Aqueous Iron Research Articles

A strategy of consistent X-ray and neutron double-difference pair distribution function analysis of nanoparticle dispersions

AbstractIt has been demonstrated that the X-ray pair distribution function (PDF) formalism allows for the identification of very small signal contributions in multi-component systems by the difference and double-difference PDF (dd-PDF) approach. Due to their stronger interaction with light elements compared to X-rays, neutrons are often beneficial or complementary for the characterization of modern materials. Here, it is demonstrated that the dd-PDF strategy previously developed for X-ray PDF data can successfully be applied to neutron PDF data despite much lower count rates compared to X-rays. The dd-PDF strategy was employed for the investigation of aqueous iron oxide nanoparticle (IONP) dispersions. At the Near and InterMediate Range Order Diffractometer (NIMROD) at ISIS, the IONPs could even be investigated in pure water, whereas at the Nanoscale Ordered Materials Diffractometer (NOMAD) at SNS, heavy water had to be used, but additional information could be retrieved from modelling the data of IONP powder in the dry state and with adsorbed (heavy) water. The simple and robust approach can easily be adapted for the use in other multicomponent systems, like heterogenous catalysts or battery systems. Graphical Abstract

Improving the adsorption properties of low surface area hardwood biochar for the removal of Fe+ and PO₄3- from aqueous solution.

Biochar produced from wood residues may provide a new method and material for managing the environment, particularly in terms of carbon sequestration and contaminant remediation. Additionally, biochar produced from wood residues is free of chemical fertilizers, likewise in rice straw, wheat straw, corn straw, etc. This study investigated the removal of iron from aqueous solutions by a novel low-cost and eco-friendly biochar made from hardwood trees and modified by adding MgCl2 for effective phosphate removal. Optimal adsorption conditions were determined through studies of adsorption time, pH, and adsorbent dosage. Batch equilibrium isotherm and kinetic experiments and pre/post-adsorption characterizations using FESEM-EDS, XRD, and FTIR suggested that the presence of carboxyl group elements and colloidal and nano-sized MgO (periclase) particles on the biochar surface were the main adsorption sites for aqueous iron and phosphate respectively. In this study, the HW and MgO-HW biochar showed excellent Dubinin-Radushkevich isotherm (D-R) maximum adsorption capacities of 289.45 and 828.82mg/g for iron and phosphate. The kinetic study for iron and phosphate adsorption was described well by pseudo second-order model and pseudo second-order model respectively. The HW biochar and the prepared MgO-HW biochar exhibited commendable iron adsorption (98.25%) performance at 10 pH units and phosphate (96.22%) at pH 6 respectively. Thus, this research reveals a waste-to-wealth strategy by converting hardwood waste into mineral-biomass biochar with excellent Fe and P adsorption capabilities and environmental adaptability.

Colorimetric Detection of Aqueous N-Nitrosodimethylamine via Photonitrosation of a Naphtholsulfonate Indicator.

N-Nitrosamines are contaminants found throughout the environment, including in drinking water, and many nitrosamines are likely potent carcinogens. Correspondingly, there is a need for rapid and cost-effective in-field detection methods that can provide timely information about their contamination levels in water. This study details a colorimetric assay for detecting aqueous N-nitrosodimethylamine (NDMA) by photochemical nitrosation of a commercial naphtholsulfonate, to offer an attractive alternative to traditional laboratory-based analysis. The resulting naphthoquinone-oxime coordinates to aqueous iron(II) ions to form a green complex, allowing for direct visual detection. Characterization via Mössbauer and electron paramagnetic resonance (EPR) spectroscopy, alongside single-crystal structure determination, provides comprehensive structure information on the iron indicator complex. Optimization of detection conditions, including UV irradiation and response times, led to an improved colorimetric detection method with a limit of detection of 0.66 ppm for NDMA. The practical applicability and selectivity of this colorimetric detection scheme make it a promising candidate for the development of field-deployable sensors for NDMA in environmental water samples.

Comparison between Co(II) and Ni(II) cycling at goethite-water interfaces: Interplay with Fe(II)-catalyzed recrystallization

Cobalt (Co) and nickel (Ni) are critical metals for modern renewable energy technologies as well as essential micronutrients for terrestrial plant health and marine primary production. Both metals are commonly surface-adsorbed onto and/or structurally-incorporated into iron (oxyhydr)oxide minerals, such as goethite (α-FeOOH), that are ubiquitously present in soils and sediments at the Earth’s surface. In sub- and anoxic environments, aqueous ferrous iron (Fe(II)) generated from dissimilatory Fe(III) reduction can induce the recrystallization of goethite and subsequently influences the speciation and mobilization of associated metals, e.g., Co(III) being reduced to Co(II). While it is generally considered that divalent Co and Ni behave similarly at goethite-water interfaces, there lacks a direct comparison of their cycling through goethite in response to Fe(II)-catalyzed recrystallization. Here, under circumneutral anoxic conditions with and without addition of aqueous Fe(II), we performed batch reaction experiments on Co(II)-substituted goethite and Co(II) and Ni(II) sorption experiments on pure goethite. The redox state and coordination environment of Co associated with goethite were determined using high energy resolution fluorescence detected X-ray absorption spectroscopy at the Co K-edge, and the distribution of solid-bound Co and Ni in goethite following sorption was revealed by sequential dissolution. Our results show that substitution of Co(II) for Fe(III) in goethite has less negative feedback on Fe(II)-catalyzed recrystallization than Ni(II), which may be related to their differing structural distortions as evidenced by EXAFS. In the absence of Fe(II), aqueous Co(II) is more favourably adsorbed onto and incorporated deeper into goethite than Ni(II), suggesting that Co(II) is more structurally compatible with goethite. The presence of Fe(II) markedly enhances the structural incorporation of both Co(II) and Ni(II) as a result of goethite recrystallization, which in turn can be inhibited by the accumulation of metals at the mineral surface. Furthermore, structurally-incorporated Co(II) is more difficult to be released back into solution (i.e. sum of aqueous and extract fractions) than Ni(II) during Fe(II)-catalyzed goethite recrystallization. Overall, our work highlights the significant differences between Co(II) and Ni(II) in their cycling at goethite-water interfaces and intricate interplay with Fe(II)-catalyzed recrystallization. This improves our understanding of their mobilization and distribution in anoxic goethite-rich systems and can provide useful insights for their enrichment and extraction from natural and artificial laterites generated from the enhanced weathering of ultramafic mine tailings.

Treatment of gestational diabetes by Acroptilon repens leaf aqueous extract green-formulated iron nanoparticles in rats

Abstract In recent years, researchers have been utilizing nanotechnology more and more to study diabetic complications, with a particular emphasis on prevention and treatment. In this investigation, we analyzed the effects of Acroptilon repens extract on iron nanoparticles (FeNPs), which demonstrated significant anti-diabetic characteristics both in living organisms and in laboratory settings. To assess the effectiveness of the FeNPs produced through the interaction of iron salt solutions stabilized by A. repens extract, we utilized a range of methodologies. The FeNPs were manufactured in a spherical shape, ranging in size from 10 to 60 nm. During the in vivo experiment, gestational diabetes was induced through streptozotocin (STZ) intraperitoneal injection. The animals were then categorized into four groups: FeNPs-60 μg/kg group, FeNPs-120 μg/kg group, normal pregnancy group, and gestational diabetes mellitus group (n = 10). FeNPs were administered intragastrically for 25 days. On the final day, the levels of ALP, AST, ALT, and blood glucose in the serum samples were assessed. Following tissue processing, 5 μm liver sections were prepared and the overall volume of the hepatic arteries, bile ducts, central vein, portal vein, sinusoids, hepatocytes, and liver, were approximated. FeNPs have the potential to reduce the elevated levels of ALP and AST enzymes. In gestational diabetes rats, the administration of FeNPs lead to a decrease in blood glucose levels. The administration of STZ significantly increased the volume of sinusoids and hepatocytes. However, after the treatment with a high dose of FeNPs, there was a notable decrease in their volume. In contrast, the volume of the bile ducts and portal vein remained unchanged in the experimental groups. Nevertheless, the volume of the hepatic arteries and central vein exhibited changes due to the presence of FeNPs. The current study showcases the hepatoprotective and anti-diabetic characteristics of FeNPs, providing a potential option as a supplement to prevent gestational diabetes mellitus while also offering hepatoprotective benefits.

Enhancing Proton Co-Intercalation in Iron Ion Batteries Cathodes for Increased Capacity.

Recently, aqueous iron ion batteries (AIIBs) using iron metal anodes have gained traction in the battery community as low-cost and sustainable solutions for green energy storage. However, the development of AIIBs is significantly hindered by the limited capacity of existing cathode materials and the poor intercalation kinetic of Fe2+. Herein, we propose a H+ and Fe2+ co-intercalation electrochemistry in AIIBs to boost the capacity and rate capability of cathode materials such as iron hexacyanoferrate (FeHCF) and Na4Fe3(PO4)2(P2O7) (NFPP). This is achieved through an electrochemical activation step during which a FeOOH nanowire layer is formed in situ on the cathode. This layer facilitates H+ co-intercalation in AIIBs, resulting in a high specific capacity of 151 mAh g-1 and 93% capacity retention over 500 cycles for activated FeHCF cathodes. We found that this activation process can also be applied to other cathode chemistries, such as NFPP, where we found that the cathode capacity is doubled as a result of this process. Overall, the proposed H+/Fe2+ co-insertion electrochemistry expands the range of applications for AIBBs, in particular as a sustainable solution for storing renewable energy.

Dimerization of Fe(III) Ion in an Aqueous Medium: Mechanistic Modelling and Effects of Ligands.

Aqueous iron solutions generally undergo spontaneous hydrolysis followed by aggregation resulting in the precipitation of nanocrystalline oxyhydroxide minerals. The mechanism of nucleation of such multinuclear oxyhydroxide clusters are unclear due to limited experimental evidence. Here, we investigate the mechanistic pathway of dimerization of Fe(III) ions using density functional theory (DFT) in aqueous medium considering effects of other ligands. Two hydrolyzed monomeric Fe(III) ions in aqueous medium may react to form two closely related binuclear products, the μ-oxo and the dihydroxo Fe2 dimer. Our studies indicate that the water molecules in the second coordination sphere and those co-ordinated to the Fe(III) ion, both participate in the dimerization process. The proposed mechanism effectively explains the formation of dihydroxo and μ-oxo Fe2 dimers with interconversion possibilities, for the first time. Results show, with only water molecules present in the second co-ordination sphere, dihydroxo Fe2 dimer is the thermodynamically and kinetically favored product with a low activation free energy. We calculated the step-wise reaction free energies of dimerization in the presence of nitrate ions in the first and second coordination sphere of Fe(III) ion separately, which shows that with nitrate ions in the second co-ordination sphere, the μ-oxo Fe2 dimer is the kinetically favored product.

The Influence of Aqueous Iron on River Sand’s Arsenic Adsorption: Characteristics and Mechanisms

Iron-containing minerals are key factors controlling arsenic (As) transport in groundwater environments. However, few studies have observed the effect of aqueous Fe [Fe(aq)] on As behavior in a water environment. In this study, river sand in the riparian zone was collected for batch experiments to analyze the effect of Fe(aq) on the adsorption of As on river sand, utilizing characterization analyses to identify the reaction mechanism. The results showed that (1) as the concentration of Fe(aq) in the reaction system increased from 0.1 to 20 mg/L, the equilibrium adsorption capacity (Qe) of river sand for As(III) and As(V) gradually increased. For concentrations of Fe(aq) equal to or greater than 1 mg/L, the Qe for As(V) exceeds that for As(III), whereas at a Fe(aq) concentration of 0.1 mg/L, the Qe for As(III) is higher than that for As(V). (2) Compared to the reaction system without added Fe(aq), the adsorption of As(V) onto river sand was inhibited, while the adsorption of As(III) was enhanced under conditions with low concentrations (0.1, 1 mg/L) of Fe(aq). (3) At higher Fe(aq) concentrations (5, 20 mg/L), the adsorption of both As(V) and As(III) by river sand was more effective than in systems without Fe(aq). Characterization tests confirmed this, while Fe(II) reduced As(V), and Fe(aq) adhered to the surface of river sand to form Fe(OH)3 colloids, thereby facilitating the adsorption of As onto river sand.

Phosphonate-based iron complex for a cost-effective and long cycling aqueous iron redox flow battery

A promising metal-organic complex, iron (Fe)-NTMPA2, consisting of Fe(III) chloride and nitrilotri-(methylphosphonic acid) (NTMPA), is designed for use in aqueous iron redox flow batteries. A full-cell testing, where a concentrated Fe-NTMPA2 anolyte (0.67 M) is paired with a Fe-CN catholyte, demonstrates exceptional cycling stability over 1000 charge/discharge cycles, and noteworthy performances, including 96% capacity utilization, a minimal capacity fade rate of 0.0013% per cycle (1.3% over 1,000 cycles), high Coulombic efficiency and energy efficiency near 100% and 87%, respectively, all achieved under a current density of 20 mA·cm-². Furthermore, density functional theory unveils two potential coordination structures for Fe-NTMPA2 complexes, improving the understanding between the ligand coordination environment and electron transfer kinetics. When paired with a high redox potential Fe-Dcbpy/CN catholyte, 2,2′-bipyridine-4,4′-dicarboxylic (Dcbpy) acid and cyanide (CN) ligands, Fe-NTMPA2 demonstrates a notably elevated cell voltage of 1 V, enabling a practical energy density of up to 9 Wh/L.

Mycofiltration of Aqueous Iron (III) and Imidacloprid Solutions, and the Effects of the Filtrates on Selected Biomarkers of the Freshwater Snail Helisoma duryi

To alleviate the burden of water contamination, a newly developed form of bioremediation known as mycofiltration can be employed. Mycofiltration is an environment-friendly technology involving the treatment of contaminated water by passing it through a network of saprophytic fungal mycelium. A mycofilter made of Pleurotus ostreatus was used for the removal of iron (III) and imidacloprid from aqueous solutions. Batch mycofiltration, at a dosage of 1 g of mycofilter per 50 mL, was performed on iron (III) solutions of different concentrations (0.99, 10.7, 22.9, and 27.72 mg/L) and pH (3.3, 7 and 11). For column mycofiltration, the mycofilter was packed into pyrex columns (3.3 × 15 cm) to desired bed heights. Iron (III) and imidacloprid solutions of 18.99 mg/L and 234.70 ng/L, respectively, were filtered at a constant flow rate. Thereafter, Helisoma duryi snails were exposed for 96 h to the respective filtrates, and their catalase and acetylcholinesterase activities were assessed. Batch mycofiltration showed iron (III) removal rates as high as 85%. Column mycofiltration showed removal rates of 94 and 31% for iron (III) and imidacloprid, respectively. Catalase activity was significantly reduced (p < 0.05) in the snails exposed to iron (III) or imidacloprid filtrates, compared to the snails exposed to the non-mycofiltered media. A significantly higher acetylcholinesterase activity was induced by iron (III) filtrates in comparison with the non-mycofiltered media (p < 0.05). There were no significant differences in acetylcholinesterase activity (p > 0.05) in the snails exposed to mycofiltered and non-mycofiltered imidacloprid media. Mycofilter characterisation using Fourier Transform Infrared Spectrophotometry revealed significant changes in transmittance intensity in the mycofilters used for the iron (III) vs the ones used for the imidacloprid solutions. Mycofiltration was found to improve water quality although iron (III) was removed more effectively than imidacloprid.

Role of Water during the Early Stages of Iron Oxyhydroxide Formation by a Bacterial Iron Nucleator.

Understanding the nucleation of iron oxides and the underlying hydrolysis of aqueous iron species is still challenging, and molecular-level insights into the orchestrated response of water, especially at the hydrolysis interface, are lacking. We follow iron(III) hydrolysis in the presence of a synthetic bacterial iron nucleator, which is a magnetosome membrane specific peptide, by using a constant pH titration technique. Three distinct hydrolysis regimes were identified. Interface-selective sum frequency generation (SFG) spectroscopy was used to probe the interfacial reaction and water in direct contact with the peptide. SFG data reveal that iron(III) species react quickly with interfacial peptides while continuously enhancing water alignment into the later stages of hydrolysis. The gradually aligning water molecules are associated with initially promoted (regimes I and II) and later suppressed (regime III) hydrolysis after the saturation of water alignment has occurred until regime II. These interfacial insights are crucial for understanding the early stage of iron oxide biomineralization.

A Double‐ligand Chelating Strategy to Iron Complex Anolytes with Ultrahigh Cyclability for Aqueous Iron Flow Batteries

AbstractAqueous all‐iron flow batteries (AIFBs) are attractive for large‐scale and long‐term energy storage due to their extremely low cost and safety features. To accelerate commercial application, a long cyclable and reversible iron anolyte is expected to address the critical barriers, namely iron dendrite growth and hydrogen evolution reaction (HER). Herein, we report a robust iron complex with triethanolamine (TEA) and 2‐methylimidazole (MM) double ligands. By introducing two ligands into one iron center, the binding energy of the complex increases, making it more stable in the charge‐discharge reactions. The Fe(TEA)MM complex achieves reversible and stable redox between Fe3+ and Fe2+, without metallic iron growth and HER. AIFBs based on this anolyte perform a high energy efficiency of 80.5 % at 80 mA cm−2 and exhibit a record durability among reported AIFBs. The efficiency and capacity retain nearly 100 % after 1,400 cycles. The capital cost of this AIFB is $ 33.2 kWh−1 (e.g., 20 h duration), cheaper than Li‐ion battery and vanadium flow battery. This double‐ligand chelating strategy not only solves the current problems faced by AIFBs, but also provides an insight for further improving the cycling stability of other flow batteries.

A Double-ligand Chelating Strategy to Iron Complex Anolytes with Ultrahigh Cyclability for Aqueous Iron Flow Batteries.

Aqueous all-iron flow batteries (AIFBs) are attractive for large-scale and long-term energy storage due to their extremely low cost and safety features. To accelerate commercial application, a long cyclable and reversible iron anolyte is expected to address the critical barriers, namely iron dendrite growth and hydrogen evolution reaction (HER). Herein, we report a robust iron complex with triethanolamine (TEA) and 2-methylimidazole (MM) double ligands. By introducing two ligands into one iron center, the binding energy of the complex increases, making it more stable in the charge-discharge reactions. The Fe(TEA)MM complex achieves reversible and stable redox between Fe3+ and Fe2+ , without metallic iron growth and HER. AIFBs based on this anolyte perform a high energy efficiency of 80.5 % at 80 mA cm-2 and exhibit a record durability among reported AIFBs. The efficiency and capacity retain nearly 100 % after 1,400 cycles. The capital cost of this AIFB is $ 33.2 kWh-1 (e.g., 20 h duration), cheaper than Li-ion battery and vanadium flow battery. This double-ligand chelating strategy not only solves the current problems faced by AIFBs, but also provides an insight for further improving the cycling stability of other flow batteries.

Selective lithium extraction from brine via chemical reduction of iron phosphate with aqueous iron compounds

Lithium production has increased with surges in demand. Iron based redox mediators were developed to extract Li+ from brine, showing promise using brines with low amounts of lithium and high concentrations of competing ions.

Screening of First-Row Transition Metal Complexes for Aqueous Redox Flow Batteries: Experimental and Density Functional Theory Approaches

The development of redox flow batteries took new directions in the last decades. From initial metal-based systems, it evolved towards organic and hybrid approaches in aqueous media. Furthermore, redox targeting flow batteries are an emerging alternative to the traditional redox flow battery architecture which offer improved energy density via an added electroactive solid ‘booster’. Whatever the system, there is a need of soluble electroactive species with potentials allowing large cell potentials within the water stability window or imperative redox potentials matching between soluble redox mediator and the solid for redox targeting. Transition metal complexes are a promising class of redox electroactive centers due to the tunability of their solubility and electrochemical potential, and the ability to take into account sustainability1. Recent reports underlined for instance that either the modification of the ligand2 or using heteroleptic complexes3, can lead to iron complexes with solubilities higher than 1 M and potentials higher than 1 V vs SHE. Furthermore, reliable and time-efficient prediction tools for the redox potentials of transition metal complexes are needed to help the search for new potential systems. While density functional theory usually provides a good trade-off between computational cost and accuracy, calculations on transition metal complexes often result in large errors. We thus developed a procedure and compared different solvation methods and levels of theory using an initial experimental data set based on aqueous iron complexes with bidentate ligands (Figure 1).In the present contribution, we will illustrate this coordination approach through a screening of new complexes based on non-toxic and affordable transition metal complexes. In this perspective, electrochemical characterization at different pH, coupled with NMR and UV-Visible studies will be presented, to screen for new candidates as electrolyte in redox flow batteries. Finally, we will show how the calculations corrected using a simple linear regression using training data yields a good prediction of redox potentials (mean average error =0.09 V).

Eggshell-Mediated Hematite Nanoparticles: Synthesis and Their Biomedical, Mineralization, and Biodegradation Applications

The present study demonstrates the synthesis of phase pure hematite (α-Fe2O3) nanoparticles (NPs) using collagen protein and calcium carbonate extracted from eggshell membranes and eggshells, respectively, as organic additives. To test the influence of organic additives on the quality of the resulting NPs, the amount of eggshell powder was varied between 1 to 5 g in aqueous iron nitrate solution. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and RAMAN analysis confirmed the formation of hematite NPs without any impurities. FTIR spectra revealed the presence of polyphenolic constituents on the surface of the resulting NPs as stabilizers, which may potentially be responsible for the observed antioxidant and antibacterial properties. Furthermore, the stable phase and the presence of low defects divulged the high hardness value (~983 HV) and fracture toughness (8.59 MPa m1/2), which can be exploited for bone implantation. The FE-SEM results demonstrate the formation of spherical particles, which are well-separated NPs. The results of a biodegradation study which was carried out in phosphate-buffered saline (PBS) revealed that the as-prepared NPs retained their hardness even after 72 h of soaking. These prepared NPs showed 95% radical scavenging activity (RSA) and were good carriers against S. aureus bacteria. Moreover, the SEM images of the mineralization of iron oxide NPs confirmed the formation of new bone. After 5 weeks, all pores were filled, and the minerals were deposited on the surfaces of the scaffolds.

Mathematical model of magnetic hyperthermia therapy for breast tumour via intratumoural injection of iron–platinum nanoparticles

The present study explores magnetic hyperthermia for a treatment of a breast tumour with a surrounding healthy breast gland region and overlying fat and skin regions. A mathematical model that utilizes the Brinkman–Forchheimer-extended Darcy equations and non-Newtonian (Carreau–Yasuda) constitutive equation is constructed for the intratumoural injection of an aqueous iron–platinum (FePt) nanoparticle suspension, blood perfusion through the tissue regions, and the temperature and nanoparticle distributions during the process of hyperthermia therapy. The equations governing nanofluid flow, heat transfer and the suspended and deposited nanoparticle volume fractions are solved numerically via the finite element technique, and numerical results are computed in the FreeFEM++ software. Using the obtained results, the impact of the Reynolds number, nanoparticle diameter and haematocrit on the efficacy of magnetic hyperthermia therapy is investigated. The results revealed that the tissue penetration of nanoparticles is more pronounced when the red blood cell concentration and nanoparticle diameter are lower. Furthermore, the required duration for effective magnetic hyperthermia and the healthy tissue damage decrease with increasing haematocrit and nanoparticle diameter.

Kinetic and Parametric Analysis of the Separation of Ultra-Small, Aqueous Superparamagnetic Iron Oxide Nanoparticle Suspensions under Quadrupole Magnetic Fields.

Superparamagnetic iron oxide nanoparticles (SPIONs) have gathered tremendous scientific interest, especially in the biomedical field, for multiple applications, including bioseparation, drug delivery, etc. Nevertheless, their manipulation and separation with magnetic fields are challenging due to their small size. We recently reported the coupling of cooperative magnetophoresis and sedimentation using quadrupole magnets as a promising strategy to successfully promote SPION recovery from media. However, previous studies involved SPIONs dispersed in organic solvents (non-biocompatible) at high concentrations, which is detrimental to the process economy. In this work, we investigate, for the first time, the magnetic separation of 20 nm and 30 nm SPIONs dispersed in an aqueous medium at relatively low concentrations (as low as 0.5 g·L-1) using our custom, permanent magnet-based quadrupole magnetic sorter (QMS). By monitoring the SPION concentrations along the vessel within the QMS, we estimated the influence of several variables in the separation and analyzed the kinetics of the process. The results obtained can be used to shed light on the dynamics and interplay of variables that govern the fast separation of SPIONs using inexpensive permanent magnets.

Reversible Covalent Binding of Desferrioxamine B (DFOB) to Polystyrene Microspheres for the Chelation of Aqueous Iron Citrate

Reversible Covalent Binding of Desferrioxamine B (DFOB) to Polystyrene Microspheres for the Chelation of Aqueous Iron Citrate

Modeling the Coulombic Efficiency of the Aqueous Iron Electrode

The aqueous iron electrode is attractive for large-scale energy storage because of its long life and low materials cost. The redox potential of the Fe ↔ Fe2+ reaction is approximately 50 mV negative of that of the hydrogen evolution reaction. Hydrogen evolution therefore causes self discharge of the iron electrode during rest and competes with the iron reaction during charge. Here we model the effect of electrode design and cell operation on the coulombic efficiency of charging the iron electrode at modest charging rates (<C/20). Kinetic parameters (exchange current density and transfer coefficients) for the iron dissolution-precipitation reaction and for the hydrogen evolution reaction are estimated from experimental measurements of electrode overpotential and hydrogen generation rate. The volume change from Fe(OH)2 to Fe metal results in a significant increase in porosity during charge and results in change in electrochemically active surface area. The porous-electrode model includes transport in the electrolyte, Butler-Volmer kinetics, and change in volume and surface area.The model provides a theoretical explanation for experimental observations that coulombic efficiency decreases with decreasing charge rate, and that coulombic efficiency is lower in thicker electrodes. We then use the model to explore the impact for large-format cells of electrode size and design on coulombic efficiency.