Mn-doped Sequentially Electrodeposited Co-based Oxygen Evolution Catalyst for Efficient Anion Exchange Membrane Water Electrolysis.

Designing high-performance and durable oxygen evolution reaction (OER) catalysts is important for green hydrogen production through anion exchange membrane water electrolysis (AEMWE). Herein, a series of Mn-doped Co-based OER catalysts supported on FeOxHy (FCMx) are presented to enhance the OER activity. Mn doping effectively reduces the size of the Co oxide particles, thereby augmenting the active surface area. Moreover, Mn doping induces the creation of oxygen vacancies, leading to an efficient structural conversion during the OER, which is confirmed via in situ Raman spectroscopy. Under optimal conditions, the catalyst exhibits an overpotential of 234.4 mV at 10 mA cm-2 and a Tafel slope of 37.2 mV dec-1 under half-cell conditions. The AEMWE single-cell system demonstrates a current density of 1560 mA cm-2 at 1.8 V at 60 °C with a degradation rate of 0.4 mV h-1 for 500 h at 500 mA cm-2. Our development of a robust OER catalyst represents notable progress in the field of nonprecious-metal water electrolysis, marking a step toward cost-effective green hydrogen production.

Electrochemical production of hydroxylamine from nitrate on metal electrodes: A comparative study of selectivity and efficiency.

Despite the great potential of electrochemical nitrate reduction as a hydroxylamine production method, this strategy has not been sufficiently examined, and the effects of electrode material type on the selectivity and efficiency of this reduction remain underexplored. To bridge this gap, the present study evaluated six metals (Ag, Cu, Ni, Sn, Ti, and Zn) as cathode materials for the electrochemical reduction of nitrate to hydroxylamine, showing that the selectivity of hydroxylamine production was maximal for Sn, while the corresponding faradaic and energy utilization efficiencies were maximal for Ti. Although all tested materials favored nitrate reduction over hydrogen evolution, the disparity in the onset potentials of these reactions did not adequately explain the variations in nitrate removal efficiency, which was found to be influenced by material resistance and charge-transfer properties. The rate constants of elementary nitrate reduction steps determined from the time-dependent concentrations of nitrate and its reduction products (nitrous acid, hydroxylamine, and ammonium) were used to calculate the selectivity and efficiency of hydroxylamine production for each electrode. In turn, these selectivities and efficiencies were correlated with the density functional theory-computed adsorption energies of a key hydroxylamine precursor on different electrodes to afford a volcano-type plot with Ti and Sn at its pinnacle. Thus, this study introduces valuable descriptors and methods for the further screening of electrocatalysts for hydroxylamine generation and the establishment of more environmentally friendly hydroxylamine production techniques utilizing sustainable electricity.

Translating the Optimized Durability of Co-Based Anode Catalyst into Sustainable Anion Exchange Membrane Water Electrolysis.

Development of robust electrocatalysts for the oxygen evolution reaction (OER) underpins the efficient production of green hydrogen via anion exchange membrane water electrolysis (AEMWE). This study elucidates the factors contributing to the degradation of cobalt-based (Co-based) OER catalysts synthesized via electrodeposition, thus establishing strategic approaches to enhance their longevity. Systematic variations in the electroplating process and subsequent heat treatment reveal a delicate balance between catalytic activity and durability, substantiated by comprehensive electrochemical assessments and material analyses. Building upon these findings, the Co-based anode is successfully optimized in the AEMWE single-cell configuration, showcasing an average degradation rate of 0.07 mV h-1 over a continuous operation for 1500 h at a current density of 1 A cm-2 .

Surface Electrochemistry of Carbon Electrodes and Faradaic Reactions in Capacitive Deionization.

Recent advances in electrochemical desalination techniques have paved way for utilization of saline water. In particular, capacitive deionization (CDI) enables removal of salts with high energy efficiency and economic feasibility, while its applicability has been challenged by degradation of carbon electrodes in long-term operations. Herein, we report a thorough investigation on the surface electrochemistry of carbon electrodes and Faradaic reactions that are responsible for stability issues of CDI systems. By using bare and membrane CDI (MCDI) as model systems, we identified various electrochemical reactions of carbon electrodes with water or oxygen, with thermodynamics and kinetics governed by the electrode potential and pH. As a result, a complete overview of the Faradaic reactions taking place in CDI was constructed by tracing the physicochemical changes occurring in CDI and MCDI systems.

Descriptive Role of Pt/PtOx Ratio on the Selective Chlorine Evolution Reaction under Polarity Reversal as Studied by Scanning Electrochemical Microscopy.

This study investigated competing chlorine evolution reaction (ClER) and oxygen evolution reaction (OER) on Pt electrodes under variable polarity reversal intervals (±16.7 mA cm-2, 30-600 s) in the context of distinctive roles of Pt(0) and PtOx on the surface in dilute (0.1 M) NaCl solutions. The substrate generation/tip collection mode of scanning electrochemical microscopy (SECM) quantified the current efficiency (CE) of ClER with a large tip-to-substrate distance (>500 µm) to avoid intervention of bubbles and spatial variations. Surface interrogation SECM using [Ru(NH3)6]2+/3+ coupled with X-ray photoelectron spectroscopy (XPS) identified the Pt4+-enriched surface of PtOx with a bilayer structure to give more efficient regeneration of Pt(0) under the shorter reversal interval. The in situ SECM complemented bulk electrolysis and XPS to demonstrate that ClER on Pt(0) and OER on PtOx primarily determine the CE of ClER, in agreement with a kinetic model. The descriptive role of surface Pt/PtOx ratio rationalized the enhanced selectivity for ClER upon the polarity switching, being independent on a scaling relationship. The current reversal (not allowed to IrO2 electrodes) also alleviated calcareous scale deposit in the electrolyte with hardness.

High chlorine evolution performance of electrochemically reduced TiO2 nanotube array coated with a thin RuO2 layer by the self-synthetic method.

Recently, reduced TiO2 nanotube arrays via electrochemical self-doping (r-TiO2) are emerging as a good alternative to conventional dimensionally stable anodes (DSAs) due to their comparable performance and low-cost. However, compared with conventional DSAs, they suffer from poor stability, low current efficiency, and high energy consumption. Therefore, this study aims to advance the electrochemical performances in the chlorine evolution of r-TiO2 with a thin RuO2 layer coating on the nanotube structure (RuO2@r-TiO2). The RuO2 thin layer was successfully coated on the surface of r-TiO2. This was accomplished with a self-synthesized layer of ruthenium precursor originating from a spontaneous redox reaction between Ti3+ and metal ions on the r-TiO2 surface and thermal treatment. The thickness of the thin RuO2 layer was approximately 30 nm on the nanotube surface of RuO2@r-TiO2 without severe pore blocking. In chlorine production, RuO2@r-TiO2 exhibited higher current efficiency (∼81.0%) and lower energy consumption (∼3.0 W h g-1) than the r-TiO2 (current efficiency of ∼64.7% of and energy consumption of ∼5.2 W h g-1). In addition, the stability (ca. 22 h) was around 20-fold enhancement in RuO2@r-TiO2 compared with r-TiO2 (ca. 1.2 h). The results suggest a new route to provide a thin layer coating on r-TiO2 and to synthesize a high performance oxidant-generating anode.

Selective fluoride removal in capacitive deionization by reduced graphene oxide/hydroxyapatite composite electrode.

Capacitive deionization (CDI) is an emerging desalination technology with an environmental-friendly operation and energy-efficient properties. However, activated carbon (AC) used for CDI electrode does not have a significant preference toward anions, leading to unnecessary energy consumption for treating fluoridated water. Hence, we achieved selective fluoride removal in CDI system using a reduced graphene oxide/hydroxyapatite composite (rGO/HA), a novel fluoride selective electrode material. The results showed that the rGO/HA electrode has 4.9 times higher fluoride removal capacity than the AC electrode from a ternary solution consisting of fluoride, chloride, and nitrate ions. The fluoride removal capacity increased when the adequate voltage was applied. Furthermore, the rGO/HA electrode exhibited stability and reusability without significant capacity loss even after 50-cycle operation, maintaining about 0.21 mmol g-1 of fluoride removal capacity and approximately 96% of regeneration efficiency. Thus, this study suggests a novel electrode material for effective and selective fluoride removal in the CDI system.

Performance analysis of hydrated Zr(IV) oxide nanoparticle-impregnated anion exchange resin for selective phosphate removal.

The superior removal selectivity of hydrated zirconium oxide nanoparticle-impregnated porous anion exchange resin (ZAE) highlights its use as phosphate removal adsorbent. However, most research examines selective phosphate removal performance using randomly determined single content of hydrated zirconium oxide, and thus the use of the ZAE in real applications remains limited. Therefore, this study aimed to investigate the selective phosphate removal performance of ZAE with different content of hydrated zirconium oxide nanoparticle (HZO NP, represented by zirconium content) by considering various conditions. A molybdate intermediate method was devised to fabricate ZAE with high loaded HZO by weakening the Donnan exclusion to HZO precursors produced from the fixed positively charged host. Consequently, the resultant ZAE was characterized by 17.8 wt% of zirconium. ZAE exhibited an increased selectivity to phosphate against competing ions in the synthetic and simulated real water matrices for both batch and fixed-bed modes as the zirconium content of ZAE increased. High performance was retained, and regeneration led to possible reusability. The linear correlation between selective phosphate removal performances and zirconium content indicates that the zirconium content is a fundamental factor determining the ZAE phosphate adsorption removal. The HZO NPs within ZAE slow adsorption kinetics by blocking AE pores and provide specific adsorption sites for phosphate removal by inner-sphere complexation.

Understanding the Behaviors of λ-MnO2 in Electrochemical Lithium Recovery: Key Limiting Factors and a Route to the Enhanced Performance.

Recently developed electrochemical lithium recovery systems, whose operation principle mimics that of lithium-ion battery, enable selective recovery of lithium from source waters with a wide range of lithium ions (Li+) concentrations; however, physicochemical behaviors of the key component-Li+-selective electrode-in realistic operation conditions have been poorly understood. Herein, we report an investigation on a λ-MnO2 electrode during the electrochemical lithium recovery process with regards to the Li+ concentration in source water and operation rate of the system. Three distinctive stages of λ-MnO2 originating from different limiting factors for lithium recovery are defined with regard to the rate of Li+ supply from the electrolyte: depleted, transition, and saturated regions. By characterization of λ-MnO2 at different stages using diverse X-ray techniques, the importance of Li+ concentration in the vicinity of the electrode surface is revealed. On the basis of this understanding, increasing the density of the electrode/electrolyte interface is suggested as a realistic and general route to enhance the overall lithium recovery performance and is experimentally corroborated at a wide range of operation environments.

Selective phosphate removal using layered double hydroxide/reduced graphene oxide (LDH/rGO) composite electrode in capacitive deionization.

Phosphate removal is a critical issue in water treatment because excess levels of phosphate can cause severe eutrophication. Capacitive deionization (CDI), which has several advantages, such as simple, eco-friendly, and energy efficient operations, has gained attention as a potential alternative over conventional phosphate removal technologies like activated sludge, chemical precipitation, and adsorption processes. However, CDI suffers from a lack of selectivity for phosphate, resulting from non-selective anion removal of positively biased electrodes. Herein, the layered double hydroxide/reduced graphene oxide (LDH/rGO) composite electrode in the CDI process was examined for selective phosphate removal. LDH/rGO showed the selective phosphate removal performance with sustained phosphate removal efficiency even in the presence of excess chloride. In addition, the selective phosphate removal in the CDI process with the LDH/rGO was successfully demonstrated in the simulated water, fabricated by adding a significantly low concentration of phosphate (0.4 mg∙L-1) into real river water matrix (Han River, Seoul, Korea). This result was explained by the high electrochemical selectivity of the LDH/rGO for phosphate.

Enhanced selective removal of arsenic(V) using a hybrid nanoscale zirconium molybdate embedded anion exchange resin.

Selective removal of trace arsenic is crucial for obtaining safe drinking water. Here, the selective adsorptive performance of arsenate (As(V)) on a hybrid ZMAE (nanoscale zirconium molybdate embedded a macroporous anion exchange resin) was examined. It was found that the As(V) adsorption efficiency of ZMAE was almost retained in the presence of competing ions (NO3- or SO42-) up an [SO42-]/[As] or [NO3-]/[As] ratio of 150/1, whereas that of bare AE (anion exchange resin) was negligible for [SO4]/[As] over 15/1. In addition, the As(V) maximum adsorption capacity of ZMAE was found to be 41.2 mg/g, which is in contrast with the negligible adsorption of bare AE under sulfate-rich condition. The enhanced arsenate selectivity of ZMAE can be attributed to the excellent selectivity of ZM NPs (zirconium molybdate nanoparticles), which contributed up to 45% of the adsorption capacity of ZMAE. The behavior of ZMAE towards arsenate was compared with that towards phosphate showing similar adsorption performances between them, which indicates the similar affinity of ZMAE towards arsenate and phosphate. Finally, ZMAE examined for fixed-bed column adsorption for As(V) removal from synthetic As(V) water was effective for up to 5100 BVs, treating As(V) from 0.1 mg/L to below 0.01 mg/L (meeting the WHO guidelines).

Enhancement in Desalination Performance of Battery Electrodes via Improved Mass Transport Using a Multichannel Flow System.

Desalination technologies have heavily been investigated to utilize the abundant salt water on Earth due to the global freshwater shortage. During recent years, the desalination battery (DB) has attracted attention for its low-cost, eco-friendly, and energy-efficient characteristics. However, the current DB system is subject to inevitable performance degradation because of the mass-transfer limitation at the electrode-electrolyte interface, particularly when the system is used to treat brackish water. Here, we present a novel strategy to overcome the intrinsic mass-transfer limitation of DB in brackish water using an effective cell design based on a multichannel flow system. Compared to the conventional DB that consists of one feed channel, the multichannel desalination battery (MC-DB) is configured using two side channels introducing a highly concentrated solution to the electrodes and one middle feed channel for water desalination. The MC-DB showed a desalination capacity of 52.9 mg g-1 and a maximum salt removal rate of 0.0576 mg g-1 s-1 (production rate of 42.3 g m-2 h-1) when a salinity gradient between the feed streams in the middle (10 mM NaCl) and side (1000 mM NaCl) channels was present, which were 3-fold higher than those in the case with no salinity gradient. In addition, the high concentration solution in the side channel significantly enhanced the rate capability of MC-DB, allowing the system to operate under a high current density of 40 A m-2 with a desalination capacity of 34.1 mg g-1. Considering the effect of electrolyte concentration on the battery electrode performance through electrochemical characterization, the highly saline medium at the side channel in the MC-DB creates an optimal environment for the battery electrode to fully capitalize the high desalination capacity, salt removal rate, and capacity retention of the battery electrodes.

Rapid and selective lithium recovery from desalination brine using an electrochemical system.

Due to the steep increase in the use of mobile electronics and electric vehicles, there has been a dramatic rise in the global lithium consumption. Although seawater is considered as an ideal future source of lithium, technological advances are necessary to ensure the economic feasibility of lithium recovery from seawater because the concentration and portion of Li+ are extremely low in seawater. Especially, battery-based electrochemical systems for lithium recovery have been considered as promising lithium recovery methods, though they have not been considered for seawater applications due to the extremely low concentration of Li+. In this study, we demonstrate that an electrochemical system based on a battery electrode material (λ-MnO2) can be used for efficient lithium recovery from desalination brine (2-3 times concentrated seawater). Our approach was able to capture Li+ within a substantially short period of time compared to conventional processes at a rate that was at least 3 times faster than that of adsorption processes, and our approach did not require acid or toxic chemicals unlike the other recovery technologies. Moreover, by consecutive operation of the system, a lithium recovery solution containing 190 mM of Li+ was obtained with only a small consumption of energy (3.07 Wh gLi-1), and the purity of Li+ was increased to 99.0%.

Development of nanoscale zirconium molybdate embedded anion exchange resin for selective removal of phosphate.

Development of a selective adsorbent with an enhanced removal efficiency for phosphate from wastewater is urgently needed. Here, a hybrid adsorbent of nanoscale zirconium molybdate embedded in a macroporous anion exchange resin (ZMAE) is proposed for the selective removal of phosphate. The ZMAE consists of a low agglomeration of zirconium molybdate nanoparticles (ZM NPs) dispersed within the structure of the anion exchange (AE) resin. As major results, the phosphate adsorption capacity of the ZMAE (26.1 mg-P/g) in the presence of excess sulfate (5 mM) is superior to that of the pristine AE resin (1.8 mg-P/g) although their phosphate uptake capacity was similar in the absence of sulfate and these results were supported by the high selectivity coefficient of the ZMAE toward phosphate over sulfate (SPO4/SO4) more than 100 times compared to the pristine AE resin. This superior selective performance of the ZMAE for phosphate in the presence of sulfate ions is well explained by the role of the ZM NPs that contributed to 69% of the phosphate capacity which is based on an observation that the phosphate adsorption capacity of the ZM NPs is not affected by the presence of sulfate. In addition, the behavior of the selective phosphate removal by the ZMAE was well demonstrated by not only in the batch mode experiment with simulated Mekong river water and representative wastewater effluent but also in a column test.

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide.

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe2+ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.

Electrochemical selective ion separation in capacitive deionization with sodium manganese oxide.

Electrochemical selective ion separation via capacitive deionization, for example, separation of lithium resource from brine, using lithium ion batteries is proposed and demonstrated to have the potential for separating specific ions selectively from a solution containing diverse ions. This separation method is of great industrial concern because of applicability in various fields such as deionization, water softening, purification, heavy metal removal, and resource recovery. Nevertheless, besides the selectivity of materials for lithium ion batteries toward Li+, there is very little investigation on the selectivity of the materials for sodium ion batteries toward Na+. Here, the electrochemical selectivity of sodium manganese oxide (Na0.44MnO2), one of the most widely used material in sodium ion batteries, for Na+ and other cations (K+, Mg2+, and Ca2+) is investigated. Selective Na+ separation using the system consisting of Na0.44MnO2 and a Ag/AgCl electrode is successfully demonstrated from a solution containing diverse cations (Na+, K+, Mg2+, and Ca2+) via a two-step process that involves a capturing step (charging process) and a releasing step (discharging process). The results showed that Na0.44-xMnO2 has over 13 times higher selectivity for Na+ than for K+ and 6-8times higher selectivity for Na+ than for Mg2+ and Ca2+ in the electrolyte containing equal concentrations of the respective ions. Additionally, as a practical demonstration, Na+ was successfully separated from an industrial raw material used for pure KOH production (estimated ratio of Na+:K+=1:200).

Photoelectrochemical Degradation of Organic Compounds Coupled with Molecular Hydrogen Generation Using Electrochromic TiO2 Nanotube Arrays.

Vertically aligned TiO2 nanotube arrays (TNTs) were prepared by electrochemical anodization, and then cathodically polarized with dark blue coloration for the dual-functional photoelectrochemical water treatment of organic substrates degradation and accompanying H2 generation. The resulting Blue-TNTs (inner diameter: ∼40 nm; length: ∼9 µm) showed negligible shift in X-ray diffraction pattern compared with the intact TNTs, but the X-ray photoelectron spectra indicated a partial reduction of Ti4+ to Ti3+ on the surface. The electrochemical analyses of Blue-TNTs revealed a marked enhancement in donor density and electrical conductivity by orders of magnitude. Degradations of test organic substrates on Blue-TNTs were compared with the intact TNTs in electrochemical (EC), photocatalytic (PC), and photoelectrochemical (PEC) conditions (potential bias: 1.64 VNHE; λ > 320 nm). The degradation of 4-chlorophenol was greatly enhanced on Blue-TNTs particularly in PEC condition, whereas the PC activities of the Blue- and intact TNTs were similar. The potential bias of 1.64 VNHE did not induce any noticeable activity in EC condition. Similar trends were observed for the degradation of humic acid and fulvic acid, where main working oxidants were found to be the surface hydroxyl radical as confirmed by hydroxyl radical probe and scavenger tests. H2 generation coupled with the organic degradation was observed only in PEC condition, where the H2 generation rate with Blue-TNTs was more than doubled from that of intact TNTs. Such superior PEC activity was not observed when a common TiO2 nanoparticle film was used as a photoanode. The enhanced electric conductivity of Blue-TNTs coupled with a proper band bending in PEC configuration seemed to induce a highly synergic enhancement.

Extraction of Salinity-Gradient Energy by a Hybrid Capacitive-Mixing System.

Salinity-gradient energy (SGE) is a renewable energy source available wherever two solutions with different salinity mix. Capacitive-mixing (Capmix) is a technology that directly extracts the SG potential through the movements of ions in high- and low-concentration solutions. However, the energy-harvesting performance of Capmix needs further improvement. Herein, a hybrid Capmix that consists of a battery and capacitive electrodes is proposed. In this system, sodium ions and anions are captured/released by the metal oxide and carbon electrodes, respectively. The hybrid Capmix extracted an energy density that was approximately three times higher (130 J m-2 ) and exhibited a notable power output (97 mW m-2 ) compared to the previous Capmix using ion-exchange membranes. Furthermore, the hybrid system operated successfully with real river water and seawater. These results suggest that the hybrid Capmix could be a viable option to harvest energy from salinity gradients.

Rocking Chair Desalination Battery Based on Prussian Blue Electrodes.

The demand for fresh water has been increasing, caused by the growing population and industrialization throughout the world. In this study, we report a capacitive-based desalination system using Prussian blue materials in a rocking chair desalination battery, which is composed of sodium nickel hexacyanoferrate (NaNiHCF) and sodium iron HCF (NaFeHCF) electrodes. In this system, ions are removed not only by charging steps but also by discharging steps, and it is possible to treat actual seawater with this system because the Prussian blue material has a high charge capacity with a reversible reaction of alkaline cations. Here, we demonstrate a rocking chair desalination battery to desalt seawater, and the results show that this system has a high desalination capacity (59.9 mg/g) with efficient energy consumption (0.34 Wh/L for 40% Na ion removal efficiency).