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At least 577 records · Page 32

Magma Electrolysis: An update

Electrolytic extraction of O2 from molten lunar soil is conceptually simple and thus a candidate process for producing O2 on the Moon. Possible container and electrode materials are being tested for durability in corrosive high-temperature silicate melts and looking for complications that might increase energy requirements. Gaseous oxygen is being produced by electrolysis of 1-2 gram quantities of silicate melts in spinel (MgAl2O4) crucibles; in these melts, spinel is a stable phase. The concentration of FeO was kept low because FeO decrease O2 production efficiency. Platinum electrodes were placed about 0.5 cm apart in the melt. The spinel crucible was still intact after 40 minutes of electrolysis, when the experiment was halted for examination. The Pt anode was also intact; its Pt was maintained in a dynamci state in which the anode was continuously oxidized but quickly reduced again by the silicate melt, inhibiting migration of Pt away from the anode. In melts with low concentrations of Al2O3 + SiO2 (2 wt percent), the energy of resistance heating was only approximately equal to 10 to 20 percent of the theoretical amount required to produce O2. In melts substantially more concentrated in Al2O3 + SiO2, higher melt viscosity resulted in frothing that, in the worst case, caused high enough melt resistivities to raise the energy requirements to nearly 10 times theoretical. Both Fe and Si are produced at the cathode; in iron-rich melts, a- and c-iron and molten ferrosilicon were observed. Production was also observed at the cathode of a previously unrecognized gas; which is not yet identified. The solubility of metallic species was measured in silicate melts. They are too low to reduce significantly the efficiency of O2 production.

Colson, Russell O.↗

Tuning the Co/Fe ratio in BaCo x Fe 0.8– x Zr 0.1 Y 0.1 O 3– δ , a promising triple ionic and electronic conducting oxide, to boost electrolysis and fuel cell performance

The triple conducting oxide BaCo 0.4 Fe 0.4 Zr 0.1 Y0.1O 3–δ (BCFZY4411), which accommodates simultaneous transport of protons, oxygen ions, and p-type electronic carriers, has been intensively investigated in recent years as a high-performance positive electrode material for fuel cell and electrolysis applications. The heavy Co and Fe-based transition metal doping in BCFZY4411 ensures adequate electrical conductivity while the multiple oxidation states of Co and Fe assist the electrocatalytic and redox ability. Despite the considerable role of Co and Fe transition metal doping in controlling electrochemical activity, however, the study of alternative BCFZY compositions with varying Co/Fe ratios has not yet been pursued. Here, we evaluate the electrochemical performance of a series of BaCo x Fe 0.8–x Zr 0.1 Y0.1O 3–δ compositions with varying Co/Fe ratio (x = 0.1, 0.2, 0.4, 0.6, 0.7) and use oxygen ion tracer diffusion and in situ high-temperature X-ray diffraction to investigate the effect of Co/Fe ratio on electrocatalytic activity, electronic conductivity, oxygen ion incorporation and transport kinetics, and thermomechanical behavior. We find that Co-rich BCFZY7111 yields the highest performance due to exceptionally high oxygen vacancy diffusion and shows a lower and more linear thermal expansion behavior compared to Fe-rich compositions. A protonic ceramic button cell incorporating a BCFZY7111 positive electrode yields a peak power density of 695 mW cm –2 under fuel cell mode and an electrolysis current density of 1976 mA cm –2 at 1.4 V at 600 °C, underscoring the promise of this new BCFZY electrode composition.

30 DIRECT ENERGY CONVERSION↗

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

The highest performance fuel cell cathode electrocatalyst combination ever observed gives 755 mV vs hydrogen at 100 ASF on air at 180 C and shows a potential improvement to 775 mV vs hydrogen for better electrode structures. A pressurized fuel cell (UTC at 5 atm) would then give 805 mV at 320 ASF and 180 C. Another activity diagnostic is the performance of this electrocatalyst on oxygen at 900 mV vs hydrogen. The value for electrocatalyst is 44 mA per milligram of platinum and is projected to reach 60 mA per milligram of platinum with improved electrode structures. Since the electrocatalyst surface area and the electrode structure are not yet optimized there is considerable room for performance enhancement beyond these values, especially at higher temperatures.

Stonehart, P.↗

Quantification of [MTBD][beti] loading and its effects on Pt/HSC electrode performance in hydrogen fuel cells

High surface area carbon-supported platinum catalysts (Pt/HSC) are widely used in polymer electrolyte membrane fuel cells but often suffer from limited proton and oxygen transport within porous domains. To address these challenges, we integrate the ionic liquid [MTBD][beti] into Pt/HSC catalyst layers using two deposition methods-one-pot and sequential deposition-to tune IL distribution within micropores and mesopores. A combination of ex situ and in operando techniques were employed to elucidate electrode structure-performance relationships across a range of IL loadings. Sequential deposition achieved more efficient pore filling and higher IL retention at lower IL:C ratios, enabling enhanced proton conductivity and protection of active sites. Compared to the IL-free Pt/HSC, IL-modified electrodes demonstrated up to 28% improvement in mass activity and enhanced high-current-density performance under low relative humidity, while maintaining comparable performance under humidified conditions. Electrochemical impedance spectroscopy and CO displacement experiments reveal that improvements are linked to reduced ionic resistance and lower sulfonate adsorption on Pt sites, rather than changes in electrochemical surface area. However, excessive IL loading leads to mass transport losses. These results highlight the importance of selective pore filling and efficient IL distribution in achieving kinetic gains without compromising ionic and gas transport.

08 HYDROGEN↗

Light-triggered electrochemical biosensor using singlet oxygen for self-powered operation and glucose detection

This study introduces a light-activated sensing strategy that integrates photosensitization with electrochemical detection. The sensor employs Eosin Y, a photosensitizer that generates singlet oxygen ( 1 O 2 ) via type II photosensitization. Immobilized within a thin polymer matrix on a carbon working electrode, Eosin Y produces 1 O 2 , under green light (520 nm) illumination, initiating a redox process that yields a measurable current. To incorporate biosensing capabilities and enable self-powered operation, this 1 O 2 – mediated process was coupled with glucose oxidase (GOx) to construct a fully operational glucose biosensor. The addition of glucose reverses the current flow by causing GOx to compete for electrons, with the resulting current magnitude correlating with glucose concentration providing a sensitive measure of glucose. The biosensor, as proof-of-principle, demonstrated excellent performance over a range of glucose concentrations (0–73 mM), achieving a detection limit (LOD) of 2.8 mM for steady state photocurrent under oxygen-saturated conditions. This platform leverages light and 1 O 2 as stimuli for tunable, on-demand signal control, offering a novel approach for adaptive, real-time biosensing technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable Solid Electrolyte Interphase Layer Formed by Electrochemical Pretreatment of Gel Polymer Coating on Li Metal Anode for Lithium–Oxygen Batteries

Lithium (Li)-oxygen (O2) batteries (LOBs) exhibit the highest theoretical specific energy density among candidates of the next-generation energy storage systems, but the instability of Li metal anode (LMA), air electrode, and electrolyte largely limit the practical energy density of these batteries. Herein, we report an effective method to protect LMA against side reactions between LMA and crossover contaminants such as highly reactive oxygen moieties. A solid electrolyte interphase (SEI) layer rich in inorganic components was formed on a LMA coated with polyethylene oxide thin-film through an in-situ electrochemical pre-charging step under oxygen atmosphere. This uniformly distributed stiff SEI layer interacted with flexible polymer matrix and formed a submicron-sized gel-like polymer layer. This polymer supported SEI layer leads to much longer cycle life (130 vs. 65 cycles) as compared to those of pristine cell under the same testing conditions (1.0 mAh cm-2 at 0.2 mA cm-2 in the voltage range of 2 to 5 V without any catalysts). It is also very effective during low voltage (2 to 4.5 V) cycling with a redox mediator (0.1 and 0.15M (2,2,6,6-tetramethylpiperidin-1-yl) oxidanyl). Therefore, this approach can be used to stabilize LMA/electrolytes interphase and improve the cycle life of rechargeable LOBs.

lithium-oxygen batteries, lithium metal anodes, ar↗

Amorphous Pd-Loaded Ti 4 O 7 Electrode for Direct Anodic Destruction of Perfluorooctanoic Acid

In this work we present a novel Ti 4 O 7 -based electrode loaded with amorphous Pd clusters that achieve efficient anodic destruction of perfluorooctanoic acid (PFOA), a persistent water pollutant with significant environmental and human health concerns. These amorphous Pd clusters were characterized by the disordered, noncrystalline arrangement of Pd single atoms in close proximity, in contrast to crystalline Pd nanoparticles that have been often employed to tailor the electronic properties of an electrode. We found that the Ti 4 O 7 electrode loaded with amorphous Pd clusters significantly outperformed the Ti 4 O 7 electrode loaded with crystalline Pd particles due to enhanced electron transfer through dominant Pd–O bonds. Combined with the efficient binding of PFOA and its degradation intermediates to the fluorinated electrode surface, this electrode was capable of mineralizing PFOA and releasing fluoride as F – . The reaction pathway was found to proceed without involving reactive oxygen species and therefore was not quenched by common anions in complex natural water systems such as chloride ions.

36 MATERIALS SCIENCE↗

Zinc batteries for grid-scale energy storage: Challenges, opportunities, and future directions

The global electricity sector is undergoing rapid transformation, increasing demand for reliable stationary energy storage and intensifying the need for safe, cost-effective, and scalable technologies for grid-scale applications. While lithium-ion batteries currently dominate the market, concerns over cost, safety, and resource availability motivate the exploration of alternative chemistries. Zinc-based batteries have emerged as a promising option due to the abundance, low cost, and wide geographic distribution of zinc, combined with the inherent safety of aqueous electrolytes. This perspective examines the potential of zinc batteries for stationary energy storage, with particular focus on rechargeable zinc-air systems. We discuss the evolution of zinc battery technologies and compare zinc-air, zinc-bromine, nickel-zinc, and aqueous zinc-ion chemistries, highlighting their advantages for grid applications. Key challenges limiting rechargeable zinc battery performance are analyzed, including dendrite formation and corrosion at the zinc anode, electrolyte degradation from carbonation and evaporation, and sluggish oxygen electrocatalysis at the air cathode. Emerging strategies to address these limitations are reviewed, including advanced electrode architectures, electrolyte engineering, catalyst development, and system-level design improvements. Lastly, we outline future research directions and opportunities for developing durable, efficient, and economically viable zinc-based energy storage systems for grid-scale applications.

Aqueous electrolytes↗

Low-Temperature Electrochemical Wastewater Oxidation

Here, we demonstrated the Clean Sustainable Electrochemical Treatment (CleanSET) process that enables the distributed clean-up of biomass-derived wastewater while simultaneously generating hydrogen (H 2 ). The specific goal of this project is to 1) demonstrate the selective removal of chemical oxygen demand (COD), total carbon (TC), and total nitrogen (TN) of different wastewaters, 2) optimize the electrode composition to improve electrochemical performance, and 3) perform a high-level techno-economic analysis to obtain levelized costs of disposal (LCOD) .

08 HYDROGEN↗

The structures of the sintered plaque in the nickel hydroxide electrode

The various failure mechanisms were identified for the nickel electrode. The nickel sinter is involved in all these failure modes. The first one, chemical attack by carbonate, nitrate or other electrolyte components, involves corrosion of the nickel sinters. The second is the physical mode, which involves swelling of the electrode and physical shifting of the sinter in the electrodes. The third is the mechanical failure mode, and is due to fatigue or to the oxygen pressure that causes deformation or fracture of the sinter.

Vyas, B.↗

Effect of TiO x Substrate Interactions on the Electrocatalytic Oxygen Reduction Reaction at Au Nanoparticles

Here, we report a robust model for studying electrocatalytic reactions at metal nanoparticles (NPs) in contact with metal oxide surfaces. The metal oxide layer (TiO x ) is prepared by atomic layer deposition, and it is sufficiently thin that it does not hinder electron transfer from the underlying conductive electrode to the supported AuNP electrocatalysts. In advance of the experiments, density functional theory (DFT) predicted that direct contact between AuNPs and TiO x would lead to enhanced activity for the oxygen reduction reaction (ORR). DFT attributes the observed ORR enhancement to partial charge transfer from oxygen vacancies within the TiO x film to the supported AuNPs and hence formation of anionic Au species. The experimental findings are in near quantitative agreement with the DFT results. Specifically, compared to isolated AuNPs, decreases of ~ 100 and ~ 50 mV in the ORR onset potential are observed experimentally for AuNPs supported on TiO 1.9 and TiO 2.0 films, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of LiNiO 2 at Moderate Oxygen Pressure and Long-Term Cyclability in Lithium-Ion Full Cells

The widespread adoption of electric vehicles necessitates higher-energy-density and longer-life cathode materials for Li-ion batteries. LiNiO 2 offers a higher energy density at a lower cost than other high-Ni-content cathodes containing additional transition-metal ions. However, detrimental phase transformations and impedance growth, resulting from structural defects formed during synthesis, lead to poor cyclability and limit the practical viability of LiNiO 2 . Herein, we demonstrate a considerably improved cycle life for LiNiO 2 by synthesizing it under a pressurized oxygen environment. The capacity retention in pouch-type full cells with a graphite anode after 1000 cycles is increased from 59 to 76% by applying a mere 1.7 atm of oxygen pressure during the synthesis of LiNiO 2 . With iodometric titration and inductively coupled plasma optical emission spectroscopy analysis, we provide clear evidence that oxygen pressure during synthesis reduces the occurrence of lattice oxygen vacancies and increases the content of Ni 3+ in LiNiO 2 , improving its structural integrity and cyclability. Post-mortem analysis of the cycled cathodes provides insights into the sources of degradation occurring during long-term cycling. Here, this work demonstrates a practically viable, synthetic approach combined with doping and coating to achieve improved performance with high-Ni layered oxide materials. Furthermore, this work represents the first report of extended cycling of LiNiO 2 in pouch full cells with graphite anode and will, therefore, serves as an important benchmark for future research on LiNiO 2 .

25 ENERGY STORAGE↗

Anodic electrocatalytic conversion of carboxylic acids on thin films of RuO 2 , IrO 2 , and Pt

The electrocatalytic upgrading of carboxylic acids, abundant biomass-derived molecules, remains a challenging task. In this paper, we report an electrocatalytic decarboxylation (ECDX) approach for the conversion of carboxylic acids into paraffins, olefins, and alcohols via (non-)Kolbe electrolysis on thin films (TFs). The ECDX rate, product selectivity, and current efficiency were potential and electrode dependent. For example, the ECDX activity of RuO 2 -TF was similar to that of Pt foil, but the selectivity to Kolbe products was lower on the former. RuO 2 -TF showed about five times higher rates for the oxygen evolution reaction than Pt foil, which resulted in lower current efficiency. The ECDX and O 2 evolution activities of IrO 2 -TF were potential dependent, but this electrode was selective to non-Kolbe products with low current efficiency (<10 %). This work highlights the performance of thin films as an alternative to bulk metals as anodes for oxidative upgrading of carboxylic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A simple convertible electrolyzer in membraneless and membrane-based modes for understanding water splitting mechanism

State-of-the-art membrane-based electrolyzers such as proton exchange membrane electrolyzer cells, are costly, susceptible to degradation, and time-consuming for electrode evaluation and triple-phase boundary electrochemical reaction studies. Here, a simple convertible electrolyzer in membraneless and membrane-based modes is proposed. For the first time, this enables comprehensive investigations of water splitting with pure water, acidic and alkaline electrolytes in one cell. With the simple electrolyzer and high-speed visualization system, the influences of flow rate, electrolytes, concentration, and Nafion membrane on the oxygen evolution reactions (OERs), hydrogen evolution reactions (HERs) and electrolyzer performance are comprehensively investigated. Visualization results reveal that water splitting only occurred at the edge between the electrode and the Nafion membrane in pure water. However, they occurred on the whole electrode surface in alkaline and acidic electrolytes, indicating easily tunable reaction sites with the convertible electrolyzer. This demonstrates the feasibility of using the simple convertible electrolyzer for understanding the water splitting mechanism. The relation between electrolyte thickness and resistances with different electrolytes is also quantified. This research provides an insight for optimizing electrochemical devices while delivering an inexpensive and fast way for electrode evaluations and electrochemical reaction studies.

25 ENERGY STORAGE↗

High-Temperature 2D Optical Relaxation Visualizes Enhanced Oxygen Exchange Kinetics at Metal-Mixed Conducting Oxide Interfaces

Solid-state heterointerfaces are of interest for emergent local behavior that is distinct from either bulk parent compound. One technologically relevant example is the case of mixed ionic/electronic conductor (MIEC)–metal interfaces, which play an important role in electrochemistry. Metal–MIEC composite electrodes can demonstrate improved catalytic activity vs single-phase MIECs, improving fuel cell efficiency. Similarly, MIEC surface reaction kinetics are often evaluated using techniques that place metal current collectors in contact with the surface under evaluation, potentially altering the response vs the native surface. Here, techniques enabling direct and local in situ observation of the behavior at and around such heterointerfaces are needed. Here, we develop a spatially resolved optical transmission relaxation (2D-OTR) method providing continuous evaluation of local, high-temperature, controlled atmosphere defect kinetics across a ~1 cm2 sample area simultaneously in a contact-free manner. We apply it to observe the spatial variance of oxygen incorporation and evolution rates at ~525–620 °C, in response to step changes in oxygen partial pressure, on MIEC SrTi 0.65 Fe 0.35 O 3–x films as a function of distance from porous Pt and Au layers. Using this model geometry, we find significant enhancements in kinetics adjacent to the metals that decay over a few millimeter distance. To extract kinetic parameters, we fit the short-term optical data (initial portion of relaxations) with an exponential decay function appropriate for surface-exchange-limited kinetics, yielding apparent surface exchange coefficients (k chem ) with spatial resolution, decreasing with distance from the metal. To understand the kinetic processes governing the complete (long-term) optical relaxations, we performed COMSOL simulations, which demonstrated that a combination of laterally varying k chem and in-plane diffusion controls the observed kinetics over the full time range. Further support for spatially varying kchem comes from demonstrations of changing surface and bulk chemistry vs distance from the metal–MIEC interface, by X-ray photoelectron and optical absorption spectroscopies, respectively. Although microporous Pt and Au are not excellent electrodes in isolation, both metals exert a synergistic effect on the oxygen surface exchange rate in the presence of the mixed conducting film.

36 MATERIALS SCIENCE↗

Electrolytic Coagulant Generation for Treating Flowback and Produced Water for Reuse

This research investigated a novel electrochemical process for producing a ferric iron coagulant for use in treating flowback and produced water (FPW) from hydraulic fracturing and oil production operations. The electrolytic coagulant generation (ECG) system uses an electrochemical cell to produce acid and base from oilfield brine solutions. The acid is used to dissolve scrap iron to provide a Fe 3+ coagulating agent, and the base is used to neutralize the treated water. The costs for generating the ferric iron coagulant were determined as a function of current density and feed water salinity. The process was shown to be effective for removing colloidal bentonite particles from brine solutions. Here, the process has several advantages over conventional electrocoagulation using iron anodes, including: the ability to treat anoxic waters, elimination of electrode fouling, lower cost for the coagulant, and the ability to deliver Fe 3+ doses greater than 1 mM, since it is not limited by the amount of dissolved oxygen required to oxidize ferrous to ferric iron.

54 ENVIRONMENTAL SCIENCES↗

The electrochemical generation of useful chemical species from lunar materials

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Tsai, Kan J.↗