LTE-P-6 AEM Conductivity
A procedure for measuring the hydroxide conductivity of an anion exchange membrane (AEM). A four-electrode In-plane conductivity is measured as a function of relative humidity (RH).
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A procedure for measuring the hydroxide conductivity of an anion exchange membrane (AEM). A four-electrode In-plane conductivity is measured as a function of relative humidity (RH).
Zeoponics is only in its developmental stages at the Johnson Space Center and is defined as the cultivation of plants in zeolite substrates that contain several essential plant growth cations on their exchange sites, and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth anions. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations with the ability to exchange most of their constituent exchange cations as well as hydrate/dehydrate without change to their structural framework. Because zeolites have extremely high cation exchange capabilities, they are very attractive media for plant growth. It is possible to partially or fully saturate plant-essential cations on zeolites. Zeoponic systems will probably have their greatest applications at planetary bases (e.g., lunar bases). Lunar raw materials will have to be located that are suited for the synthesis of zeolites and other exchange resings. Lunar 'soil' simulants have been or are being prepared for zeolite/smectite synthesis and 'soil' dissolution studies.
An approach is described for measuring hydration-induced volume change within ion conductive polymer membranes and thin films by adapting the technique of confocal Raman microscopy. With careful consideration of factors that affect excitation and scattering within the confocal probe volume region, material swelling and deswelling were estimated from the intensities of polymer matrix spectral features. A high numerical aperture oil-immersion objective was used to achieve tight focusing within samples and the efficient collection of Raman scattered light. The approach is demonstrated for a fluorinated cation-exchange ionomer (Nafion) and the hydrocarbon anion-exchange ionomer Sustainion. Samples were monitored while under a nitrogen atmosphere that was cycled between dry and humid (∼50% relative humidity, RH) states. The volume changes estimated from the Raman spectra were in close agreement with those derived from conventional measurements. The reported work advances understanding needed to adapt confocal Raman microscopy for quantitative in situ and operando studies of ionomers within electrochemical devices, such as polymer electrolyte membrane fuel cells and electrolyzers, and lays a foundation for broader applications in the study of hydration-induced polymer swelling and the associated molecular level water and polymer framework structural changes.
Atomically dispersed Fe-N-C materials recently hold great interest in costly Pt substitution for the cathodic oxygen reduction reaction of fuel cells. However, the heat treatment involved in the materials preparation excites Fe aggregating into low activity of nanosized species rather than high activity of single-atom Fe sites. Herein we proposed a new "ceria-assisted" strategy to preferentially generate the active single-atom Fe sites in Fe-N-C materials, which involves oxidative polymerization of pyrrole, Ce 3+ and Fe 3+ adsorption, and subsequent heat treatment. Owing to its spatial confinement and strong trapping for Fe atoms, ceria can effectively suppress agglomeration of isolated Fe atoms and stabilize the Fe atoms by bonding to O in the lattice during the heat treatment, leading to a high content of atomically dispersed Fe (4.6 wt.%). Accordingly, the final catalyst showed ultrahigh ORR activity with a half-wave potential of 0.915 V and kinetic current density of 7.15 mA cm -2 at 0.9 V. When it was as assembled an anion exchange membrane fuel cell, a large maximum power density of 496 mW cm -2 was achieved.
Direct borohydride fuel cells (DBFCs) can operate at double the voltage of proton exchange membrane fuel cells (PEMFCs) by employing an alkaline NaBH 4 fuel feed and an acidic H 2 O 2 oxidant feed. The pH-gradient-enabled microscale bipolar interface (PMBI) facilitates the creation and maintenance of an alkaline environment at the anode and an acidic environment at the cathode for the borohydride oxidation and peroxide reduction reactions. However, given the need to dissociate water at the interface to ensure ionic conduction, PMBI can be efficient only when anion exchange ionomer (AEI) moieties enable fast water transport for autoprotolysis. Herein, a series of polynorbornene-based AEIs with a range of water uptake values are examined to unravel the optimum water uptake required to enable high performance DBFCs. The DBFC with PMBI configuration containing the optimal AEI composition delivers a current density of 302 mA cm –2 at 1.5 V and a peak power density of 580 mW cm –2 at 1 V. This AEI composition exhibits high hydroxide ionic conductivity of 90.7 mS cm –1 at 80 °C with an IEC of 2.01 mequiv g –1 and demonstrates impressive chemical stability by retaining 98.75% of its initial ionic conductivity after immersion into anolyte (3 M KOH and 1.5 M NaBH 4 ) at 70 °C for 536 h.
A procedure for the measurement of gas permeability of an anion exchange membrane (AEM). During the course of the electrochemical reaction, low gas permeation of hydrogen and oxygen through the membrane is crucial to run the process efficiently. The gas permeation rate can be measured using (A) pressure permeation cell, (B) electrochemical monitoring cell, (C) microelectrode and (D) in-situ measurement in MEA. The process relies on a chronoamperometric technique to accurately measure the gas permeation rate across the membrane.
Characterization of the internal architecture of polymer materials plays an important role in the development of energy devices such as fuel cells. The beam sensitivity of polymer materials coupled with their inherent low contrast makes imaging using conventional TEM and STEM techniques a challenge. Here, we demonstrate robust mapping of the internal architecture of fuel cell polymer membranes using cryo-4D-STEM and cryo-STEM-EELS. Here, we will focus on characterization of alkaline anion exchange membranes (AAEMs) used in AAEM fuel cells, a cheaper alternative to current fuel cell technologies as they allow for platinum group metal-free catalysts. In fuel cell polymer membranes, the internal architecture is critical in performance metrics such as conductivity, mechanical durability, and chemical stability.
The use of radioisotopes in cancer therapy is becoming increasingly important. As a potential candidate for targeted alpha therapy, 230 U (t 1/2 = 20.8 d), the decay daughter of 230 Pa (t 1/2 = 17.4 d) is currently being investigated for cancer treatment. For radioisotopes to be used in biomedicine, they must be radiochemically pure and free from carrier interference. This can be challenging given their short half-life. Thus, in this study, radiological separation methods for harvesting isotopes for use in biomedicine must be simple, fast, and capable of obtaining the required purity levels. Herein, we demonstrate a new rapid method for the separation of 230 U and 230 Pa from a proton-irradiated 232 Th metal target and from coproduced fission products with high recovery and purity. A dual-column approach was used, in which the first column was an anion exchange (AX) column and the second column was a DGA column. The MP-1 AX resin was used for the primary separation of the three major components (U, Pa, and Th, as well as fission products), and the DGA column was used for further purification of the separated 230 U. The method is simple and allows for straightforward separation of U, Pa, Th, and fission products; also, the entire process from target dissolution to shipment of 230 U could be completed in 3 days with an overall 230 U recovery yield of 96 ± 3%. Additionally, separated 230 Pa fractions can be used to harvest ingrown 230 U after initial separation.
Hydrogen can be electrochemically produced in microbial electrolysis cells (MECs) by current generated from bacterial anodes with a small added voltage. MECs typically use a liquid catholyte containing a buffer or salts. However, anions in these catholytes result in charge being balanced predominantly by ions other than hydroxide or protons, leading to anode acidification. To enhance only hydroxide ion transport to the anode, we developed a novel vapor-fed MEC configuration lacking a catholyte with closely spaced electrodes and an anion exchange membrane to limit the acidification. This MEC design produced a record-high sustained current density of 43.1 ± 0.6 A/m 2 and a H 2 production rate of 72 ± 2 LH 2 /L-d (cell voltage of 0.79 ± 0.00 V). There was minimal impact on MEC performance of increased acetate concentrations, solution conductivity, or anolyte buffer capacity at applied voltages up to 1.1 V, as shown by a nearly constant internal resistance of only 6.8 ± 0.3 mΩ m 2 . At applied external voltages >1.1 V, the buffer capacity impacted performance, with current densities increasing from 28.5 ± 0.6 A/m 2 (20 mM phosphate buffer solution (PBS)) to 51 ± 1 A/m 2 (100 mM PBS). Furthermore, these results show that a vapor-fed MEC can produce higher and more stable performance than liquid-fed cathodes by enhancing transport of hydroxide ions to the anode.
Anion exchange membrane water electrolyzers (AEMWEs) can generate hydrogen with a pure water feed using noble metal-free catalysts. Here, the development of highly active and stable catalysts for oxygen evolution reaction (OER) is required for improving performance of AEMWEs systems. Ni-Fe (oxy)hydroxides show high OER catalytic activity in alkaline media, but typically have low surface area. In this work, we investigate a series of Ni-Fe oxides with high surface area and disordered morphology, obtained using an aerogel synthesis method. We evaluate the impact of different synthesis variables on the OER activity and demonstrate that heat treatment at high temperatures generates more ordered structure, resulting in a decrease in OER activity. Advanced characterization reveals that maintaining highly disordered and porous structure of the aerogel is essential to achieving high OER activity, as it enables the formation of highly OER-active lamellar structures of the catalyst.
Microbial electrolysis cells (MECs) are appealing for recovering the chemical energy contained in domestic and industrial liquid wastes as hydrogen gas. Despite several years of research in the field, there is still a lack of critical analysis of how the reactor architecture dictates the electrochemical performance of the cell. In this study, internal resistance and onset voltage from the electrode potential slope analysis (EPS) were used in combination with current density, hydrogen production rate, reactor packing density, electrode spacing, membrane type and composition from 23 different studies to identify the reactor design parameters that primarily govern electrochemical performance of MECs. Using anion exchange membranes resulted in smaller internal resistances (AEM R int = 41± 40 mΩ m 2 ) and larger current density (18 ± 14 A m −2 ) compared to single chamber reactors (SC R int = 68 ± 58 mΩ m 2 ; 22 ± 16 A m −2 ) or MECs with cation exchange membranes (CEM R int = 376 ± 280 mΩ m 2 ; 3.0 ± 2.1 A m −2 ). Higher electrochemical performance for AEM- and SC-MECs translated in larger hydrogen gas production rates (0.122 mL H 2 C −1 for AEM vs 0.117 mL H 2 C −1 for SC), but only when inhibitors against hydrogen scavengers were added in single chamber systems (0.080 mL H 2 C −1 for SC without inhibitors). Following membrane type and composition, maintaining a small electrode spacing was the most critical parameter to improve MEC performance, indicating that the low conductivity of the media primarily limit performance by increasing ohmic resistance. Here, reactor volume and electrode surface area negatively correlated with internal resistance and current density, indicating that better performance of scaled-up reactors can likely be obtained by stacking multiple smaller units rather than just increasing reactor size. Although challenges remain in the implementation of MECs for hydrogen production from liquid wastes, advances in electrochemical engineering of the reactors can facilitate scale up and performance prediction at scale.
This study provides a comprehensive structural characterization of commercially available alkaline anion-exchange polymers (Fumasep FAA-3 and IRA 900) used in moisture-driven direct air capture (DAC) of carbon dioxide. Using X-ray diffraction, SAXS/WAXS, atomic force microscopy, FIB-SEM, and transmission electron microscopy, the authors identify nanoscale clustering, porosity, swelling behavior, and humidity-dependent structural changes that influence CO₂ adsorption and release. These findings establish structure–function relationships critical for designing more durable and energy-efficient DAC polymer materials.
The slow kinetics of the anodic hydrogen oxidation reaction (HOR) in alkaline medium is one of the limitations for anion exchange membrane fuel cells (AEMFCs). Hence, accurately regulate and understand catalytic interface structure are essential to solve this bottleneck and reveal the structure-activity relationship. In this work, a novel trimetal core-shell model with mono-layer Pt-shell is employed for hydrogen electrooxidation to avoid thermodynamic driven bulk/surface composition deviation. On account of the atomic radius discrepancies of 3d-transition metals M (M = Fe, Co and Cu), the electronic structure of mono-layer Pt is regulated by the strain-engineered Pd-M core and the electrocatalytic activity for HOR is tuned accordingly. Nevertheless, step-by-step electrochemical monitoring and surface-treatment experiments indicate that the oxophilicity optimization by low-valence M(OH) x species, rather than the hydrogen binding energy (HBE) optimization caused by strain engineering, influence the activity obviously. It is mainly derived from the enhanced adsorption of OH ad and accelerated desorption of the H ad . The trimetal core-shell model breathes new life into the low-Pt catalyst design for hydrogen electrooxidation reaction.
Abstract Background Epidermal cell walls have special structural and biological roles in the life of the plant. Typically they are multi-ply structures encrusted with waxes and cutin which protect the plant from dehydration and pathogen attack. These characteristics may also reduce chemical and enzymatic deconstruction of the wall for sugar analysis and conversion to biofuels. We have assessed the saccharide composition of the outer epidermal wall of onion scales with different analytical methods. This wall is a particularly useful model for cell wall imaging and mechanics. Results Epidermal walls were depolymerized by acidic methanolysis combined with 2M trifluoracetic acid hydrolysis and the resultant sugars were analyzed by high-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Total sugar yields based on wall dry weight were low (53%). Removal of waxes with chloroform increased the sugar yields to 73% and enzymatic digestion did not improve these yields. Analysis by gas chromatography/mass spectrometry (GC/MS) of per- O -trimethylsilyl (TMS) derivatives of the sugar methyl glycosides produced by acidic methanolysis gave a high yield for galacturonic acid (GalA) but glucose (Glc) was severely reduced. In a complementary fashion, GC/MS analysis of methyl alditols produced by permethylation gave substantial yields for glucose and other neutral sugars, but GalA was severely reduced. Analysis of the walls by 13 C solid-state NMR confirmed and extended these results and revealed 15% lipid content after chloroform extraction (potentially cutin and unextractable waxes). Conclusions Although exact values vary with the analytical method, our best estimate is that polysaccharide in the outer epidermal wall of onion scales is comprised of homogalacturonan (~ 50%), cellulose (~ 20%), galactan (~ 10%), xyloglucan (~ 10%) and smaller amounts of other polysaccharides. Low yields of specific monosaccharides by some methods may be exaggerated in epidermal walls impregnated with waxes and cutin and call for cautious interpretation of the results.
The behavior of the oxygen-evolving positive electrode (i.e. anode) in the anion exchange membrane water electrolyzer (AEMEL) is complex and influenced by several factors. Very few studies have been performed to understand oxygen evolution reaction (OER) behavior by optimizing the individual factors that influence performance. Here, this study highlights the effects of catalyst loading, catalyst selection, porous transport layer (PTL) type and conductive additive content. The influence of each factor is elucidated through a design of experiments (DoE) approach with a full statistical analysis. Electrochemical data, alongside Pareto charts, parametric trends and their mutual interactions are discussed. This DoE approach is also helpful in making useful predictions and discovering new combinations to be tested. The end result was a high-performance AEMEL able to operate at a current density of 1.0 A/cm 2 at 1.80 V with IrOx OER and PtNi hydrogen evolution reaction (HER) catalysts using 0.3 M KOH fed to the anode. Even lower operating voltage was observed with PbRuOx catalyst at the anode, 1.64 V @ 1.0 A/cm 2 , though the cell decay rate was higher. Lastly, a IrOx/PtNi cell was stably operated continuously for 30 days (720 h) at 1.0 A/cm 2 . This study can serve as a guide for optimal electrode design with insights into component-performance compromises, which can aid in making design choices and performing techno-economic analyses.
Two direct air capture (DAC) systems were designed and demonstrated to passively capture CO 2 from ambient air and use moisture to release the CO2 into an alkaline medium. A bench-scale system delivering ∼1 g CO 2 d –1 was demonstrated in a laminar flow hood, and a small pilot-scale system that could deliver ∼100 g CO 2 d –1 was operated outdoors in a 4.2 m 2 raceway pond. Novel elongated mesh-tube packets containing anion-exchange resin (AER) beads were found to reduce drying and CO 2 loading time 4.3-fold compared to larger mesh bags. Technoeconomic analysis (TEA) estimates the cost of capturing CO 2 into an alkaline solution, suitable for cultivating photosynthetic microorganisms, to be $\$229$ per tonne for a practical scenario based on current results and $\$72$ per tonne for an aspirational scenario considering improvements to sorbent capacity, hydrophobicity, and sorbent lifetime. TEA further estimates an additional $\$110$ per tonne to extract CO 2 from solution, purify it, and compress it to 15 MPa, suitable for sequestration. Furthermore, moisture-driven processes have the potential to use up to 87% less energy than thermal and/or vacuum swing DAC by using energy from water evaporation.
Anion exchange membrane water electrolyzers (AEMWEs) represent a promising technology for hydrogen production. The big advantage of the technology is that it allows for the use of platinum group metal-free (PGM-free) electrocatalysts at both electrodes, including catalysts for the hydrogen evolution reaction (HER) at the cathode. In addition to fulfilling the cost requirement, PGM-free HER catalysts need to meet the activity and durability targets of the AEMWEs. Here, in this work, we developed several carbon-supported, xerogel-derived nickel (Ni) HER electrocatalysts and evaluated the effect of various synthesis conditions, such as the type of carbon support, Ni-to-carbon ratio, and heat-treatment temperature and time, on their performance. Scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy (STEM-EDS), X-ray diffraction spectroscopy (XRD), and X-ray photoelectron spectroscopy (XPS) revealed the formation of Ni nanoparticles with an oxygen-rich layer on the outside. Durability of the best-performing catalyst was assessed via a constant-current hold at 10 mA cm –2 over 100 h. This catalyst was found to be more active and durable than the reference PGM-free material, a commercial Ni catalyst supported on a Vulcan XC-72. The catalyst was also tested in the cathode of a fully PGM-free AEMWE, allowing to reach 1.90 V (1.84 V HFR-free) at 1 A cm –2 at 80 °C.
ASU’s DAC polymer-enhanced cyanobacterial bioproductivity (AUDACity) project aims to demonstrate a novel, scalable method for removing carbon dioxide (CO 2 ) directly from ambient air and delivering it to cyanobacterial cultures to produce commodity biofuel, mid-value protein for supplements, and high value phycocyanin (PC), a natural blue colorant (Figure A). This approach uses low-cost, reusable anion exchange polymers embedded in modular mesh packets, which capture CO 2 during drying cycles when exposed to ambient air, and release concentrated CO 2 into aqueous cultivation systems. The project addresses a critical challenge in energy research needed for developing sustainable, economically viable methods of Direct Air Capture (DAC) that can be integrated with bio-based systems for fuel and chemical production. AUDACity contributes to scientific understanding by integrating materials chemistry, cyanobacterial biology, and system engineering to create a distributed CO 2 delivery platform. Key insights have emerged around the design of biocompatible sorbents, optimization of CO 2 capture-release cycles, and durability of packet-based delivery systems under outdoor conditions. Notably, the team has synthesized and tested a range of polymer sorbents, identified mechanisms of material degradation and fouling, and advanced both lab- and pilot-scale cultivation systems to evaluate performance. From a technical and economic standpoint, AUDACity shows promise for achieving cost-effective CO 2 capture and delivery into aqueous media and biofuel production. Preliminary techno-economic analysis (TEA) indicates that the DAC system based on current performance can reach $\$$680/tonne CO 2 delivered into aqueous solution; with reasonable improvements to sorbent lifetime, sorbent capacity, reducing water uptake the approach could reach $\$$66/tonne by avoiding the need for energy-intensive sorbent regeneration and CO 2 compression, making it more feasible for decentralized deployment. With these costs for CO 2 and by extracting and selling high-value PC ($\$$50/kg) and mid-value protein supplement ($\$$6/kg), the remaining biomass can be hydrothermally treated into biofuel for $\$$2.50/gallon, and would support a small first-of-a-kind biorefinery capable of producing 500 barrels per day of biofuel. The project offers meaningful public benefits by advancing carbon removal technologies that are low-energy, modular, and adaptable to non-arable land and brackish water use. It aligns with national goals to develop advanced biotechnology and supports future pathways for bio-based fuels and products. By enabling direct coupling of CO 2 transfer into aqueous medium and biological carbon utilization, AUDACity lays the groundwork for effective algae cultivation without wasteful CO 2 delivery and is a promising and innovative solution for low-carbon fuel and bioproduct generation contributing to a vigorous bioeconomy.