Transport Sites Research Articles

Molecular insights into substrate translocation in an elevator-type metal transporter

The Zrt/Irt-like protein (ZIP) metal transporters are key players in maintaining the homeostasis of a panel of essential microelements. The prototypical ZIP from Bordetella bronchiseptica (BbZIP) is an elevator transporter, but how the metal substrate moves along the transport pathway and how the transporter changes conformation to allow alternating access remain to be elucidated. Here, we combine structural, biochemical, and computational approaches to investigate the process of metal substrate translocation along with the global structural rearrangement. Our study reveals an upward hinge motion of the transport domain in a high-resolution crystal structure of a cross-linked variant, elucidates the mechanisms of metal release from the transport site into the cytoplasm and activity regulation by a cytoplasmic metal-binding loop, and unravels an unusual elevator mode in enhanced sampling simulations that distinguishes BbZIP from other elevator transporters. This work provides important insights into the metal transport mechanism of the ZIP family.

Mitigating Mercury Accumulation and Enhancing Methylmercury Degradation in Rice: Insights from Zinc-Mercury Antagonism at Molecular Levels.

Zn as an essential element has the potential to protect against mercury (Hg) toxicity in rice. However, the antagonistic effects between Zn and Hg in rice and their mechanisms remain unknown. This study proposed a promising strategy for Zn application to mitigate Hg accumulation and toxicity in rice and revealed the underlying molecular mechanisms. The findings revealed that Zn supplementation significantly reduced the uptake and transportation of both IHg and MeHg in rice, thereby alleviating Hg phytotoxicity. In particular, Zn profoundly mitigated Hg-induced oxidative damage to rice, which was attributed to the redistribution of Hg and Zn in the root and Zn competing for binding sites on glutathione. The co-binding of Zn2+ and HgCH3+ within the same active sites of Zn transporters can promote the transfer of regions with a high charge density distribution at the highest occupied molecular orbital (HOMO) level. This process facilitates proton attack on the Hg-C bond, thereby enhancing MeHg demethylation in rice. By elucidating the molecular mechanisms of Zn, IHg, and MeHg interactions in rice, this study offers new insights for developing efficient strategies to mitigate Hg risks while boosting the Zn content in crops, thereby fortifying food safety.

Harnessing the Unconventional Cubic Phase in 2D LaNiO3 Perovskite for Highly Efficient Urea Oxidation

AbstractPhase engineering is a critical strategy in electrocatalysis, as it allows for the modulation of electronic, geometric, and chemical properties to directly influence the catalytic performance. Despite its potential, phase engineering remains particularly challenging in thermodynamically stable perovskites, especially in a 2D structure constraint. Herein, we report phase engineering in 2D LaNiO3 perovskite using the strongly non‐equilibrium microwave shock method. This approach enables the synthesis of conventional hexagonal and unconventional trigonal and cubic phases in LaNiO3 by inducing selective phase transitions at designed temperatures, followed by rapid quenching to allow precise phase control while preserving the 2D porous structure. These phase transitions induce structural distortions in the [LaO]+ layers and the hybridization between Ni 3d and O 2p states, modifying local charge distribution and enhancing electron transport during the six‐electron urea oxidation process (UOR). The cubic LaNiO3 offers optimal electron transport and active site accessibility due to its high structural symmetry and open interlayer spacing, resulting in a low onset potential of 1.27 V and a Tafel slope of 33.1 mV dec−1 for UOR, outperforming most current catalysts. Our strategy features high designability in phase engineering, enabling various electrocatalysts to harness the power of unconventional phases.

Harnessing the Unconventional Cubic Phase in 2D LaNiO3 Perovskite for Highly Efficient Urea Oxidation

AbstractPhase engineering is a critical strategy in electrocatalysis, as it allows for the modulation of electronic, geometric, and chemical properties to directly influence the catalytic performance. Despite its potential, phase engineering remains particularly challenging in thermodynamically stable perovskites, especially in a 2D structure constraint. Herein, we report phase engineering in 2D LaNiO3 perovskite using the strongly non‐equilibrium microwave shock method. This approach enables the synthesis of conventional hexagonal and unconventional trigonal and cubic phases in LaNiO3 by inducing selective phase transitions at designed temperatures, followed by rapid quenching to allow precise phase control while preserving the 2D porous structure. These phase transitions induce structural distortions in the [LaO]+ layers and the hybridization between Ni 3d and O 2p states, modifying local charge distribution and enhancing electron transport during the six‐electron urea oxidation process (UOR). The cubic LaNiO3 offers optimal electron transport and active site accessibility due to its high structural symmetry and open interlayer spacing, resulting in a low onset potential of 1.27 V and a Tafel slope of 33.1 mV dec−1 for UOR, outperforming most current catalysts. Our strategy features high designability in phase engineering, enabling various electrocatalysts to harness the power of unconventional phases.

Empowering Indigenous-Led Contaminant Monitoring through Collaborative Partnerships and Two-Way Capacity Sharing

Climate-driven landscape change, legacy waste and ongoing infrastructural investment are leading to concerns about contaminant release in Arctic Indigenous and Local communities. Sustainable development that considers threats posed by accelerating environmental change requires accessible, appropriate, and sustained environmental data to inform strategic decision-making. Collaborative partnerships and capacity sharing are necessary to promote resilient and sustainable environmental monitoring approaches, however effective collaboration has been hindered by mismatches in priorities and timelines between communities and research programs. We outline the development and later evolution of a community-based environmental research program focused on monitoring contamination threats posed by legacy infrastructure sourced from industry, transportation and domestic waste sites. Capacities and insights from diverse knowledge systems guided each stage of our research approach. Reflections provided by an Indigenous and non-Indigenous Early Career Researcher (ECR) share insights into different aspects of the research process. We highlight how cross-cultural partnerships and capacity sharing have enabled evolving and reflexive community-based contaminant monitoring. Our approach facilitates a structural shift from collaborative monitoring with external analysis to autonomous monitoring that supports equity in research outcomes. Appropriately considered and resourced co-development at regular points of the research process has been critical to developing a complete and effective Indigenous-led research project.

Urea‐based construction of hydrogen bonding networks for poly(biphenyl alkylene)s anion exchange membrane for fuel cells

AbstractIn recent decades, the “trade‐off” problem of anion exchange membranes (AEMs) has been a concern. Herein, a series of urea‐based multication poly(biphenyl alkylene)s AEMs are prepared by obtaining an ether bond‐free backbone through ultra‐strong acid catalysis, grafting it with multication side chains, and then by accessing urea‐based groups in different ratios. By accessing the urea group, noncovalent bonds are used to link the molecules to act as cross‐links, giving them solubility that chemical cross‐links do not have. The PBTA‐DQA‐35U membrane possessed the highest ionic conductivity of 62.43 mS/cm. Compared with the PBTA‐DQA membrane (80°C, WU = 20.45%, SR = 17.67%), the PBTA‐DQA‐25U membrane showed an increase in water uptake but not much change in swelling (WU = 30.23%, SR = 19.36%), which was attributed to the fact that the hydrophilic urea groups provide cation transport sites while hydrogen bonding inhibits membrane swelling. The PBTA‐DQA‐35U ionic conductivity is retained above 75% after 960 h of alkali stability testing. The power density of the MEA device assembled using PBTA‐DQA‐35U membrane is 421.78 mW/cm2.

Fabrication of endothelialized capillary-like microchannel networks using sacrificial thermoresponsive microfibers.

In the body, capillary beds fulfill the metabolic needs of cells by acting as the sites of diffusive transport for vital gasses and nutrients. In artificial tissues, replicating the scale and complexity of these capillary vessels has proved challenging, especially in a three-dimensional context. In order to better develop thick artificial tissues, it will be necessary to recreate both the form and function of capillaries. Here we demonstrate a top-down method of patterning hydrogels using sacrificial templates formed from thermoresponsive microfibers whose size and architecture approach those of natural capillaries. Within the resulting microchannels, we cultured endothelial monolayers that remain viable for over three weeks and exhibited functional barrier properties. Additionally, we cultured endothelialized microchannels within hydrogels containing fibroblasts and characterized the viability of the co-cultures to demonstrate this approach's potential to when applied to cell-laden hydrogels. This method represents a step forward in the evolution of artificial tissues and a path towards producing viable capillary-scale microvasculature for engineered organs.

Research on the evolution and venting characteristics of gasoline–air mixture explosions in confined pipeline trench spaces

In recent years, international energy cooperation has become more extensive, and the safe and reliable transportation of oil and gas resources has become increasingly important. However, storage and transportation sites can have confined spaces in engineering practice, which can lead to safety problems. There is a risk of gasoline–air mixture explosions in confined spaces such as pump rooms, valve operation rooms, and inspection wells, particularly in Class B and Class C pipeline trench areas that utilize non-sand-filled trenches or where the local depth exceeds 2.0 m. These locations are equipped with doors, manholes, or ventilation openings for personnel access within oil storage zones. To investigate the combustion characteristics of gasoline–air mixture explosions in such confined spaces, experimental research was conducted on a simulation platform (L/D = 15, V = 0.015 m3). The findings reveal the following: (1) the most hazardous initial gasoline–air mixture volume fraction for ignition at the upper ignition point is 1.7%; (2) the morphology of the internal flame evolves through four distinct stages, with the post-explosion flame shapes resembling “brush-like” and “mushroom cloud” formations; (3) low YCH = 1.1%, medium YCH = 1.7%, and high YCH = 2.3% volume fractions of hydrocarbons were selected to analyze the progression of the explosion development process; (4) the external overpressure distribution during venting explosions, with varying initial gasoline–air mixture volume fractions, conforms to the function y = ae−bx as the distance L varies, with venting pressure waves exhibiting a trend of exponential decay.

Gd3Ga5O12: a wide bandgap semiconductor electrolyte for ceramic fuel cells, effective at temperatures below 500 °C

Searching for compatible electrolytes with Ni0.8Co0.15Al0.05LiO2 (NCAL) electrodes with high ionic conductivity at low operational temperatures (<550 °C) is essential for the research on ceramics fuel cells (CFCs). In this work, the experimental and theoretical analyses demonstrate that the highly stable single-phase Gd3Ga5O12 (GGO) garnet structure, composed of Gd-O octahedrons and Ga-O tetrahedrons, provides more active sites for ion transport, resulting in enhanced peak power density (PPD) and stable open circuit voltage (OCV) at low operational temperature. The unique internal garnet structure effectively reduces the interfacial impedance of the prepared fuel cell device, provides many active sites at triple-phase boundaries and increases the electrochemical stability. As a result, the constructed cell can deliver a superior peak power density of 770 mW/cm2 at 490 °C. In addition, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy and theoretical calculations further demonstrate electrolyte effectiveness of GGO, enabling stable OCV even at a low temperature of 370 °C under a H2/air environment. This work can help in improving the understanding of the underlying mechanisms of a single-layer fuel cell device, which is essential to further develop this potential energy technology even at a very low temperature of 370 °C.

Highly Anion-Conductive Viologen-Based Two-Dimensional Polymer Membranes as Nanopower Generators.

Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3 nm), much smaller than the duple Debye length in the diluted electrolyte (6-20 nm), as well as low charge density (<4.5 mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55 W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

Conductivity-enhanced Poly(biphenyl piperidine) anion exchange membranes with organic tubes

Anion exchange membrane fuel cells (AEMFCs) present an economically efficient alternative to proton exchange membrane fuel cells because of the use of non-precious metals. The development of high-performance and durable AEMFCs necessitates the use of highly conductive and robust anion exchange membranes (AEMs). In this study, a novel organic-organic composite AEM was synthesized by preparing poly(arylene piperidinium) polymer through Friedel-Crafts acid condensation and incorporating one-dimensional organic tubes as reinforcing materials. The composite AEM exhibits high conductivity (235 mS cm−1 at 80 °C) due to the chain orientation within the organic tubes and the availability of abundant transport sites. Furthermore, in contrast to the incompatibility of inorganic materials with polymers, the flexible nature of organic tubes enhanced polymer entanglement, significantly boosting the mechanical strength (120 MPa) of the AEM. Crosslinking the polymer backbone with the organic tubes facilitated simultaneous swelling, effectively mitigating interfacial compatibility issues, result in high dimensional stability. The H2–O2 fuel cell employing the developed AEM demonstrated a peak power density of 1018 mW cm−2 at 80 °C. This study provides a comprehensive synthetic strategy for producing stable AEMs with high hydroxide ion conductivity and outstanding mechanical properties tailored for alkaline membrane fuel cell applications.

Enhanced electrocatalytic activity of hafnium doped tungsten oxide (Hf-WO3) for ultrasensitive detection of nonsteroidal anti-inflammatory drug

Efficient hafnium-doped tungsten oxide nanoparticles (Hf-WO3) were developed by hydrothermal approach and characterization was carried out by X-ray diffraction pattern (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) techniques. Cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques were employed to assess the electrochemical response of the fabricated carbon paste electrodes (CPE) for the analysis of mefenamic acid (MA). The objective of this work is to develop and optimize parameters to enhance the selectivity and sensitivity of Hf-WO3 modified sensor for the trace-level detection of MA, addressing its critical importance in both pharmaceutical and environmental analysis. The Hf-WO3 predominantly showed a monoclinic phase with some hexagonal peaks, confirming its good crystallinity and 1-D structure, which enhances charge transport and catalytic sites. XPS analysis confirmed the formation of pure Hf-WO3 by showing distinct W and Hf peaks and verifying their valences: W in the +6 state and Hf in the +4 state. CV showed that the Hf-WO3/CPE greatly enhances the electrochemical oxidation of MA compared to unmodified and tungsten oxide-modified electrodes, with a six-fold increase in peak current and notable redox activity attributed to improved surface properties and charge transfer efficiency. Under optimum experimental conditions, the Hf-WO3/CPE exhibits a low limit of detection (LOD) of 3.94 nM with dynamic concentration linearity ranging from 0.01 to 100.0 μM with good sensitivity of 1.74 μAμM−1cm−2. Furthermore, the Hf-WO3/CPE was employed in real-time analysis of MA in spiked urine samples and pharmaceutical tablet samples, which showed satisfactory recovery results ⁓ 98 %. Moreover, the electrode showed good stability over multiple measurements, and these results demonstrate that Hf-WO3/CPE is a promising sensor for MA detection.

A Method for Predicting the Action Sites of Regional Mudstone Cap Rock Affecting the Diversion of Hydrocarbons Transported along Oil Source Faults

Regional mudstone cap rock has an important influence on the oil and gas distribution of the oil source faults below it. Therefore, studying the influence of these mudstone cap rocks on the hydrocarbon distribution pattern is fundamental to understanding the oil and gas distribution of the lower generation and upper reservoir reservoirs in the Bohai Bay Basin. This study classified two types of hydrocarbon diversion from oil source faults: blockage diversion and seepage diversion. To locate them, we established a method to predict the areas with blockage diversion and seepage diversion separately by superimposing the sealing and leakage parts of the regional mudstone cap rock with the regions of the connected distribution of sand bodies and the favorable hydrocarbon transport sites of the oil source faults, respectively. We used this approach to predict the locations where hydrocarbons are diverted by the oil source faults under the regional mudstone cap rocks in the first and second sections of the Dongying Formation (E3d1-2) in the Liuchu area of the Raoyang Sag, Bohai Bay Basin. The results show that the regional mudstone cap rock’s blockage diversion occurs mainly in the south-central area of Liuchu, with a localized distribution in the northern part. The seepage diversion site is primarily located in the northeastern area and is also found locally in the west. Both diversions are beneficial for the accumulation of hydrocarbons from the source rocks of the first member of the Shahejie Formation (E3s1) to the upper second member of the Dongying Formation (E3d2U). The latter can also accumulate hydrocarbons in the Guantao Formation (N1g). The results align with the hydrocarbon distribution, demonstrating the feasibility of our method to predict various oil source fault diversion sites under the regional mudstone cap rock. This prediction method offers valuable guidance for exploring the lower generation and upper reservoir hydrocarbon accumulations in hydrocarbon-bearing basins.

Molecular insights into substrate translocation in an elevator-type metal transporter.

The Zrt/Irt-like protein (ZIP) metal transporters are key players in maintaining the homeostasis of a panel of essential microelements. The prototypical ZIP from Bordetella bronchiseptica (BbZIP) is an elevator transporter, but how the metal substrate moves along the transport pathway and how the transporter changes conformation to allow alternating access remain to be elucidated. Here, we combined structural, biochemical, and computational approaches to investigate the process of metal substrate translocation along with the global structural rearrangement. Our study revealed an upward hinge motion of the transport domain in a high-resolution crystal structure of a cross-linked variant, elucidated the mechanisms of metal release from the transport site into the cytoplasm and activity regulation by a cytoplasmic metal-binding loop, and unraveled an unusual elevator mode in enhanced sampling simulations that distinguishes BbZIP from other elevator transporters. This work provides important insights into the metal transport mechanism of the ZIP family.

Identification of human-specific amino acid residues governing atenolol transport via organic cation transporter 2

Organic cation transporter 2 (OCT2/SLC22A2) is predominantly localized on the basolateral membranes of renal tubular epithelial cells and plays a crucial role in the renal secretion of various cationic drugs. Although variations in substrate selectivity among renal organic cation transport systems across species have been reported, the characteristics of OCT2 remain unclear. In this study, we demonstrated that atenolol, a β1-selective adrenergic antagonist, is transported almost exclusively by human OCT2, contrasting with OCT2s from other selected species. Using chimeric constructs between human OCT2 (hOCT2) and the highly homologous monkey OCT2 (monOCT2), along with site-directed mutagenesis, we identified non-conserved amino acids Val8, Ala31, Ala34, Tyr222, Tyr245, Ala270, Ile394, and Leu503 as pivotal for hOCT2-mediated atenolol transport. Kinetic analysis revealed that atenolol was transported by hOCT2 with a 12-fold lower affinity than MPP+, a typical OCT2 substrate. The inhibitory effect of atenolol on MPP+ transport was 6200-fold lower than that observed for MPP+ on atenolol transport. Additionally, we observed weaker inhibitory effects on MPP+ transport compared to atenolol transport with ten different OCT2 substrates. Altogether, this study suggests that eight hOCT2-specific amino acids constitute the low-affinity recognition site for atenolol transport, indicating differences in OCT2-mediated drug elimination between humans and highly homologous monkeys. Our findings underscore the importance of understanding species-specific differences in drug transport mechanisms, shedding light on potential variations in drug disposition and aiding in drug development.

Highly Anion‐Conductive Viologen‐Based Two‐Dimensional Polymer Membranes as Nanopower Generators

AbstractTwo‐dimensional polymers (2DPs) and their layer‐stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (&lt;3 nm), much smaller than the duple Debye length in the diluted electrolyte (6–20 nm), as well as low charge density (&lt;4.5 mC m−2). Here, we introduce a π‐conjugated viologen‐based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m−2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m−2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl−, contributing to an outstanding power density of ~55 W m−2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N‐containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl− ion transport pathway. This work demonstrates the great promise of large‐area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

Imidazole and triazine framed porous aromatic framework with rich proton transport sites for high performance high-temperature proton exchange membranes

Phosphoric acid-doped polybenzimidazole (PA-PBI) membranes for high-temperature proton exchange membranes (HT-PEMs) exhibit low proton conductivity under low phosphoric acid loading and poor mechanical properties under high phosphoric acid loading. In order to overcome these disadvantages, a novel kind of porous aromatic framework framed with imidazole and triazine groups (PAF-227) was designed and synthesized, phosphoric acid (PA) was incorporated into PAF-227 by utilizing vacuum-assisted infusion to yield the product PAF-227-PA. Subsequently, this dopant was combined with polybenzimidazole (OPBI) to create the PAF-227-PA/OPBI composite high-temperature proton exchange membranes (HT-PEMs). The PAF-227-PA/OPBI exhibited high proton conductivity (0.24 S cm−1) at 200 °C, as well as a favorable mechanical property (6.73 MPa) and a high PA absorption rate (250.2 %), and the peak power density of the fabricated fuel cells was significantly increased to 678.21 mW cm−2 at 200 °C with the Pt loading of 0.3 mg cm−2. The basic sites of PAF-227 framed with rigid imidazole and triazine groups can anchoring the PA to achieve a high PA retention rate through the acid-basic interaction with PA, and provide sufficient proton conduction sites by forming hydrogen bonds with PA, and synergized with OPBI membranes to form a multiple hydrogen bond and proton transfer network for enhanced mechanical properties and dimensional thermal stability. Thus, this work provided a novel approach to the preparation of HT-PEMs, which exhibited excellent overall performance for HT-PEMs fuel cells.

Core-shell structured MgCo2O4@Ni(OH)2 nanorods as electrode materials for high-performance asymmetric supercapacitors

In the field of energy storage, supercapacitors have received extensive attention in recent years. However, achieving the expected electrochemical performance and energy density of supercapacitors is still a huge challenge. The design and synthesis of binder-free composite electrode with core–shell structure is an effective strategy to improve the electrochemical performance of supercapacitors. In this paper, a heterogeneous core–shell structured and binder-free electrode material MgCo2O4@Ni(OH)2 (MCO@NH) grown on nickel foam (NF) is prepared by a simple hydrothermal and oil bath method. The unique core–shell structure makes the MCO@NH have a large specific surface area, which provides abundant active sites for ion transport and storage, thereby improving the electrochemical performance. The MCO@NH/NF nanocomposite demonstrates a high specific capacitance (Cs) of 1583 F g−1 at 1 A/g. A solid-state asymmetric supercapacitor (ASC) assembled with MCO@NH/NF and active carbon (AC) exhibits excellent energy density (45 Wh kg−1 at 457.5 W kg−1) and outstanding capacitance (89.51 %) and coulombic efficiency (97.8 %) after 12,000 cycles, evidencing its good operation stability and potential practical applications. Therefore, the prepared core–shell MCO@NH/NF electrode can be a promising candidate for energy storage devices.

Molecular-Level Modification of Sulfonated Poly(arylene ether ketone sulfone) with Polyoxovanadate-Ionic Liquid for High-Performance Proton Exchange Membranes.

In this work, a proton-conductive inorganic filler based on polyoxovanadate (NH4)7[MnV13O38] (AMV) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (EMIM TFSI) was synthesized for hybridization with sulfonated poly(aryl ether ketone sulfone) (SPAEKS) to address the "trade-off" between high proton conductivity and mechanical strength. The novel inorganic filler AMV-EMIM TFSI (AI) was uniformly dispersed and stable within the polymer matrix due to the enhanced ionic interaction. AI provided additional proton transport sites, leading to an elevated ion exchange capacity (IEC) and improved proton conductivity, even at low swelling ratios. The optimized SPAEKS-50/AI-5 (50 for degree of sulfonation of SPAEKS and 5 for weight percentage of AI filler) membrane exhibited the highest proton conductivity of 0.188 S·cm-1 at 80 °C with an IEC of 2.38 mmol·g-1. The enhancement of intermolecular forces improved the mechanical strength from 35 to 55 MPa and improved the elongation at break from 17 to 45%, indicating excellent mechanical properties. The hybrid membrane also demonstrated reinforced methanol resistance due to the hydrogen bonding network and blocking effect, making it suitable for direct methanol fuel cell (DMFC) applications, which exhibited a power density of 15.1 mW·cm-2 at 80 °C. The possibility of further functionalizing these hybrid membranes to tailor their properties for specific applications presents exciting new avenues for research and development. By modification of the type and distribution of fillers or incorporation of additional functional groups, the membranes could be customized to meet the unique demands of various energy storage and conversion systems, enhancing their performance and broadening their application scope. This work provides new insights into the design of polymer electrolyte membranes through inorganic filler hybridization.

Anion exchange membrane with enhanced alkaline stability through radiation grafting of ETFE for solid polymer electrolytes

AbstractSolid polymer electrolyte membranes are considered as the nub of many electrochemical devices. Given the climate crisis and related concerns, the evolution of new membrane materials to support the sustainable systems is inevitable. Building on recent advances with the radiation technique and polymer chemistry, herein, anion exchange membranes (AEMs), ETFE‐g‐1VIm/4VP, were fabricated through graft copolymerization of vinyl heterocyclic monomer binary mixture, such as 1‐vinylimidazole (1‐VIm) and 4‐vinylpyridine (4‐VP) onto ethylene tetrafluoroethylene (ETFE), a main polymer backbone without aryl ether bonds. The grafting reaction was achieved at 60°C and then followed by quaternization as a subsequent step. The effects of various reaction grafting conditions were investigated. The ETFE‐g‐1VIm/4VP AEM were characterized w.r.t the morphological and structural features. The dense surface of the grafted membranes is proved by field emission‐scanning electron microscopy (FE‐SEM) images, which also show that the vinyl entities are clearly distributed in the prepolymer, which may lead to a continuous ion transport channel. AEMs processed from the highest graft yield showed good hydroxide conductivity at 90°C, reaching 16.9 mS/cm due to the presence of more transport sites. The same membrane has a relatively good alkaline stability, which is studied through weight percentage method and FT‐IR. Hence, we assume that the introduction of multi‐cationic moieties, pyridinium and imidazolium, contributes to the performance of anion exchange membranes and makes a perfect balance, especially the hydrophilicity and hydrophobicity. These data highlight the potential of the copolymer as an anion exchange membrane for wide spectra of electrochemical applications.Highlights AEMs based on ETFE‐g‐1VIm/4VP are developed via radiation grafting. The membrane exhibits remarkable alkaline stability. FT‐IR, SEM, and weight percentage methods were used to prove the alkaline stability. The membrane has the potential to be used for different electrochemical applications.