Gas Diffusion Research Articles

Exploring the impact of ionomer content and distribution on inkjet printed cathodes for anion exchange membrane fuel cells

Electrode composition optimization is critical to achieving high and stable anion exchange membrane fuel cell (AEMFC) performance. In this article, inkjet printing is pioneered as a method to fabricate AEMFC electrodes with varying and graded cathode ionomer loading in order to assess its impact on electrode electrochemical properties, cell performance and stability. Inkjet printed catalyst layers (CLs) exhibited decreasing porosity with increasing ionomer content, maintaining a constant active area at 50 °C under fully humidified conditions. The increase in active area and ionic conductivity with increasing ionomer content was detectable only at higher temperatures. At 60 °C with 90% relative humidity inlet gases, the AEMFCs with cathode electrodes with optimal 20 wt% uniform ionomer content achieved a highly repeatable and stable performance of 0.53 W/cm2 with a total loading of 0.3 mgPt/cmCL2. Grading the cathode ionomer content, with higher concentration near the membrane and lower near the gas diffusion layer (GDL), does not improve cell performance, indicating neither cathode conductivity nor mass transport limits performance. When tested at 80 °C, AEMFCs with a graded cathode ionomer structure (30 wt% near the membrane and 20 wt% near the GDL) demonstrated improved stability compared to those with a uniform 20 wt% ionomer content. This stability improvement is attributed to better water retention with more cathode ionomer content, as evidenced by the cell’s ability to maintain low resistance.

Mechanically robust MOF beads for efficient ethylene/ethane separation with fast adsorption kinetics

Shaping of metal-organic frameworks (MOFs) without obvious mass transfer resistance is crucial for scaled-up adsorption separation process. Herein, mechanically robust ultramicroporous MOF (ZU-901, also termed CPL-1-CH3) beads with hierarchical porosity were structured through the calcium alginate (CA) method, which preserved the adsorption separation performance and demonstrated fast gas diffusion rates. The highly crosslinked networks of CA contributed to the excellent mechanical properties of 95 % ZU-901@CA beads with Young’s modulus up to 1.81 MPa and a low abrasion rate of 0.32 %, superior to that of 95 % ZU-901@HPC extrudates (1.13 %). Compared with powder of ZU-901, the C2H4 capacity of ZU-901@CA beads showed only 3 % loss at 298 K. The C2H4 diffusion time constant of 95 % ZU-901@CA beads (7.06 × 10−3 s−1) was comparable to that of the powders (7.61 × 10−3 s−1) and higher than that of ZU-901@HPC extrudates (2.95 × 10−3 s−1). Breakthrough experiments confirmed that ZU-901@CA beads performed well in the dynamic separation of C2H4/C2H6 binary mixture, and could be easily regenerated at room temperature. In addition, after post modification on the exterior of ZU-901 beads, the water contact angle increased from 0° to 119°. Therefore, the mechanically robust ZU-901@CA beads showed great potential in energy-efficient C2H4/C2H6 separation.

CO2 hydrate formation in superabsorbent hydrogels for carbon capture—A comparison of water-confined framework vs non-water framework

This study investigates the kinetics of CO2 hydrate formation in saturated hydrogel particles—water-confined frameworks—through both experimental and numerical methods, and compares the results with those obtained in silica gels, silicon-based frameworks. Three hydrogel materials with varying swelling ratios were synthesized via radical polymerization. An advanced shrinking core model was developed, incorporating factors of CO2 solubility, gas diffusion, gas–water reaction, capillary effects, and hydrogel functional groups. Results showed rapid CO2 hydrate growth within the first 100 min, with CO2 uptake reaching 78%–82% of the final amount by 600 min. The highest percent water conversion achieved was 96.6%. Simulations indicated a significant decrease in CO2 diffusion coefficient through the hydrate shell over time, especially in hydrogels with higher methacrylic acid content. Capillary effects diminished as the reaction proceeded, with final water consumption via capillaries accounting for 14.4%–26.7% of the total. Hydrogels with higher swelling ratios and higher agglomeration degree formed more porous hydrate shells, enhancing CO2 diffusion but resulting in lower overall CO2 uptake due to their lower water content. Comparisons with hydrophilic porous silica gel revealed that, although hydrogels initially posed greater mass transfer resistance, they ultimately exhibited superior CO2 absorption capacity and rate.

PGC 44685: A Dwarf Star-forming Lenticular Galaxy with a Wolf–Rayet Population

Lenticular galaxies (S0s) are formed mainly from the gas stripping of spirals in the cluster. But how S0s form and evolve in the field is still in need of being resolved. Based on spatially resolved observations from the optical Hispanic Astronomical Center in Andalusia 3.5 m telescope with the PPAK Integral Field Spectroscopy instrument and Northern Extended Millimeter Array, we study a dwarf (M * < 109 M ⊙) S0, PGC 44685, with triple star-forming regions in the central region, namely, A, B, and C, respectively. In northwest region C, we clearly detect the spectral features of Wolf–Rayet (W-R) stars and quantify the W-R population by stacking spectra with high W-R significance. Most of the molecular gas is concentrated in region C(W-R), and there is diffuse gas around regions A and B. The W-R region possesses the strongest intensities of Hα, CO(1–0), and 3 mm continuum, indicating its ongoing violent star formation (gas depletion timescale ≲25 Myr) with tentative hundreds (<500) km s−1 of stellar winds accompanied by the W-R phase. Most (∼96%) of the three star-forming regions show relatively low-metallicity distributions, suggesting possible (minor) accretions of metal-poor gas that trigger the subsequent complex star formation in a field S0 galaxy. We speculate that PGC 44685 will become quiescent in less than 30 Myr if there is no new molecular gas to provide raw materials for star formation. The existence of this dwarf star-forming S0 presents an example of star formation in the low-mass/metallicity S0 galaxy.

Poisoning Mechanism Map for Metal Hydride Hydrogen Storage Materials.

The effective utilization of hydrogen storage materials (HSMs) is hindered by impurity gas poisoning, posing a significant challenge for large-scale applications. This study elucidates the poisoning mechanisms of various impurities gases (CO, CO2, O2, Ar, He, CH4, N2) on ZrCo, Pd, U and LaNi5. Impurities gases are categorized into active and inactive types based on their effecting behaviors and mechanisms on the hydrogenation of HSMs. During the hydrogenation process, active impurities chemically poison the hydrogenation reaction by limiting hydrogen absorption at interface, while inactive impurities physically hinder hydrogenation reaction by impeding hydrogen diffusion in hydrogen-impurity mixed gas. In situ Scanning Tunneling Microscope clarifies these behaviors, and a novel criterion based on hydrogen spontaneous dissociation energy is introduced to explain and predict impurity-substrate interaction characteristics. The novel findings of this work provide a comprehensive framework for designing long-lived HSMs with poisoning resistance, guiding the development of more resilient hydrogen storage systems.

Measurements of Drying and Wetting Gas Diffusion Coefficients and Gas Permeability of Unsaturated Soils Using a New Flexible-Wall Device

Measurements of Drying and Wetting Gas Diffusion Coefficients and Gas Permeability of Unsaturated Soils Using a New Flexible-Wall Device

Characterization of Oxygen Diffusion and Catalytic Behavior of Composite Materials in Solid Oxide Fuel Cells Using the Non-destructive Adler-Lane-Steele Method

Solid oxide fuel cells (SOFCs) are technologically interesting because they provide high-efficiency energy conversion via an electrochemical reaction within the cells. To bring SOFC to market, researchers must develop highly electroactive, low-cost devices that are chemically stable in both high (800 – 1000 °C) and low (600 – 800 °C) temperatures, as well as optimize oxygen reduction in electrodes. The electrochemical performance of SOFC is highly dependent on the catalytic activity (or catalyst behaviours) of the electrode materials involved in the oxygen reduction reaction due to the slower oxygen reduction kinetics at lower temperatures. Understanding the fundamental properties of oxygen self-diffusion in solid-state ionic systems is critical for developing nextgeneration electrolyte and electrode material compositions and microstructures that enable SOFCs to operate at lower temperatures more effectively, durably, and affordably. To date, the most common method for evaluating electrocatalytic performance is electrochemical impedance spectroscopy (EIS), which causes sample damage due to its set-up procedure. As a result, modelling approaches have been used to better understand the reaction mechanism, oxygen diffusion coefficient, and kinetics of SOFC electrode reactions, including the mixed ionic electronic conductor (MIEC)-based electrode. Several models have recently been developed to represent the reaction mechanisms of SOFCs, with Adler-Lane-Steele (ASL) mathematical theory believed to be suitable for predicting oxygen gas diffusion through the pores of the MIEC-based materials. Hence, the aim of this paper is to validate the area-specific resistance of composite electrodes using the ASL modeling technique rather than the standard EIS analysis. The findings are significant in contributing to the development of a new non-destructive method for analyzing the catalytic behavior of SOFC components.

Numerical Model for Investigating Effects of Cracks and Perforation on Polymer Electrolyte Fuel Cell Performance

The presence of cracks in the microporous layer (MPL) of polymer electrolyte fuel cells (PEFCs), often occurring during the membrane electrode assembly manufacturing process, has a significant impact on cell performance. However, the exact influence of crack presence, density, and patterns within MPLs on cell performance and transport behaviors remains unclear. This study introduces a three-dimensional macroscale model of PEFCs aimed at investigating the effects of MPL cracks and gas diffusion layer (GDL) perforations on cell performance and transport behavior. This model offers several advantages, including the ability to potentially integrate the effects of flow channel design in future. Additionally, the model can seamlessly incorporate electrochemical reactions and explore phenomena within the catalyst layers (CLs), expanding simulation capabilities beyond water transport alone. The findings suggest that MPL cracks contribute positively to performance by facilitating water drainage. Furthermore, when combined with perforations in GDLs, MPL cracks can significantly enhance performance by providing pathways for water transport. Overall, this study provides valuable insights into developing models for optimizing PEFC performance and underscores the need for further research and development in this area.

Electrolyte design for high hydrogen peroxide production rates utilizing commercial carbon gas diffusion electrodes

Electrolyte design for high hydrogen peroxide production rates utilizing commercial carbon gas diffusion electrodes

Unlocking the Activity of Molecular Assemblies for CO2 Electroreduction in Zero-Gap Electrolysers via Catalyst Ink Engineering.

In recent years, CO2 electrolysis, particularly the electrochemical reduction of CO2 to CO in zero-gap systems, has gained significant attention. While Ag-coated gas diffusion electrodes are commonly used in state-of-the-art systems, heterogenized molecular catalysts like bis-coordinated homoleptic silver(I) N,N-bis(arylimino)-acenaphthene (Ag-BIAN) complexes are emerging as a promising alternative due to their tunability and high mass activity. In this study, the influence of ink composition on the performance of Ag-BIAN-based GDEs in zero-gap electrolyzers (ZGEs) are systematically explored at 60°C and 600mA cm⁻2. Sedimentation analyses across various solvents informed the selection of optimal solvent-catalyst and solvent-carbon additive combinations, streamlining the GDE optimization process and reducing associated costs and time. These results demonstrate that solvent choice and dilution state of the ink are critical factors impacting CO2 reduction, achieving faradaic efficiencies for CO production (FECO) up to 67% at 600mA cm⁻2 with catalyst loadings as low as 0.2mg cm⁻2. These findings lay the groundwork for advancing from homogeneous H-type cells to industrial ZGE systems through tailored ink engineering.

Deep learning based segmentation of binder and fibers in gas diffusion layers

Gas diffusion layers (GDLs) are vital parts for the performance of proton-exchange membrane fuel cells (PEMFCs). In many cases, they are made of Carbon-Carbon Composite Paper (CCCP), which consists of carbon fibers and a carbonized binder material. The distribution of the fibers and binder in the GDL strongly influences the performance of a PEMFC. Synchrotron scans are a great way to obtain information about the microstructural composition of carbon paper GDLs (Figure 2), but there is one major obstacle. Binder and fibers tend to have the same attenuation and, consequently, the same gray values in the scans. To overcome this, we introduce a machine learning-based method that segments fibers and binder from the local morphology of a CCCP. The training data is generated using FiberGeo, a module in the GeoDict software for fibrous microstructure generation. FiberGeo creates fibers based on stochastic geometry and adds binder using morphological opening and closing operations. We applied the machine learning-based method to four Scans of samples of Toray Carbon Paper with varying amounts of binder in them. The result is the quantification of individual voxels as fiber or binder material that can be used, for example, in performance simulations of property simulations in PEMFCs [1–4]. Here, we focus on the differences in the spatial distribution of the binder both in the through-plane and in-plane directions.

Resolving optimal ionomer interaction in fuel cell electrodes via operando X-ray absorption spectroscopy

To bridge the gap between oxygen reduction electrocatalysts development and their implementation in real proton exchange membrane fuel cell electrodes, an important aspect to be understood is the interaction between the carbon support, the active sites, and the proton conductive ionomer as it greatly affects the local transportations to the catalyst surface. Here we show that three Pt/C catalysts, synthesized using the polyol method with different carbon supports (low surface area Vulcan, high surface area Ketjenblack, and biomass-derived highly ordered mesoporous carbon), revealed significant variations in ionomer-catalyst interactions. The Pt/C catalysts supported on ordered mesoporous carbon derived from biomass showed the best performance under the gas diffusion electrode configuration. Through a unique approach of operando X-ray Absorption Spectroscopy combined with gas sorption analysis, we were able to demonstrate the beneficial effect of mesopore presence for optimal ionomer-catalyst interaction at both molecular and structural level.

Repurposing trityl-substituted triphenylamine-based polyimides for gas separation membranes by blending with a fluorinated polyimide

In the attempt to develop gas separation membranes by reusing polymers with no film-forming ability but with great potential for this purpose, blending has been approached as a simple, time- and cost-effective strategy. Herein, blends of trityl-substituted triphenylamine (TTA)-based polyimides and a fluorinated polyimide (6F-PI) were involved to prepare dense membranes by drop-casting technique. The two blend components involved in variable amounts led to different film morphologies with a strong impact on most blends' properties and gas separation performance. According to optical microscopy, SEM, AFM, and FTIR investigations, the blend series containing hexafluoroisopropylidene (6F) groups in both polyimide components proved to be fully miscible at the molecular levels. When a single 6F-based component was integrated into the blend, the polymers proved to be compatible, but only partially miscible, with a two-phase structure, in which 6F-PI wrapped around the TTA-PI growth fibrillar domains. However, all blends displayed a single glass transition and FTIR bands which do not sum the ones of the polymer components, as well as a high thermal stability, close to that of 6F-PI. Regardless of their miscibility level, all blends behaved as classical polyimide films, with good mechanical properties and chemical resistance to corrosive media like acid vapors or basic solutions. The blend composition and diimide structure of TTA-PI little affected the dielectric behavior, unlike the gas separation performance that strongly depended on these characteristics. The higher amount of 6F groups in the miscible blends endowed the membranes with superior permeability and selectivity, allowing in some cases to surpass the trade-off rule. Generally, the gas permeability decreased with the increase of TTA-PI content, with some exceptions. The low intermolecular interfacial interactions promoted by TTA-PI were found to be beneficial in preserving a good selectivity of gas molecules with a small kinetic diameter (He, CO2) though their permeability is lost. The gas permeability changes as a function of the blend composition and structure were mostly due to changes in the solubility coefficient and less from gas diffusion capability, at least for CO2 and N2.

Preparation of conductive bimetallic phthalocyanine with acceptor and their electrocatalytic properties for CO2 reduction

Abstract In order to develop a catalyst for electrochemical CO2 reduction with high power efficiency, we prepared molecular crystals with 2 types of metal phthalocyanine. Charge transfer complexes with acceptor were selected as the molecular crystal system to reduce the electrical resistance. Various bimetallic phthalocyanine systems consisting of cobalt phthalocyanine and another metal phthalocyanine were obtained as highly conductive separated stacked charge transfer complexes with iodine as an acceptor. The obtained catalysts for CO2 reduction were evaluated using gas diffusion electrodes. The catalysts containing the bimetallic phthalocyanine system of cobalt and copper phthalocyanines showed higher CO2 reduction current and higher CO production, indicating that the CO2 reduction on cobalt phthalocyanine is enhanced by the H2 formation reaction on copper phthalocyanine.

Use of Modified Silica as Selective Adsorbent on Exhaust and Dissolved Gases

Emissions are substances that enter the air, whether or not they have the potential as pollutants. Emission gases can have adverse effects on the health of living beings, especially humans, and can contribute to an increase in the Earth's temperature. Therefore, separation efforts are needed to minimize the negative impacts caused by them. Adsorption method was categorized as absorption, cryogenic distillation, and membrane. Although there were shortcomings in adsorbing emission gases through the method, it remained a promising approach. Adsorption was recognized for its economic viability, technological effectiveness, thermally stability, corrosion resistance, high load capacity, and tunable surface properties. However, adsorption materials were categorized as porous carbon, zeolites, metal-organic frameworks (MOFs), porous polymers, and porous silica. A significant limitation of the method was its susceptibility to decreased capacity in the presence of water vapor. The analysis results showed that porous silica became a superior adsorption material due to its high porosity, which facilitated rapid gas diffusion. To enhance selectivity and adjust pore size, material modifications, particularly silica, became necessary. This showed that surface modification for silicasupported the improvements in selectivity and pore size.

Effects of droplet dynamical behavior in flow channel of proton exchange membrane fuel cell under vibration conditions on cell performance

Proton exchange membrane fuel cells are subjected to severe vibration in aerospace applications. Understanding the droplet transport characteristics in the flow channelunder vibration conditions is essential for improving cell performance. However, the underlying patterns and mechanisms of the vibration effects on cell performance and its internal water transport remain unclear, and there is a lack of improvement methods for drainage under vibration conditions. This study experimentally investigates the effect of vibration on cell performance. Experimental results indicate that vibration predominantly affects cell performance through its modulation of water transport. Therefore, the droplet dynamic behavior in the flow channel is further studied using the volume of fluid method. The results indicate that vibrations can enhance the average performance of the fuel cells, with the largest increase of 8.30 %. This is attributed to vibrations promoting the detachment of droplets from the gas diffusion layer surface and reducing the water coverage ratio on said surface. Under conditions of low gas velocity, high surface hydrophobicity, and large droplet size, droplets exhibited oscillatory and jumping behavior in the flow channel due to vibration, resulting in the largest 53.5 % increase in peak water coverage ratio on the gas diffusion layer surface compared to no-vibration conditions. Furthermore, enhancing the hydrophobicity of the gas diffusion layer and the hydrophilicity of the channel walls promotes droplet detachment and discharge compared to no-vibration, as well as contributing to the improvement of vibration effects on the drainage process.

Electrochemical activation and characterization of carbon cloth

Here, carbon cloth (CC), which is a disposable, inexpensive, conductive substrate, was electrochemically activated for the formation of function al groups on the electrode surface. The electrochemical activation of commercial CC was achieved in various acidic solutions such as 0.1 M H2SO4, 0.1 M HCl and 0.1 M HNO3 to create functional groups on the surface of the gas diffusion layer by applying a constant 100 mA current (galvanostatic) for 10 s, 20 s, and 30 s, respectively. The electrochemical measurements were conducted using a 3-electrode system, including disposable carbon cloth as a working electrode, saturated Ag/AgCl as a reference electrode and Pt wire as a counter electrode. The modified CCs were tested via cyclic voltammetry using 5 mM Fe(CN)63−/Fe(CN)64− redox probe. Electrochemical experiment results showed that acid treatment of CC resulted in a significant increase in peak current compared to bare CC, indicating formation of functional groups on the electrode surface and improved electrical conductivity.

Studying the Effect of Operating Conditions and NO2 Cathode Contamination on PEM Fuel Cells Using Distribution Function of Relaxation Times Analysis.

The effect of NO2, an air pollutant, on the durability of polymer electrolyte membrane fuel cells (PEMFCs) and the affected electrochemical processes in the PEMFC following the contamination were investigated. In-situ Electrochemical Impedance Spectroscopy (EIS) measurements were conducted on PEMFCs under different operating conditions of temperature and relative humidity (RH). NO2 was introduced to the cathode inlet flow. Analyses of the EIS measurements were performed using a genetic algorithm called ISGP (Impedance Spectroscopy by Genetic Programming) to obtain the distribution function of relaxation times (DFRT, a.k.a. DRT) models. Utilizing ISGP enabled us to differentiate the various phenomena in PEMFC and study how they are affected by NO2 contamination. Moreover, the experiments demonstrate the effectiveness of the mitigation method to flush the PEMFC and regenerate its performance after being contaminated, particularly at low operating temperatures. Energy-dispersive X-ray spectroscopy (EDS) technique is performed on the contaminated PEMFC to detect the presence of any nitrogen components in the FC's gas diffusion layer and the catalyst layer post the mitigation step. Cyclic Voltammetry is also performed on the contaminated cell to determine the effect of the contamination on the electrochemically active surface area of the cathode by evaluating the double-layer capacitance.

Step Towards Enzymatic Bioelectrorefinery: Design of a Ligninolytic Hybrid Air‐Breathing Biocathode

AbstractLignins, abundant aromatic biopolymers and one of the major components of lignocellulosic biomass, remain the most underutilized renewable bioresources of aromatics and hydrocarbons on the Earth. Numerous physical and chemical processes have been developed for lignin valorization; however, they generally suffer from environmentally unfriendly, harsh conditions and lack reaction specificity. On the other hand, milder methods involving biocatalysts exist but are impeded by many limitations, such as cofactor regeneration, deleterious enzyme–lignin interactions, and low stability. In this work, we attempt to eliminate the constrains encountered in enzyme‐based lignin valorization processes through the development of a novel electrochemically assisted bioprocess. This “all‐in‐one” biocathode incorporates a hybrid electrocatalytic interface combining a hydrogen peroxide‐generating passive air‐breathing gas diffusion electrode with an immobilized hydrogen peroxide‐consuming lignin peroxidase on a single surface and catalyzing the depolymerization of lignins. The ligninolytic potential of this bioelectrochemical device is demonstrated using both lignin models (veratryl alcohol and veratrylglycerol β‐guaiacyl ether) and a technical lignin at room temperature in aqueous media with the reaction efficiency of 14.9% per hour.

Targeted Delivery of Celastrol by GA-Modified Liposomal Calcium Carbonate Nanoparticles to Enhance Antitumor Efficacy Against Breast Cancer.

Breast cancer, a leading health threat affecting millions worldwide, requires effective therapeutic interventions. Celastrol (CEL), despite its antitumor potential, is limited by poor solubility and stability. This study aimed to enhance CEL's efficacy by encapsulating it within glycyrrhizic acid (GA)-modified lipid calcium carbonate (LCC) nanoparticles for targeted breast cancer therapy. The 4T1 mouse breast cancer cells were used for the study. GA-LCC-CEL nanoparticles were prepared using a gas diffusion method and a thin-film dispersion method. GA-LCC-CEL were characterized using the zeta-potential, dynamic light scattering and transmission electron microscope (TEM). The in vitro release behavior of nanoparticles was assessed using the in vitro dialysis diffusion method. Cellular uptake was examined using flow cytometry and confocal microscopy. Intracellular ROS and Rhodamine 123 levels were observed under fluorescence microscopy. MTT and colony formation assays assessed cytotoxicity and proliferation, and apoptosis was analyzed by Annexin V-FITC/PI staining. Wound healing and transwell assays evaluated migration, and Western blotting confirmed protein expression changes related to apoptosis and migration. GA-LCC-CEL nanoparticles displayed a well-defined core-shell structure with a uniform size distribution. They showed enhanced anti-proliferative and pro-apoptotic effects against 4T1 cells and significantly reduced breast cancer cell invasion and migration. Additionally, GA-LCC-CEL modulated epithelial-mesenchymal transition (EMT) protein expression, downregulating Snail and ZEB1, and upregulating E-cadherin. GA-LCC-CEL nanoparticles represent a promising targeted drug delivery approach for breast cancer, enhancing CEL's antitumor efficacy and potentially inhibiting cancer progression by modulating EMT-related proteins.