Through Anodes on Water Purification.

A flow-through anode has demonstrated high efficiency for micropollutant abatement in water purification. In addition to developing novel electrode materials, a rational design of its porous structure is crucial to achieve high electrooxidation kinetics while sustaining a low cost for flow-through operation. However, our knowledge of the relationship between the pore structure and its performance is still incomplete. Therefore, we systematically explore the effect of pore size (with a median from 4.7 to 49.4 µm) on the flow-through anode efficiency. Results showed that when the pore size was <26.7 µm, the electrooxidation kinetics was insignificantly improved, but the permeability declined dramatically. Traditional empirical evidence from hydrodynamic modeling and electrochemical tests indicated that a flow-through anode with a smaller pore size (e.g., 4.7 µm) had a high mass transfer capability and large electroactive area. However, this did not further accelerate the micropollutant removal. Combining an overpotential distribution model and an imprinting method has revealed that the reactivity of a flow-through anode is related to the catalytically active volume/sites. The rapid overpotential decay as a function of depth in the anode would offset the merits arising from a small pore size. Herein, we demonstrate an optimal pore size distribution (∼20 µm) of typical flow-through anodes to maximize the process performance at a low energy cost, providing insights into the design of advanced flow-through anodes in water purification applications.

Heterogenous Iron Oxide Assemblages for Use in Catalytic Ozonation: Reactivity, Kinetics, and Reaction Mechanism.

Heterogeneous catalytic ozonation (HCO) has gained increasing attention as an effective process to remove refractory organic pollutants from industrial effluents. However, widespread application of HCO is still limited due to the typically low efficacy of catalysts used and matrix passivation effects. To this end, we prepared an Al2O3-supported Fe catalyst with high reactivity via a facile urea-based heterogeneous precipitation method. Due to the nonsintering nature of the preparation method, a heterogeneous catalytic layer comprised of γ-FeOOH and α-Fe2O3 is formed on the Al2O3 support (termed NS-Fe-Al2O3). On treatment of a real industrial effluent by HCO, the presence of NS-Fe-Al2O3 increased the removal of organics by ∼100% compared to that achieved with a control catalyst (i.e., α-Fe2O3/Al2O3 or γ-FeOOH/Al2O3) that was prepared by a conventional impregnation and calcination method. Furthermore, our results confirmed that the novel NS-Fe-Al2O3 catalyst demonstrated resistance to the inhibitory effect of high concentration of chloride and sulfate ions usually present in industrial effluent. A mathematical kinetic model was developed that adequately describes the mechanism of HCO process in the presence of NS-Fe-Al2O3. Overall, the results presented here provide valuable guidance for the synthesis of effective and robust catalysts that will facilitate the wider industrial application of HCO.

Metal-Organic Framework with a Redox-Active Bridge Enables Electrochemically Highly Selective Removal of Arsenic from Water.

Selective removal of trace, highly toxic arsenic from water is vital to ensure an adequate and safe drinking water supply for over 230 million people around the globe affected by arsenic contamination. Here, we developed an Fe-based metal-organic framework (MOF) with a ferrocene (Fc) redox-active bridge (termed Fe-MIL-88B-Fc) for the highly selective removal of As(III) from water. At a cell voltage of 1.2 V, Fe-MIL-88B-Fc can selectively separate and oxidize As(III) into the less harmful As(V) state in the presence of a 100- to 1250-fold excess of competing electrolyte, with an uptake capacity of >110 mg-As g-1 adsorbent. The high affinity between the uncharged As(III) and the µ3-O trimer (-36.55 kcal mol-1) in Fe-MIL-88B-Fc and the electron transfer between As(III) and redox-active Fc+ synergistically govern the selective capture and conversion of arsenic. The Fe-based MOF demonstrates high selectivity and capacity to remediate arsenic-contaminated natural water at a low energy cost (0.025 kWh m-3). This study provides valuable guidance for the tailoring of effective and robust electrodes, which can lead to a wider application of electrochemical separation technologies.

Ferryl Ion in the Photo-Fenton Process at Acidic pH: Occurrence, Fate, and Implications.

Fenton processes produce reactive species that can oxidize organic compounds in natural and engineered systems. While it is well-documented that Fenton reactions produce hydroxyl radical (HO•) under acidic conditions, we demonstrated the generation of ferryl ion (FeIVO2+) in the UV/Fe(III) and UV/Fe(III)/H2O2 systems at pH 2.8 using methyl phenyl sulfoxide (PMSO) as the probe compound. Moreover, we clarified that FeIVO2+ is parallelly formed via the oxidation of Fe(III) by HO• and the O-O homolysis of [FeIII-OOH]2+ in the photo-Fenton process. The rate constant for the reaction between HO• and Fe3+ measured by laser flash photolysis was 4.41 × 107 M-1 s-1. The rate constant and quantum yield for thermal and photo O-O homolysis of [FeIII-OOH]2+ complex were 1.4 × 10-2 s-1 and 0.3, respectively, which were determined by fitting PMSO2 formation. While FeIVO2+ forms predominantly through the reaction between HO• and Fe3+ in the absence of H2O2, the relative contribution of [FeIII-OOH]2+ O-O homolysis to FeIVO2+ formation highly depends on the molar ratio of [H2O2]0/[Fe(III)]0, the level of HO• scavenging, and incident irradiance in the UV/Fe(III)/H2O2 system. Accordingly, an optimized kinetic model was developed by incorporating FeIVO2+-involved reactions into the conventional photo-Fenton model, which can accurately predict Fe(II) formation and contaminant decay in the UV/Fe(III) and UV/Fe(III)/H2O2 systems. Our study illuminated the underlying formation mechanism of reactive oxidative species in the photo-Fenton process and highlighted the role of FeIVO2+ evolution in modulating the iron cycle and pollutant abatement therein.

Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity.

Singlet oxygen (1 O2 ) is an excellent reactive oxygen species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to the huge dilemma in synthesizing single-site type catalysts, the control and regulation of 1 O2 generation in AOPs is still challenging and the underlying mechanism remains largely obscure. Here, taking advantage of the well-defined and flexibly tunable sites of covalent organic frameworks (COFs), we report the first achievement in precisely regulating ROSs generation in peroxymonosulfate (PMS)-based AOPs by site engineering of COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway with 100 % 1 O2 , whereas biphenyl-based COFs (BPD-COFs) with almost identical structures activate PMS to produce radicals (⋅OH and SO4 .- ). The BPY-COFs/PMS system delivers boosted performance for selective degradation of target pollutants from water, which is ca. 9.4 times that of its BPD-COFs counterpart, surpassing most reported PMS-based AOPs systems. Mechanism analysis indicated that highly electronegative pyridine-N atoms on BPY-COFs provide extra sites to adsorb the terminal H atoms of PMS, resulting in simultaneous adsorption of O and H atoms of PMS on one pyridine ring, which facilitates the cleavage of its S-O bond to generate 1 O2 .

Direct Electron Transfer Coordinated by Oxygen Vacancies Boosts Selective Nitrate Reduction to N2 on a Co-CuOx Electroactive Filter.

Atomic hydrogen (H*) is used as an important mediator for electrochemical nitrate reduction; however, the Faradaic efficiency (FE) and selective reduction to N2 are likely compromised due to the side reactions (e.g., ammonia generation and hydrogen evolution reactions). This work reports a Co-CuOx electrochemical filter with CoOx nanoclusters rooted on vertically aligned CuOx nanowalls for selective nitrate reduction to N2, utilizing the direct electron transfer between oxygen vacancies and nitrate to suppress the contribution by H*. At a cathodic potential of -1.1 V (vs Ag/AgCl), the Co-CuOx filter showed 95.2% nitrate removal and 96.0% N2 selectivity at an influent nitrate concentration of 20 N-mg L-1. Meanwhile, the energy consumption and FE were 0.60 kW h m-3 and 53.5%, respectively, at a permeate flux of 60 L m-2 h-1. The presence of abundant oxygen vacancies on Co-CuOx was due to the change in the electron density of the Cu atom and a decrease of the coordination numbers of Cu-O via cobalt doping. Theoretical calculations and electrochemical tests showed that the oxygen vacancies coordinated nitrate adsorption and subsequent reduction reactions, thus suppressing the contribution of H* to nitrate reduction and leading to a thermodynamically favorable process to N2 via direct electron transfer.

Development of a Mechanically Flexible 2D-MXene Membrane Cathode for Selective Electrochemical Reduction of Nitrate to N2: Mechanisms and Implications.

The contamination of water resources by nitrate is a major problem. Herein, we report a mechanically flexible 2D-MXene (Ti3C2Tx) membrane with multilayered nanofluidic channels for a selective electrochemical reduction of nitrate to nitrogen gas (N2). At a low applied potential of -0.8 V (vs Ag/AgCl), the MXene electrochemical membrane was found to exhibit high selectivity for NO3- reduction to N2 (82.8%) due to a relatively low desorption energy barrier for the release of adsorbed N2 (*N2) compared to that for the adsorbed NH3 (*NH3) based on density functional theory (DFT) calculations. Long-term use of the MXene membrane for treating 10 mg-NO3-N L-1 in water was found to have a high faradic efficiency of 72.6% for NO3- reduction to N2 at a very low electrical cost of 0.28 kWh m-3. Results of theoretical calculations and experimental results showed that defects on the MXene nanosheet surfaces played an important role in achieving high activity, primarily at the low-coordinated Ti sites. Water flowing through the MXene nanosheets facilitated the mass transfer of nitrate onto the low-coordinated Ti sites with this enhancement of particular importance under cathodic polarization of the MXene membrane. This study provides insight into the tailoring of nanoengineered materials for practical application in water treatment and environmental remediation.

Kinetic Modeling-Assisted Mechanistic Understanding of the Catalytic Ozonation Process Using Cu-Al Layered Double Hydroxides and Copper Oxide Catalysts.

In this study, copper aluminum layered hydroxides (Cu-Al LDHs) and copper oxide (CuO) were utilized as catalysts for heterogeneous catalytic ozonation (HCO). Target compounds oxalate and formate were used with removal by adsorption and oxidation quantified to elucidate the role of the catalyst in contaminant removal. Oxidation of oxalate mostly occurred on the catalyst surface via interaction of surface oxalate complexes with surface-located oxidants. In contrast, the oxidation of formate occurred in the bulk solution as well as on the surface of the catalyst. Measurement of O3 decay kinetics coupled with fluorescence microscopy image analysis corresponding to 7-hydroxycoumarin formation indicates that while surface hydroxyl groups in Cu-Al LDHs facilitate slow decay of O3 resulting in the formation of hydroxyl radicals on the surface, CuO rapidly transforms O3 into surface-located hydroxyl radicals and/or other oxidants. Futile consumption of surface-located oxidants via interaction with the catalyst surface was minimal for Cu-Al-LDHs; however, it becomes significant in the presence of higher CuO dosages. A mechanistic kinetic model has been developed which adequately describes the experimental results obtained and can be used to optimize the process conditions for the application of HCO.

Self-Enhanced Decomplexation of Cu-Organic Complexes and Cu Recovery from Wastewaters Using an Electrochemical Membrane Filtration System.

Heavy metals in industrial wastewaters are typically present as stable metal-organic complexes with their cost-effective treatment remaining a significant challenge. Herein, a self-enhanced decomplexation scenario is developed using an electrochemical membrane filtration (EMF) system for efficient decomplexation and Cu recovery. Using Cu-EDTA as a model pollutant, the EMF system achieved 81.5% decomplexation of the Cu-EDTA complex and 72.4% recovery of Cu at a cell voltage of 3 V. The •OH produced at the anode first attacked Cu-EDTA to produce intermediate Cu-organic complexes that reacted catalytically with the H2O2 generated from the reduction of dissolved oxygen at the cathode to initiate chainlike self-enhanced decomplexation in the EMF system. The decomplexed Cu products were further reduced or precipitated at the cathodic membrane surface thereby achieving efficient Cu recovery. By scavenging H2O2 (excluding self-enhanced decomplexation), the rate of decomplexation decreased from 8.8 × 10-1 to 4.1 × 10-1 h-1, confirming the important role of self-enhanced decomplexation in this system. The energy efficiency of this system is 93.5 g kWh-1 for Cu-EDTA decomplexation and 15.0 g kWh-1 for Cu recovery, which is much higher than that reported in the previous literature (i.e., 7.5 g kWh-1 for decomplexation and 1.2 g kWh-1 for recovery). Our results highlight the potential of using EMF for the cost-effective treatment of industrial wastewaters containing heavy metals.

Flow Electrode Capacitive Deionization (FCDI): Recent Developments, Environmental Applications, and Future Perspectives.

With the increasing severity of global water scarcity, a myriad of scientific activities is directed toward advancing brackish water desalination and wastewater remediation technologies. Flow-electrode capacitive deionization (FCDI), a newly developed electrochemically driven ion removal approach combining ion-exchange membranes and flowable particle electrodes, has been actively explored over the past seven years, driven by the possibility of energy-efficient, sustainable, and fully continuous production of high-quality fresh water, as well as flexible management of the particle electrodes and concentrate stream. Here, we provide a comprehensive overview of current advances of this interesting technology with particular attention given to FCDI principles, designs (including cell architecture and electrode and separator options), operational modes (including approaches to management of the flowable electrodes), characterizations and modeling, and environmental applications (including water desalination, resource recovery, and contaminant abatement). Furthermore, we introduce the definitions and performance metrics that should be used so that fair assessments and comparisons can be made between different systems and separation conditions. We then highlight the most pressing challenges (i.e., operation and capital cost, scale-up, and commercialization) in the full-scale application of this technology. We conclude this state-of-the-art review by considering the overall outlook of the technology and discussing areas requiring particular attention in the future.

Selective Arsenic Removal from Groundwaters Using Redox-Active Polyvinylferrocene-Functionalized Electrodes: Role of Oxygen.

In this work, we investigate selective sorption of arsenic from simulated groundwaters at pH 8 by a redox-active polyvinylferrocene (PVF)-functionalized electrode using a modified double potential step chronoamperometry (DPSC) method. Our results show that effective and sustainable As(III) removal can be achieved at 0 V once the electrode is activated via anodic polarization. During activation, ferrocene (Fc) in PVF is oxidized to the ferrocenium ion (Fc+) with the latter facilitating As(III) sorption and subsequent oxidation as well as As(V) sorption. The high affinity of Fc+ to As and weak attraction to competing anions at 0 V ensure high selectivity of As over Cl-, SO42-, and NO3- at concentrations typical of groundwaters. Following the removal process, efficient regeneration of the electrode is achieved at -1.2 V wherein Fc+ is reduced to Fc thereby facilitating As desorption from the electrode surface. Our results further show that O2 and associated generation of hydrogen peroxide during the regeneration step drive the oxidation of Fc to Fc+, thereby maintaining the constant generation of Fc+ required to achieve As(III) removal in subsequent cycles. Our results show that 91.8 ± 0.6% of As(III) could be selectively removed from simulated groundwater over 10 cycles at an ultralow energy consumption of 0.12 kWh m-3.

Effect of the Presence of Carbon in Ti4O7 Electrodes on Anodic Oxidation of Contaminants.

Magnéli phase titanium suboxide, Ti4O7, has attracted increasing attention as a potential electrode material in anodic oxidation as a result of its high efficiency and (electro)chemical stability. Although carbon materials have been amended to Ti4O7 electrodes to enhance the electrochemical performance or are present as an unwanted residual during the electrode fabrication, there has been no comprehensive investigation of how these carbon materials affect the electrochemical performance of the resultant Ti4O7 electrodes. As such, we investigated the electrochemical properties of Ti4O7 electrodes impregnated with carbon materials at different contents (and chemical states). Results of this study showed that while pure Ti4O7 electrodes exhibited an extremely low rate of interfacial electron transfer, the introduction of minor amounts of carbon materials (at values as low as 0.1 wt %) significantly facilitated the electron transfer process and decreased the oxygen evolution reaction potential. The oxygen-containing functional groups have been shown to play an important role in interfacial electron transfer with moderate oxidation of the carbon groups aiding electron uptake at the electrode surface (and consequently organic oxidation) while the generation of carboxyl groups-a process that is likely to occur in long-term operation-increased the interfacial resistance and thus retarded the oxidation process. Results of this study provide a better understanding of the relationship between the nature of the electrode surface and anodic oxidation performance with these insights likely to facilitate improved electrode design and optimization of operation of anodic oxidation reactors.

Simultaneous solid-liquid separation and wastewater disinfection using an electrochemical dynamic membrane filtration system.

An electrochemical dynamic membrane filtration (EDMF) system for simultaneous solid-liquid separation (also protecting electrodes against fouling) and sewage disinfection was developed. At a low voltage of 2.5 V, efficient disinfection performance was achieved in the EDMF, with ~100% log removal efficiency (no detectable bacteria in the effluent). Results also demonstrated that the EDMF system, operated at membrane flux of 100 L/(m2 h), could maintain long-lasting bacterial disinfection efficiency of real wastewater (~100% log removal) in continuous flow tests. Transmembrane pressure (TMP) increased from 0.8 kPa to 22 kPa within 80 d (one operation cycle), and cleaning of EDMF could effectively restore TMP and biocidal behaviors for subsequent filtration cycles. In contrast, without dynamic membrane, the disinfection efficiency was decreased from initial ~100% log removal (with no detectable live bacteria) to ~44.4% log removal within 7 d. Reactive oxygen species (ROS)-mediated oxidation was responsible for bacteria disinfection in the EDMF, and HO• and H2O2 generated in this system played a dominant role, causing damage to cell membranes and K+ leakage from cytosol. Moreover, catalase and superoxide dismutase for intracellular ROS attenuation were inhibited, resulting in the increase of intracellular oxidative stress and thus high-efficient disinfection. These results highlight the potential of EDMF system to be used for wastewater treatment and disinfection.

Modified Double Potential Step Chronoamperometry (DPSC) Method for As(III) Electro-oxidation and Concomitant As(V) Adsorption from Groundwaters.

Constrained by low energy efficiency and ineffectiveness in As(III) removal under circumneutral pH conditions by many exsiting technologies, As(III) removal has become an issue. In this work we present proof of concept of a modified double potential step chronoamperometry (DPSC) method of As(III) oxidation and concomitant As(V) electro-sorption from aqueous solution. Results show that in situ anodic As(III) oxidation, As(V) electro-sorption, and As(V) electro-desorption are affected by aqueous pH with high oxidation and sorption/desorption rates observed at the elevated pH. We particularly show that effective As(III) oxidation and concomitant As(V) adsorption are related to (i) the rapid oxidation of the deprotonated species compared to the protonated species and (ii) stronger electrochemical interaction between the multicharged As(V) species and the electrodes. At 1.2 V and an electric energy consumption of 0.06 kWh m-3, the total As concentration can be reduced from 150 to 15 µg L-1 using an electrochemical cell with electrode area of 10 × 8 cm2 and electro-sorption time of 120 min. On the basis of the experimental results, we have developed a mathematical model to describe the kinetics and mechanism of arsenic removal by the modified DPSC method with this model of use in predicting, and potentially optimizing, process performance under various conditions.

Water Recovery Rate in Short-Circuited Closed-Cycle Operation of Flow-Electrode Capacitive Deionization (FCDI).

While flow-electrode CDI is a promising desalination technology that has major advantages when the electrodes are operated in the short-circuited closed-cycle (SCC) mode, little attention has been paid to the water recovery rate, which, in the SCC mode, is determined by the need for partial replacement of the saline electrolyte of the flow electrodes. Results of this study show that an extremely high water recovery rate of ∼95% can be achieved when desalting a 1000 mg NaCl L-1 brackish influent to a potable level of 150 mg L-1. The improved performance with regard to the electrical cost is related, at least in part, to the alleviated concentration polarization at the membrane/electrolyte interface during electrosorption. In effect, the current efficiency decreases with an increase in the water recovery rate. This finding is ascribed to inevitable co-ion leakage since the flow electrodes reject ions with the same charge. In addition, water transport across the ion exchange membranes also influences the water recovery rate. The effect of partial replacement of the saline electrolyte during (semi-)continuous operation requires particular consideration because the associated dilution of the carbon content in the flow electrodes results in a decrease in process performance.

Integrated Flow-Electrode Capacitive Deionization and Microfiltration System for Continuous and Energy-Efficient Brackish Water Desalination.

Flow-electrode capacitive deionization (FCDI) is an emerging electrochemically driven technology for brackish and/or sea water desalination with merits of large salt adsorption capacity, high flow efficiency, and easy electrode management. While FCDI holds promise for continuous operation, there are very few investigations with regard to the regeneration/reuse of flowable electrodes and the separation of brine from electrodes with these operation prerequisites for real nonintermittent water desalination. In this study, we propose a novel module design to achieve these critical steps involving integration of an FCDI cell and a ceramic microfiltration (MF) contactor. Our investigations reveal that the brine discharge rate is the dominant factor for stable and efficient operation of the integrated module. Results obtained show that the integrated FCDI/MF system can be used to successfully separate brackish water (of salinities 1, 2 and 5 g L-1) into both a potable stream (<0.5 g L-1) and a brine stream (concentrated by 2-20 times) in a continuous manner with extremely high water recovery rates (up to 97%) and reasonable energy consumption. Another notable characteristic of the integrated system is the high thermodynamic energy efficiency (∼30%) with such efficiencies 4-5 times larger than those of conventional capacitive deionization units and comparable to reverse osmosis and electrodialysis systems achieving similar separation efficiencies. In brief, the results of studies described here indicate that continuous and efficient operation of FCDI is a real possibility and pave the way for scale-up of this emerging technology.

Flow-Electrode CDI Removes the Uncharged Ca-UO2-CO3 Ternary Complex from Brackish Potable Groundwater: Complex Dissociation, Transport, and Sorption.

Unacceptably high uranium concentrations in decentralized and remote potable groundwater resources, especially those of high hardness (e.g ., high Ca2+, Mg2+, and CO32- concentrations), are a common worldwide problem. The complexation of alkali earth metals, carbonate, and uranium(VI) results in the formation of thermodynamically stable ternary aqueous species that are predominantly neutrally charged (e.g ., Ca2(UO2)(CO3)30). The removal of the uncharged (nonadsorbing) complexes is a problematic issue for many water treatment technologies. As such, we have evaluated the efficacy of a recently developed electrochemical technology, termed flow-electrode capacitive deionization (FCDI), to treat a synthetic groundwater, the composition of which is comparable to groundwater resources in the Northern Territory, Australia (and elsewhere worldwide). Theoretical calculations and time-resolved laser fluorescence spectroscopy analyses confirmed that Ca2(UO2)(CO3)30 was the primary aqueous species followed by Ca(UO2)(CO3)32- (at circumneutral pH values). Results under different operating conditions demonstrated that FCDI is versatile in reducing uranium concentrations to <10 µg L-1 with low electrical consumption (e.g ., ∼0.1 kWh m-3). It is concluded that the capability of FCDI to remove uranium under these common conditions depends on the dissociation kinetics of the Ca2(UO2)(CO3)30 complex in the electrical field. The subsequent formation of the negatively charged Ca(UO2)(CO3)32- species results in the efficient transport of uranium across the anion exchange membrane followed by immobilization on the positively charged flow (anode) electrode.