A Hybrid Metal-Organic Framework-Reduced Graphene Oxide Nanomaterial for Selective Removal of Chromate from Water in an Electrochemical Process.

Hexavalent chromium Cr(VI) is a highly toxic groundwater contaminant. In this study, we demonstrate a selective electrochemical process tailored for removal of Cr(VI) using a hybrid MOF@rGO nanomaterial synthesized by in situ growth of a nanocrystalline, mixed ligand octahedral metal-organic framework with cobalt metal centers, [Co2(btec)(bipy)(DMF)2]n (Co-MOF), on the surface of reduced graphene oxide (rGO). The rGO provides the electric conductivity necessary for an electrode, while the Co-MOF endows highly selective adsorption sites for CrO42-. When used as an anode in the treatment cycles, the MOF@rGO electrode exhibits strong selectivity for adsorption of CrO42- over competing anions including Cl-, SO42-, and As(III) and achieves charge efficiency (CE) >100% due to the strong physisorption of CrO42- by Co-MOF; both electro- and physisorption capacities are regenerated with the reversal of the applied voltage, when highly toxic Cr(VI) is reduced to less toxic reduced Cr species and subsequently released into brine. This approach allows easy regeneration of the nonconducting Co-MOF without any chemical addition while simultaneously transforming Cr(VI), inspiring a novel electrochemical method for highly selective degradation of toxic contaminants using tailor-designed electrodes with high affinity adsorbents.

A Comparison of Capacitive Deionization and Membrane Capacitive Deionization Using Novel Fabricated Ion Exchange Membranes.

Another technique for desalination, known as membrane capacitive deionization (MCDI), has been investigated as an alternative. This approach has the potential to lower the voltage that is required, in addition to improving the ability to renew the electrodes. In this study, the desalination effectiveness of capacitive deionization (CDI) was compared to that of MCDI, employing newly produced cellulose acetate ion exchange membranes (IEMs), which were utilized for the very first time in MCDI. As expected, the salt adsorption and charge efficiency of MCDI were shown to be higher than those of CDI. Despite this, the unique electrosorption behavior of the former reveals that ion transport via the IEMs is a crucial rate-controlling step in the desalination process. We monitored the concentration of salt in the CDI and MCDI effluent streams, but we also evaluated the pH of the effluent stream in each of these systems and investigated the factors that may have caused these shifts. The significant change in pH that takes place during one adsorption and desorption cycle in CDI (pH range: 2.3-11.6) may cause problems in feed water that already contains components that are prone to scaling. In the case of MCDI, the fall in pH was only slightly more noticeable. Based on these findings, it appears that CDI and MCDI are promising new desalination techniques that has the potential to be more ecologically friendly and efficient than conventional methods of desalination. MCDI has some advantages over CDI in its higher salt removal efficiency, faster regeneration, and longer lifetime, but it is also more expensive and complex. The best choice for a particular application will depend on the specific requirements.

Energy Consumption in Capacitive Deionization for Desalination: A Review.

Capacitive deionization (CDI) is an emerging eco-friendly desalination technology with mild operation conditions. However, the energy consumption of CDI has not yet been comprehensively summarized, which is closely related to the economic cost. Hence, this study aims to review the energy consumption performances and mechanisms in the literature of CDI, and to reveal a future direction for optimizing the consumed energy. The energy consumption of CDI could be influenced by a variety of internal and external factors. Ion-exchange membrane incorporation, flow-by configuration, constant current charging mode, lower electric field intensity and flowrate, electrode material with a semi-selective surface or high wettability, and redox electrolyte are the preferred elements for low energy consumption. In addition, the consumed energy in CDI could be reduced to be even lower by energy regeneration. By combining the favorable factors, the optimization of energy consumption (down to 0.0089 Wh·gNaCl-1) could be achieved. As redox flow desalination has the benefits of a high energy efficiency and long lifespan (~20,000 cycles), together with the incorporation of energy recovery (over 80%), a robust future tendency of energy-efficient CDI desalination is expected.

Fabrication of polyvinylidene fluoride-derived porous carbon heterostructure with inserted carbon nanotube via phase-inversion coupled with annealing for capacitive deionization application.

As a promising desalination technology, capacitive deionization (CDI) has great potential to guarantee freshwater supply. It is urgently needed to explore novel electrode materials with excellent desalination performance. Herein, the PVDF-derived porous carbon heterostructure with inserted carbon nanotube (PPC/CNT) was prepared via phase-inversion coupled with annealing strategy and applied as electrode material for CDI desalination. The resultant PPC/CNT possesses the combined structural advantages of PPC and CNT, such as high specific surface, mesoporous structure and improved conductivity. By virtue of these remarkable properties, PPC/CNT exhibites an excellent electrosorption capacity of 15.1 mg/g in 500 mg/L NaCl, while that of PPC electrode is 10.3 mg/g. Specially, the charge efficiency of PPC/CNT electrode is 1.39 times higher as compared to PPC, which is largely responsible for the improvement of electrosorption capacity. Besides, PPC/CNT electrode demonstrated good cycle stability over 10 electrosorption-desorption cycles. Thus, PPC/CNT electrode presents promising prospects as CDI electrode for water desalination. This work may shed new light on the rational design of porous carbon heterostructures with suitable host matrix and improved conductivity, subsequently developing the CDI performance.

A new standard metric describing the adsorption capacity of carbon electrode used in membrane capacitive deionization.

A new standard metric has been developed to express the actual adsorption capacity of the carbon electrode in consideration of the electrode reactions. The adsorption experiments were carried out by changing the cell potentials (0.6-1.6 V) in the MCDI unit cell. The point at which the electrode reactions occur was determined from the change in instantaneous charge efficiency during the adsorption process. Then, the total charge supplied to the carbon electrode at this point was defined as the maximum allowable charge (MAC). The MAC values were constant at 59 C/g irrespective of cell potentials. In addition, the salt adsorption capacity (SACMAC) and the charge efficiency at MAC were approximately 16 mg/g and 91%, respectively, regardless of the cell potentials. Furthermore, the equivalent circuit analysis for the MCDI cell revealed that Faradaic reactions rarely occur at the MAC. The MAC is the maximum charge that can be supplied to the carbon electrode without electrode reactions. It is also unaffected by the cell components and operating conditions of the MCDI cell. Therefore, the MAC is expected to be a useful metric to objectively express the actual adsorption capacity of the carbon electrode.

Pseudocapacitive Coating for Effective Capacitive Deionization.

Capacitive deionization (CDI) features a low-cost and energy-efficient desalination approach based on electrosorption of saline ions. To enhance the salt electrosorption capacity of CDI electrodes, we coat ion-selective pseudocapacitive layers (MnO2 and Ag) onto porous carbon electrodes (activated carbon cloth) with only minimal use of a conductive additive and a polymer binder (<1 wt % in total). Optimized pseudocapacitive electrodes result in excellent single-electrode specific capacitance (>300 F/g) and great cell stability (70% retention after 500 cycles). A CDI cell out of these pseudocapacitive electrodes yields as high charge efficiency as 83% and a remarkable salt adsorption capacity up to 17.8 mg/g. Our finding of outstanding CDI performance of the pseudocapacitive electrodes with no use of costly ion-exchange membranes highlights the significant role of a pseudocapacitive layer in the electrosorption process.

Capacitive Deionization using Biomass-based Microporous Salt-Templated Heteroatom-Doped Carbons.

Microporous carbons are an interesting material for electrochemical applications. In this study, we evaluate several such carbons without/with N or S doping with regard to capacitive deionization. For this purpose, we extent the salt-templating synthesis towards biomass precursors and S-doped microporous carbons. The sample with the largest specific surface area (2830 m(2) g(-1) ) showed 1.0 wt % N and exhibited a high salt-sorption capacity of 15.0 mg g(-1) at 1.2 V in 5 mM aqueous NaCl. While being a promising material from an equilibrium performance point of view, our study also gives first insights to practical limitations of heteroatom-doped carbon materials. We show that high heteroatom content may be associated with a low charge efficiency. The latter is a key parameter for capacitive deionization and is defined as the ratio between the amounts of removed salt molecules and electrical charge.