Selective adsorption of nitrate over chloride in microporous carbons.

Activated carbon is the most common electrode material used in electrosorption processes such as water desalination with capacitive deionization (CDI). CDI is a cyclic process to remove ions from aqueous solutions by transferring charge from one electrode to another. When multiple salts are present in a solution, the removal of each ionic species can be different, resulting in selective ion separations. This ion selectivity is the result of combined effects, such as differences in the hydrated size and valence of the ions. In the present work, we study ion selectivity from salt mixtures with two different monovalent ions, chloride and nitrate. We run adsorption experiment in microporous carbons (i.e., without applying a voltage), as well as electrosorption experiments (i.e., based on applying a voltage between two carbon electrodes). Our results show that i) during adsorption and electrosorption, activated carbon removes much more nitrate than chloride; ii) at equilibrium, ion selectivity does not depend strongly on the composition of the water, but does depend on charging voltage in CDI; and iii) during electrosorption, ion selectivity is time-dependent. We modify the amphoteric Donnan model by including an additional affinity of nitrate to carbon. We find good agreement between our experimental results and the theory. Both show very high selectivity towards nitrate over chloride, [Formula: see text] ∼10, when no voltage is applied, or when the voltage is low. The selectivity gradually decreases with increasing charging voltage to [Formula: see text] ∼6 at Vch = 1.2 V. Despite this decrease, the affinity-effect for nitrate continues to play an important role also at a high voltage. In general, we can conclude that our work provides new insights in the importance of carbon-ion interactions for electrochemical water desalination.

Energy consumption in capacitive deionization - Constant current versus constant voltage operation.

In the field of Capacitive Deionization (CDI), it has become a common notion that constant current (CC) operation consumes significantly less energy than constant voltage operation (CV). Arguments in support of this claim are that in CC operation the endpoint voltage is reached only at the end of the charging step, and thus the average cell voltage during charging is lower than the endpoint voltage, and that in CC operation we can recover part of the invested energy during discharge. Though these arguments are correct, in the present work based on experiments and theory, we conclude that in operation of a well-defined CDI cycle, this does not lead, for the case we analyze, to the general conclusion that CC operation is more energy efficient. Instead, we find that without energy recovery there is no difference in energy consumption between CC and CV operation. Including 50% energy recovery, we find that indeed CC is more energy efficient, but also in CV much energy can be recovered. Important in the analysis is to precisely define the desalination objective function, such as that per unit total operational time -including both the charge and discharge steps- a certain desalination quantity and water recovery must be achieved. Another point is that also in CV operation energy recovery is possible by discharge at a non-zero cell voltage. To aid the analysis we present a new method of data representation where energy consumption is plotted against desalination. In addition, we propose that one must analyze the full range of combinations of cycle times, voltages and currents, and only compare the best cycles, to be able to conclude which operational mode is optimal for a given desalination objective. We discuss three methods to make this analysis in a rigorous way, two experimental and one combining experiments and theory. We use the last method and present results of this analysis.

Complementary surface charge for enhanced capacitive deionization.

Commercially available activated carbon cloth electrodes are treated using nitric acid and ethylenediamine solutions, resulting in chemical surface charge enhanced carbon electrodes for capacitive deionization (CDI) applications. Surface charge enhanced electrodes are then configured in a CDI cell to examine their salt removal at a fixed charging voltage and both reduced and opposite polarity discharge voltages, and subsequently compared to the salt removal of untreated electrodes. Substantially improved salt removal due to chemical surface charge and the use of a discharge voltage of opposite sign to the charging voltage is clearly demonstrated in these CDI cycling tests, an observation which for the first time validates both enhanced CDI and extended-voltage CDI effects predicted by the Donnan model [Biesheuvel et al., Colloids Interf. Sci. Comm., 10.1016/j.colcom.2015.12.001 (2016)]. Our experimental and theoretical results demonstrate that the use of carbon electrodes with optimized chemical surface charge can extend the CDI working voltage window through discharge voltages of opposite sign to the charging voltage, which can significantly enhance the salt adsorption capacity of CDI electrodes. Thus, in addition to carbon pore size distribution, chemical surface charge in carbon micropores is considered foundational for salt removal in CDI cells.

Enhanced charge efficiency and reduced energy use in capacitive deionization by increasing the discharge voltage.

Capacitive deionization (CDI) is an electrochemical method for water desalination using porous carbon electrodes. A key parameter in CDI is the charge efficiency, Λ, which is the ratio of salt adsorption over charge in a CDI-cycle. Values for Λ in CDI are typically around 0.5-0.8, significantly less than the theoretical maximum of unity, due to the fact that not only counterions are adsorbed into the pores of the carbon electrodes, but at the same time coions are released. To enhance Λ, ion-exchange membranes (IEMs) can be implemented. With membranes, Λ can be close to unity because the membranes only allow passage for the counterions. Enhancing the value of Λ is advantageous as this implies a lower electrical current and (at a fixed charging voltage) a reduced energy use. We demonstrate how, without the need to include IEMs, the charge efficiency can be increased to values close to the theoretical maximum of unity, by increasing the cell voltage during discharge, with only a small loss of salt adsorption capacity per cycle. In separate constant-current CDI experiments, where after some time the effluent salt concentration reaches a stable value, this value is reached earlier with increased discharge voltage. We compare the experimental results with predictions of porous electrode theory which includes an equilibrium Donnan electrical double layer model for salt adsorption in carbon micropores. Our results highlight the potential of modified operational schemes in CDI to increase charge efficiency and reduce energy use of water desalination.

Water desalination using capacitive deionization with microporous carbon electrodes.

Capacitive deionization (CDI) is a water desalination technology in which salt ions are removed from brackish water by flowing through a spacer channel with porous electrodes on each side. Upon applying a voltage difference between the two electrodes, cations move to and are accumulated in electrostatic double layers inside the negatively charged cathode and the anions are removed by the positively charged anode. One of the key parameters for commercial realization of CDI is the salt adsorption capacity of the electrodes. State-of-the-art electrode materials are based on porous activated carbon particles or carbon aerogels. Here we report the use for CDI of carbide-derived carbon (CDC), a porous material with well-defined and tunable pore sizes in the sub-nanometer range. When comparing electrodes made with CDC with electrodes based on activated carbon, we find a significantly higher salt adsorption capacity in the relevant cell voltage window of 1.2-1.4 V. The measured adsorption capacity for four materials tested negatively correlates with known metrics for pore structure of the carbon powders such as total pore volume and BET-area, but is positively correlated with the volume of pores of sizes <1 nm, suggesting the relevance of these sub-nanometer pores for ion adsorption. The charge efficiency, being the ratio of equilibrium salt adsorption over charge, does not depend much on the type of material, indicating that materials that have been identified for high charge storage capacity can also be highly suitable for CDI. This work shows the potential of materials with well-defined sub-nanometer pore sizes for energy-efficient water desalination.

Water Desalination with Wires.

We show the significant potential of water desalination using a novel capacitive wire-based technology in which anode/cathode wire pairs are constructed from coating a thin porous carbon electrode layer on top of electrically conducting rods (or wires). By alternately dipping an array of electrode pairs in freshwater with and in brine without an applied cell voltage, we create an ion adsorption/desorption cycle. We show experimentally how in six subsequent cycles we can reduce the salinity of 20 mM feed (brackish) water by a factor of 3, while application of a cation exchange membrane on the cathode wires makes the desalination factor increase to 4. Theoretical modeling rationalizes the experimental findings, and predicts that system performance can be significantly enhanced by material modifications. To treat large volumes of water, multiple stacks of wire pairs can be used simultaneously in a "merry-go-round" operational mode.

Theory of membrane capacitive deionization including the effect of the electrode pore space.

Membrane capacitive deionization (MCDI) is a technology for water desalination based on applying an electrical field between two oppositely placed porous electrodes. Ions are removed from the water flowing through a channel in between the electrodes and are stored inside the electrodes. Ion-exchange membranes are placed in front of the electrodes allowing for counterion transfer from the channel into the electrode, while retaining the coions inside the electrode structure. We set up an extended theory for MCDI which includes in the description for the porous electrodes not only the electrostatic double layers (EDLs) formed inside the porous (carbon) particles, but also incorporates the role of the transport pathways in the electrode, i.e., the interparticle pore space. Because in MCDI the coions are inhibited from leaving the electrode region, the interparticle porosity becomes available as a reservoir to store salt, thereby increasing the total salt storage capacity of the porous electrode. A second advantage of MCDI is that during ion desorption (ion release) the voltage can be reversed. In that case the interparticle porosity can be depleted of counterions, thereby increasing the salt uptake capacity and rate in the next cycle. In this work, we compare both experimentally and theoretically adsorption/desorption cycles of MCDI for desorption at zero voltage as well as for reversed voltage, and compare with results for CDI. To describe the EDL-structure a novel modified Donnan model is proposed valid for small pores relative to the Debye length.

Personalised image-based templates for intra-operative guidance.

The high rate of unplanned perforation, poor fixation, and nerve injury with freehand pedicle screw insertion has led to the use of image-guided navigation systems. Although these improve accuracy, they have several drawbacks that could be overcome by using image-based drilling guide templates. The accuracy of such templates was tested in a cadaveric study of screw placement in the lumbar, thoracic, and cervical regions of the spine. The dimensional stability with autoclaving of duraform polyamide, to be used for manufacturing the guides, was first determined using test specimens. Computed tomography (CT) images were acquired of 4 cadaveric spines, and placement of 4 cervical, 32 thoracic, and 14 lumbar screws was planned. Eighteen personalized drilling guide templates, in four different designs, were built. Orthopaedic surgeons experienced in the freehand techniques used the templates. CT images were acquired to assess placement position with respect to the pedicle. Duraform polyamide was found to be unaffected by sterilization. Two of the template designs facilitated the placement of 20/20 screws without error. Templates can lead to successful screw placement, even in small pedicles, providing their design is optimized for the application area, e.g. with enhanced rotational stabilization.