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At least 55 records · Page 3

Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

With the understanding that sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies

36 MATERIALS SCIENCE↗

Characterizing Structure-Dependent TiS 2 /Water Interfaces Using Deep-Neural-Network-Assisted Molecular Dynamics

As a promising layered electrode material, TiS 2 -based capacitive deionization (CDI) devices for water desalination have attracted significant attention. However, TiS 2 /H 2 O interfacial features, potentially important for device optimization, remain unidentified. Using Deep Potential Molecular Dynamics (DPMD), we characterized distinct aqueous interfaces introduced by four TiS 2 terminations expected to be present as water intercalates into TiS 2 , namely, Armchair, Zigzag, Zigzag-L, and Zigzag-R. First, we assessed important representative physical properties of the system to validate the deep potentials (DPs). DPMD simulations agree well with experiments and first-principles simulations, suggesting the DPs are accurate and reliable. Subsequent simulations of these TiS 2 /water interfaces revealed how TiS 2 surface termination influences the structure of interfacial water. This effect is most evident in the first and second water layers close to the TiS 2 surface, and more pronounced when spontaneous dissociative adsorption of water occurs. The extent of water dissociation on each surface was evaluated using enhanced sampling. Zigzag-L is the only interface where proton transfer from adsorbed water to TiS 2 surface S atoms is thermodynamically and kinetically favored. The coexistence of surface four-fold-coordinated Ti (Ti 4c ) and one-fold-coordinated S (S 1c ) is found to be essential to making proton transfer feasible on the Zigzag-L surface. Furthermore, remaining unprotonated S 1c atoms can act as good proton acceptors after water dissociation. Thus, TiS 2 with Zigzag-L termination may be a surface to avoid in CDI device construction, given that pH fluctuations adversely affect performance. Furthermore, this work provides new understanding of TiS 2 /H 2 O interfacial features that could aid future design and optimization of TiS 2 -based CDI devices for water desalination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trivalent ion overcharging on electrified graphene

We report the structure of the electrical double layer (EDL) formed near graphene in aqueous environments strongly impacts its performance for a plethora of applications, including capacitive deionization. In particular, adsorption and organization of multivalent counterions near the graphene interface can promote nonclassical behaviors of EDL including overcharging followed by co-ion adsorption. In this paper, we characterize the EDL formed near an electrified graphene interface in dilute aqueous YCl 3 solution using in situ high resolution x-ray reflectivity (also known as crystal truncation rod) and resonant anomalous x-ray reflectivity (RAXR). These interface-specific techniques reveal the electron density profiles with molecular-scale resolution. We find that yttrium ions (Y 3+ ) readily adsorb to the negatively charged graphene surface to form an extended ion profile. This ion distribution resembles a classical diffuse layer but with a significantly high ion coverage, i.e., 1 Y 3+ per 11.4 ± 1.6 Å 2 , compared to the value calculated from the capacitance measured by cyclic voltammetry (1 Y 3+ per ~240 Å 2 ). Such overcharging can be explained by co-adsorption of chloride that effectively screens the excess positive charge. The adsorbed Y 3+ profile also shows a molecular-scale gap (≥ 5 Å) from the top graphene surfaces, which is attributed to the presence of intervening water molecules between the adsorbents and adsorbates as well as the lack of inner-sphere surface complexation on chemically inert graphene. We also demonstrate controlled adsorption by varying the applied potential and reveal consistent Y 3+ ion position with respect to the surface and increasing cation coverage with increasing the magnitude of the negative potential. This is the first experimental description of a model graphene-aqueous system with controlled potential and provides important insights into the application of graphene-based systems for enhanced and selective ion separations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Covalent Organic Frameworks for Water Treatment

Covalent organic frameworks (COFs) are an emerging type of porous crystalline material with highly ordered aperture size and tunable structures with designer properties. COFs have been proposed as promising materials for water treatment because of their notable intrinsic properties like excellent chemostability, high surface area, abundant functional sites, and uniform adjustable aperture size. This review focuses on fundamental COF design principles for water treatment (stability, aperture size, and surface functionalization) and the state-of-the-art application of COFs in desalination, organic contaminant sorption, and ion capture. Additional potential promising applications of COFs for water treatment, including solar steam generation, photocatalysis for degradation of organic contaminants, and capacitive deionization are also presented along with an outlook toward future opportunities in the field.

36 MATERIALS SCIENCE↗

Desalination metamodels and a framework for cross-comparative performance simulations

There is an opportunity to save energy and reduce operational expenses when choosing a suitable desalination method aided by computational modeling. Existing models are not conducive to generalized comparisons between different desalination methods. Therefore, the work in this study developed metamodels for six desalination methods, grouped them into thermal and molecular transport families, and validated their predictive performance within 9% difference from published data. This validated framework allowed comparisons of desalination methods at their prescribed ranges of operational conditions that they were designed for. These conditions specify feed salinity ranges of 1.6 to 2.4 g/kg for Capacitive Deionization and Reverse Osmosis (RO), 2.8 to 4.2 g/kg for Electrodialysis, 28 to 42 g/kg for Thermovapor Compression and Humidification-Dehumidification, and 37 to 55 g/kg for Multi-Effect Distillation (MED). Despite different operational conditions, all models exhibit non-linear, positive correlation between energy consumption and system size in response to feed salinity and production rate. The framework is also employed in a cross-comparative analysis between MED and RO whose results suggest that energy intensity for MED is an order of magnitude greater than RO for the same operational conditions, but actual operational costs are comparable. Overall, the framework is ready for deployment in case studies of actual desalination plants.

42 ENGINEERING↗

Effects of Particle Mixing and Gravitational Settling on Charge Transport in Carbon Flow-Electrode Cells

Flowable carbon slurries are actively studied and under development for charge transport in various electrochemical systems including flow capacitors, capacitive deionization cells, semi-solid flow batteries, and lithium extraction. However, much less is known about in operando slurry flow dynamics and their corresponding effect on charge transport. We performed an experimental study of mixing and settling dynamics of slurry electrodes within an electrochemical flow cell during continuous operations. The electrochemical cell consisted of two horizontal co-flowing channels, separated by a cation-exchange membrane (CEM). Here we used high-speed optical imaging of planes parallel to gravity and simultaneous electrochemical measurements. At low flow rates, dense yet dynamic particle beds formed on the bottom electrode in each channel, which unexpectedly yielded the highest currents. This approach enables the operation of the flow cell at low system-average particle concentrations while leveraging gravity-driven particle settling to locally enhance carbon concentrations precisely at the current collector sites. Conversely, high flow rates were characterized by thin particle beds and well-mixed particle flows. In the latter case, the electrodes in closest proximity (located on either side of the CEM) achieved a current higher than the other electrode pairs. The observations have implications for slurry control and electrode designs in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bicarbonate-Carbonate Selectivity through Nanofiltration for Direct Air Capture of Carbon Dioxide

Direct air capture (DAC) of carbon dioxide is one approach among many proposed that is capable of offsetting hard-to-avoid emissions. In previous work, we developed the alkalinity concentration swing (ACS) method, which is driven through concentrating an alkaline solution that has been loaded with atmospheric CO 2 by desalination technologies, such as reverse osmosis or capacitive deionization. Though the ACS is promising in terms of energy usage and implementation, its absorption rate and water requirements are infeasible for a large-scale DAC process. Here, we propose an improvement on the ACS, the bicarbonate-enriched alkalinity concentration swing (BE-ACS), which selects bicarbonate ions from a stream of aqueous alkaline solution that has absorbed atmospheric CO 2 . The bicarbonate-rich stream is then concentrated, which greatly increases its CO 2 partial pressure, and then CO 2 is extracted from solution. We experimentally investigate the use of pressure-driven nanofiltration (NF) membrane-based separation to select bicarbonate ions over carbonate ions. We screen commercial membranes and select one high-performance membrane for detailed studies, quantifying its bicarbonate-carbonate selectivity factor and bicarbonate-passage factor. Feed pH, the combined concentration of aqueous CO 2 , bicarbonate, and carbonate species (or dissolved inorganic carbon), alkalinity, and permeation flux are systematically varied to study NF separation properties. We find that the selectivity factor, which exceeds 30 times in certain regimes, increases with higher feed pH and higher alkalinity. Lastly, the performance metrics of the selected NF membrane are input into a theoretical BE-ACS cycle analysis, and the required energy input and cycle capacity output are evaluated. Ideal cycle energy is found to be as low as around 250 kJ/mol, with opportunities identified for further decreases through process engineering and forward osmosis energy recovery.

animal feed↗

Electrochemical carbon dioxide capture to close the carbon cycle

Electrochemical CO 2 capture technologies are gaining attention due to their flexibility, their ability to address decentralized emissions (e.g., ocean and atmosphere) and their fit in an electrified industry. In the present work, recent progress made in electrochemical CO 2 capture is reviewed. The majority of these methods rely on the concept of “pH-swing” and the effect it has on the CO 2 hydration/dehydration equilibrium. Through a pH-swing, CO 2 can be captured and recovered by shifting the pH of a working fluid between acidic and basic pH. Such swing can be applied electrochemically through electrolysis, bipolar membrane electrodialysis, reversible redox reactions and capacitive deionization. In this review, we summarize main parameters governing these electrochemical pH-swing processes and put the concept in the framework of available worldwide capture technologies. We analyse the energy efficiency and consumption of such systems, and provide recommendations for further improvements. Although electrochemical CO 2 capture technologies are rather costly compared to the amine based capture, they can be particularly interesting if more affordable renewable electricity and materials (e.g., electrode and membranes) become widely available. Furthermore, electrochemical methods have the ability to (directly) convert the captured CO 2 to value added chemicals and fuels, and hence prepare for a fully electrified circular carbon economy.

54 ENVIRONMENTAL SCIENCES↗

Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials

Understanding ion transport in porous carbons is critical for a wide range of technologies, including supercapacitors and capacitive deionization for water desalination, yet many details remain poorly understood. For instance, an atomistic understanding of how ion selectivity is influenced by the molecular shape of ions, morphology of the micropores and applied voltages is largely lacking. In this work, we combined molecular dynamics simulations with enhanced sampling methods to elucidate the mechanism of nitrate and chloride selectivity in subnanometer graphene slit-pores. We demonstrate that nitrate is preferentially adsorbed over chloride in the slit-like micropores. This preferential adsorption was found to stem from the weaker hydration energy and unique anisotropy of the ion solvation of nitrate. Beside the effects of ion dehydration, we found that applied potential plays an important role in determining the ion selectivity, leading to a lower selectivity of nitrate over chloride at a high applied potential. We conclude that the measured ion selectivity results from a complex interplay between voltage, confinement, and specific ion effects-including ion shape and local hydration structure.

36 MATERIALS SCIENCE↗

Addressing Spacer Channel Resistances in MCDI Using Porous and Pliable Ionic Conductors

Membrane capacitive deionization (MCDI) is a unique electrochemical separations platform that allows for energy recovery during electrode regeneration. Similar to other electrochemical separation technologies producing deionized water (e.g. electrodialysis), ohmic resistances in the spacer channel significantly hampers the performance and energy efficiency of the process. This work devised a series of ionomer coated nylon mesh nets to address spacer channel resistances in MCDI. Under constant current operation, the ionomer coated nylon meshes displayed a 300 mV lower cell voltage rise during deionization while sustaining the same deionization rate. Furthermore, energy recovery was improved by 1.4x to 5.5x depending on the saline feed concentration. The lower cell voltage rise during deionization combined with the greater energy recovery with ionomer coated meshes resulted in energy normalized adsorbed salt (ENAS) values that were 2x to 3x greater. Addressing the spacer channel resistances in MCDI allowed for 8% to 19% increase in current density without the cell voltage exceeding 1.6 V—the upper bound set for mitigating parasitic reactions. Operating at higher current density leads to smaller MCDI units for a given deionization requirement and has implications for reducing the capital costs of the MCDI unit.

Palakkal, Varada Menon (ORCID:0000000317038323)↗

Supervisory Control and Data Acquisition for Electrochemical Separation Experimentation

The Python-based program is a laboratory automation tool designed to control and monitor electrochemical systems. The tool was developed for capacitive deionization (CDI) experiments, but it can be used for any system that requires controlled voltage or current segments and multi-parameter monitoring. The program integrates hardware components to run user-defined experimental parameters, providing operational control of a programmable power supply, peristaltic pump, and data acquisition devices. Currently, the program is structured with a workflow that includes an initialization (or pre-run) phase, a main loop, and a post-experiment stabilization (or post-run) phase. The initialization phase prepares and stabilizes the cell, ensuring that the electrodes and solution reach a baseline state before the experiment begins. The main loop consists of multiple voltage segments that repeat, controlling the experiment while recording key parameters such as time, voltage, current, pH, and conductivity. Finally, the post-experiment stabilization phase allows the system to stabilize after the experiment, returning the cell and solution to equilibrium conditions before ending the sequence. The program is designed with four variations, each tailored to different experimental needs. All variations include both the initialization and post-experiment stabilization stages, which run for a set amount of time, voltage, current, and flow rate before and after the main experiment block. The main loop runs for a set number of cycles, as defined by the user input, and each cycle is composed of 2 or 4 segments. The 4 program variations are described as follows: Program 1: The main program includes 2 segments. Each segment is defined to have a set duration, flow rate, voltage, and current. This program measures conductivity, flow rate, voltage, and current. Program 2: The main program expands Program 1 to include 4 segments. Each segment has a specified duration, flow rate, voltage, and current. Like Program 1, it measures conductivity, flow rate, voltage, and current. Program 3: The main program consists of 2 segments, each defined by time, flow rate, voltage, and current. In addition to conductivity, flow rate, voltage, and current, Program 3 collects pH and temperature data through a 4-channel data acquisition device. Program 4: This program independently controls two channels of a multi-channel power supply simultaneously. While conductivity can only be measured for one cell at a time, the dual-channel control makes it possible to operate two cells simultaneously under different voltage/current conditions. The main program includes 2 segments.For each program, all measurements are automatically logged and integrated into a single Excel output file. Data are displayed in numerical format and plotted, both in real time, to track system performance. A key feature of the program is its ability to synchronize all outputs so that every measurement shares a single timestamp, ensuring accurate alignment of voltage, current, pH, conductivity, and pH data.By combining hardware control, real-time monitoring, and unified data collection, this program significantly reduces manual workload and minimizes errors, making it a reliable platform for researchers, engineers, and laboratory technicians conducting CDI experiments, among other electrochemical tests.

Valentino, Lauren [Argonne National Laboratory (AN↗

Intensified Flue Gas Desulfurization Water Treatment for Reuse, Solidification, and Discharge

The goal of this final project report is to summarize the work conducted on project DE-FE0031555. In accordance with the Statement of Project Objectives (SOPO), the University of Kentucky Center for Applied Energy Research (UK CAER) (Recipient) developed a hybrid electrochemical-membrane technology for treating wet flue gas desulfurization (WFGD) blowdown from coal-fired power generation plants that (1) removes government-regulated species and total suspended solids (TSS) via electrocoagulation with solid/liquid separation to avoid further treatments by a biological method specifically for selenium, and (2) reduces total dissolved solids (TDS) in a nanofiltration unit to promote water recycle and reduce freshwater intake. Additional technological configurations were pursued, including (1) nanofiltration combined with zeolite dewatering for a near-zero liquid discharge (ZLD) scenario, and (2) polishing discharge from zeolite dewatering using capacitive deionization (CDI) with 90+% salt rejection to produce water with less than 100ppm TDS for more beneficial use. Project results verified that UK CAER’s hybrid approach addressed the complexities of WFGD blowdown with simplified unit operation at relatively low capital investment by demonstrating: (1) an effective in-situ generated solid sorbent material, green-rust (GR), that specifically removes regulated dissolved species in WFGD blowdown, including selenium, arsenic, and nitrates; (2) a low-cost, high flux nanofiltration treatment that removes both monovalent and divalent species at >80% rejection to adequately provide water recycle and extend the life of FGD equipment by mitigating chloride aided pitting corrosion mechanisms; and (3) a solidification and stabilization process using pozzolanic agents that retain regulated species and satisfy the Resource Conservation and Recovery Act (RCRA) leachate requirements. UK CAER proved electrocoagulation with GR to be an intensified solution for effluent limit guidelines (ELG), and based on preliminary techno-economic analysis (TEA), in comparison to DOE’s Case 1 for Biological Wastewater Treatment that had a purchased equipment cost (PEC) of $\$$5.26 million and a Total plant cost (TPC) of $\$$30.0 million, the EC process had a PEC of $\$$2.67 million and the TPC of $\$$17.0 million. While the electricity consumption for Case 1 was 53 kW, it was 110 kW for the EC process due to dissolving iron for a three-stage reaction design. However, electricity consumption for the EC process could be significantly reduced by adopting a counter-current reactor design for at least a 6-stage chemical reaction operation.

01 COAL, LIGNITE, AND PEAT↗

Experimental Demonstration of Alkalinity Concentration Swing for Direct Air Capture of CO 2

This work constitutes the first lab-scale experimental demonstration of the alkalinity concentration swing (ACS) for direct air capture (DAC) of CO 2 . ACS can be implemented by taking a dilute alkaline solution that has contacted ambient air, and then concentrating it using commercially available desalination technologies. The more concentrated solution has a higher partial pressure of CO 2 relative to the initial solution, allowing the CO 2 to be separated and stored. The ACS approach is based on simple thermodynamics but had never been verified experimentally in terms of extracting CO 2 from air until now. We tested two distinct methods for concentrating the alkaline liquid: reverse osmosis (RO) and capacitive deionization (CDI). We found that to complete the DAC cycle in feasible operating conditions, a bicarbonate-enrichment step needed to be introduced, which selects on bicarbonate ions over carbonate ions. Two approaches for CO 2 extraction to measure the CO 2 yield per amount of water processed by the ACS method were tested. The energy required per amount of CO 2 captured was quantified. We further applied an energy model to study how operating the ACS cycle under different conditions would affect energy requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rheo–Electric Foundations and Engineering of Carbon Slurry Flow Electrodes

Flowable carbon slurry electrodes promise continuous, scalable electrochemical desalination and energy storage when their rheology (flow and stability) and electronic connectivity are jointly optimized. This report integrates six complementary thrusts that we executed under the Laboratory Directed Research and Development (LDRD) project: (i) a fast, ex situ, centrifuge-compatible method to quantify pellet (packed slurry) electronic conductivity, with a validated cell constant (“shape factor”) and quantitative structure–property insights for carbon mixtures; (ii) a controlled circulation study showing that peristaltic pumping can irreversibly alter particle size and morphology over laboratory-relevant durations; (iii) development of a miniature jet pump that preserves particle integrity while achieving entrainment ratios of 2–4 at practical flow rates; (iv) a comprehensive mapping of how a representative non-ionic surfactant (Tween 20) collapses the carbon gel network, separating network-percolation losses from intrinsic particle contact resistance; (v) in-situ visualization revealing how gravitational settling and flow-driven mixing compete to control charge transport, with dynamic bed layers preventing saturation while achieving 30-fold local concentration enhancement; and (vi) a simple, widely adoptable fabrication route to structured, gas-nitrided titanium nitride (TiN) titanium current collectors that dramatically lower interfacial losses and enable geometry-driven performance gains. Together, these results provide a coherent toolchain and design rules to accelerate formulation screening, de-risk device prototyping, and standardize characterization for carbon slurry electrodes in flow-electrode capacitive deionization (FCDI), electrochemical flow capacitor (EFC), and related systems.

25 ENERGY STORAGE↗

Electrodeionization Salt Removal from Water

This project developed a method to selectively extract sodium (Na) from complex, mission-relevant wastewaters using electricity as a driving force. The team investigated capacitive deionization (CDI), which has been used for general desalination but not for selective removal of Na. Three tasks supported this overall aim: designing and building a reactor and electrodes, engineering absorption and desorption parameters, and investigating varying water compositions and sources. Potential benefits of this approach include integrating into existing Environmental Control & Life Support Systems (ECLSS) treatment trains, reducing salinity for hydroponic installations, and producing food preservatives. Significant accomplishments, including building new reactors and characterizing their optimal operations and applications, advance the frontier of in-situ resource utilization for planetary habitation.

Luke Roberson↗

System and method for high efficiency electrochemical desalination

The present disclosure relates to a capacitive deionization (CDI) system for desalinating salt water. The system may have a capacitor formed by spaced apart first and second electrodes, which enable a fluid flow containing salt water to pass either between them or through them. An input electrical power source is configured to generate an electrical forcing signal between the two electrodes. The electrical forcing signal represents a periodic signal including at least one of voltage or current, and which can be represented as a Fourier series. One component of the Fourier series is a constant, and a second component of the Fourier series is a sinusoidal wave of non-zero frequency which has the highest amplitude of the additive components of the Fourier series. The amplitude of the sinusoidal wave component is between 0.85 and 1.25 times the amplitude of the periodic signal.

Hawks, Steven↗

Compressible foam electrode

A foam electrode comprising surface treatment by the steps of: 1) impregnating soft compressible polymeric foams with a conductive coating via sequential infiltration synthesis and 2) functionalizing the chemically altered voids with an ultrathin redox coating to enhance capacitive deionization (CDI). The redox coating will allow treated foam to absorb ions under the application of a bias, and mechanical compression/decompression. The CDI apparatus uses the void volume of the foam in the uncompressed state to flow liquids through it while the compressed state is used to enhance desalination by limiting the diffusion pathways for the ions to find an adsorption surface.

Young, Matthias John↗

Understanding and Manipulating Counterion Condensation within Charged Polymer Electrolytes for Selective and Low Resistant Membrane Separations

Polymeric ion-exchange membranes are found at the heart of numerous electrochemical systems spanning separations (electrodialysis and membrane capacitive deionization) and energy conversion and storage (flow batteries, fuel cells, and electrolyzers). The ion-exchange membrane separators need to be ion conducting but electron insulating, and in many scenarios selective for a particular ion to conduct. Because of their polymeric nature, the molecular architectures of ion-exchange membranes lack the molecular precision found in many inorganic materials. Plus, they contain numerous structural defects that impede ionic transport. As a result of their poor structure, it has been difficult to carefully probe the underlying physics that governs ion transport in ion-exchange membranes. We investigated counterion condensation phenomena in ion-exchange membranes and correlated it to bulk ionic charge transport and selectivity in precisely defined and long-range ordered materials afforded through the principles of directed self-assembly. A multi-faceted approach spanning i.) advanced metrology, two-dimensional atomic force microscopy, x-ray scattering, and ion-exchange equilibria, and ii.) molecular simulations (classical molecular dynamics and ab-inito molecular dynamics) that bridge multiple time and length scales, were employed to correlate the extent of counterion condensation to ionic conductivity and selectivity. After uncovering the extent of the condensation phenomena in this project, new macromolecular chemistries were employed to manipulate the ion pairing interactions of the condensed counterions to tethered ions on the polymer backbone so more facile and selective conduction rates can be attained. The research has aided in the rational design of polymeric ion-exchange membrane separators with high current density for electrochemical systems and subsequently better energy efficiency.

36 MATERIALS SCIENCE↗