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Proton exchange membranes with high ionic conductivity and good chemical stability are critical for achieving high power density and long lifespan of direct methanol cells (DMFCs). Herein, a zwitterionic molecule was grafted onto the surface of polyvinylidene fluoride (PVDF) nanofibers to obtain functionalized PVDF porous substrate (SBMA-PDA@PVDF). Then, sulfonated poly(ether ether ketone) (SPEEK) was filled into the pores of SBMA-PDA@PVDF, and further ionic cross-linked via H 2 SO 4 to prepare the composite membrane (SBMA-PDA@PVDF/SPEEK). The basic groups on the zwitterionic interface could not only establish ionic cross-linking with SPEEK to increase chemical stability and reduce swelling, but also serve as the adsorption sites for subsequent H 2 SO 4 cross-linking to significantly enhance proton conductivity. Super-high proton conductivity (165.34 mS cm -1 , 80 °C) was achieved for the membrane, which was 2.12 times higher than that of the pure SPEEK. Moreover, the SBMA-PDA@PVDF/SPEEK membrane exhibited remarkably improved oxidative stability of 91.6 % mass retention after soaking in Fenton's agent for 12 h, while pure SPEEK completely decomposed. Satisfactorily, the DMFC assembled with SBMA-PDA@PVDF/SPEEK exhibited a peak power density of 99.01 mW cm -2 , which was twice as much as that of commercial Nafion 212 (48.88 mW cm -2 ). After 235 h durability test, only 11 % voltage loss was observed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

In field of electrochemistry, there has been a growing interest in the potential applications of proton-conducting metal-organic frameworks (MOFs). Therefore, how to design and synthesize MOFs with high proton conductivity is considered crucial. In this study, two examples of nitro-containing Cd-based MOFs, MOF-1 {[Cd3(TIPE)1.5(NO3)5Cl(H2O)2]·17H2O}n and MOF-2 {[Cd(TIPE)0.5(nip)]·10H2O}n (TIPE=1,1,2,2-tetrakis(4-(1H-imidazole-1-yl)phenyl)ethene, H2nip=5-Nitroisophthalic Acid), had been successfully designed and synthesized, and their proton-conducting properties were thoroughly investigated. Notably, both materials displayed peak proton conductivity at 98% RH and 90 °C, exhibiting values of 9.13 × 10-3 and 3.00 × 10-3 S∙cm-1 for MOF-1 and MOF-2, respectively. The plausible proton conduction pathways and mechanisms were elucidated through structural analyses, water vapor adsorption studies, and the determination of activation energy (Ea) values. It was found that the difference in proton conductivity between MOF-1 and MOF-2 was mainly associated with the different water absorption rates of the samples. The uniqueness of this study was that for the first time conducted an in-depth study of the role of nitrate in proton conduction, providing new ideas for designing materials with excellent proton conductivity., (© 2024 Wiley‐VCH GmbH.)

Proton-conducting materials have gained popularity owing to their extensive applications in biologic/chemical sensors, supercapacitors, proton sieving, and proton-exchange-membrane fuel cells. To date, the most commercially used polymer membrane has been the Nafion series that exhibits conductivity exceeding 0.1 S cm -1 , however, this series is expensive, has poor dimensional stability, and requires a complex synthesis process. The key criterion for selecting Nafion alternatives is to achieve the systematic integration of high proton conductivity with high stability through a simple and efficient approach. In this study, we used an aliovalent metal substitution strategy to design serial metal-organic frameworks (MOFs), including tetragonal T-Cd-BTC (CH 3 NH 2 CH 3 ) 2 [Cd(BTC)](H 2 O) and quasi-cubic quasi-C-In-BTC (C 4 H 7 N 2 )[In(BTC)] and Im@quasi-C-In-BTC (C 3 H 5 N 2 ) 2 [In(BTC)] frameworks, with 2-methylimidazolium and imidazolium cations as templates, respectively. Because of the aliovalent substitution of In(III) for Cd(II), both the metal-oxygen bond strength and unit cell symmetry gradually increased, resulting in an increase in the thermal stability of quasi-C-In-BTC and Im@quasi-C-In-BTC at temperatures of up to 700 K. Compared with in situ loaded 2-methylimidazolium quasi-C-In-BTC, Im@quasi-C-In-BTC prepared by incorporating the imidazolium cation into the pores of activated quasi-C-In-BTC exhibited a higher proton conductivity of 7.1 × 10 -2  S cm -1 at 338 K and 95 % relative humidity. Thus, Im@quasi-C-In-BTC demonstrated real-life application. This result was confirmed by integrating Im@quasi-C-In-BTC with a poly(vinyl pyrrolidone)-poly(vinylidene fluoride) polymer matrix. Density functional theory simulations indicated that Im@quasi-C-In-BTC was strongly acidic and had high water-adsorption capacities, which contributed to extensive hydrogen-bond networks and strong host-guest interactions, in accordance with the experimental finding., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

This review discusses the progress of research on sulfonated poly(ether ether ketone) (SPEEK) and its composite membranes in proton exchange membrane fuel cells (PEMFCs). SPEEK is a promising material for replacing traditional perfluorosulfonic acid membranes due to its excellent thermal stability, mechanical property, and tunable proton conductivity. By adjusting the degree of sulfonation (DS) of SPEEK, the hydrophilicity and proton conductivity of the membrane can be controlled, while also balancing its mechanical, thermal, and chemical stability. Researchers have developed various composite membranes by combining SPEEK with a range of organic and inorganic materials, such as polybenzimidazole (PBI), fluoropolymers, and silica, to enhance the mechanical, chemical, and thermal stability of the membranes, while reducing fuel permeability and improving the overall performance of the fuel cell. Despite the significant potential of SPEEK and its composite membranes in PEMFCs, there are still challenges and room for improvement, including proton conductivity, chemical stability, cost-effectiveness, and environmental impact assessments.

Organic π-scaffolds are being envisaged for new-age electron- and ion-responsive materials that can accumulate electrons as well as transport proton. However, such systems are extremely rare as electron-deficient scaffolds are unstable in aqueous solution. Here we detail the synthesis of a water-stable core-naphthalenediimide-nitrobenzyl-viologen based tetra-cation, which accumulates up to eight-electrons within an exceptionally narrow potential window of +0.05 V and -1.12 V. The supramolecular interactions and the ensuing ionic framework are tunable based on the three anions, e. g., Cl - , Br - and PF 6 , that are investigated in this work. The ionic framework is formed and supported by a range of H-bonds, in which, the nitro benzyl groups act as pillars connecting the 1D water-tapes and the halide anions. The water molecules are hydrogen-bonded with the halide anions and bestow a facile pathway for the proton conduction, with proton conductivity up to 3.19×10 - , that are investigated in this work. The ionic framework is formed and supported by a range of H-bonds, in which, the nitro benzyl groups act as pillars connecting the 1D water-tapes and the halide anions. The water molecules are hydrogen-bonded with the halide anions and bestow a facile pathway for the proton conduction, with proton conductivity up to 3.19×10 -3  S cm -1 anions do not host the water tapes and consequently the proton conductivity is found to be four orders of magnitude lower. This is a unique example, whereby proton conductivity is realized and is tunable within a highly electron-deficient, eight-electron acceptor, water-stable ionic supramolecular system.6 - anions do not host the water tapes and consequently the proton conductivity is found to be four orders of magnitude lower. This is a unique example, whereby proton conductivity is realized and is tunable within a highly electron-deficient, eight-electron acceptor, water-stable ionic supramolecular system., (© 2024 Wiley-VCH GmbH.)

In this work, a proton-conductive inorganic filler based on polyoxovanadate (NH 4 ) 7 [MnV 13 O 38 ] (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.

Hydrogel-based supercapacitors are an up-and-coming candidate for safe and portable energy storage. However, it is challenging for hydrogel electrolytes to achieve high conductivity and rapid self-healing at subzero temperatures because the movements of polymer chains and the reconstruction capability of broken dynamic bonds are limited. Herein, a highly conductive proton polyacrylamide-phytic acid (PAAm-PA) hydrogel electrolyte with rapid and autonomous self-healing ability and excellent adhesion over a wide temperature range is developed. PA, as a proton donor center, endows the hydrogels with high conductivity (102.0 mS cm -1 ) based on the Grotthuss mechanism. PA can also prevent the crystallization of water and form multiple reversible hydrogen bonds in the polymer network, which solves the dysfunction of self-healing hydrogels in a cryogenic environment. Accordingly, the hydrogel electrolytes demonstrate fast low-temperature self-healing ability with a self-healing efficiency of 79.4% within 3 h at -20 °C. In addition, the hydrogel electrolytes present outstanding adhesiveness on electrodes due to the generation of hydrogen bonds between PA and activated carbon electrodes. As a result, the integrated hydrogel-based supercapacitors with tight bonding electrode/electrolyte interface deliver a 139.5 mF cm -2 specific capacitance at 25 °C. Moreover, the supercapacitors display superb self-healing ability, achieving 92.1% of capacitance recovery after three cutting-healing cycles at -20 °C. Furthermore, the supercapacitors demonstrate only 6.4% capacitance degradation after 5000 charging-discharging cycles at -20 °C. This work provides a roadmap for designing all-in-one flexible energy storage devices with excellent self-healing ability over a wide temperature range.

Developing novel proton exchange membranes (PEMs) with low cost and superior performance to replace Nafion is of great significance. Polyoxometalate-doped sulfonated poly(aryl ether ketone sulfone) (SPAEKS) allows for the amalgamation of the advantages in each constituent, thereby achieving an optimized performance for the hybrid PEMs. Herein, the hybrid membranes by introducing 2MeIm-{Mo 132 } into SPAEKS are obtained. Excellent hydrophilic properties of 2MeIm-{Mo 132 } can help more water molecules be retained in the hybrid membrane, providing abundant carriers for proton transport and proton hopping sites to build successive hydrophilic channels, thus lowering the energy barrier, accelerating the proton migration, and significantly fostering the proton conductivity of hybrid membranes. Especially, SP-2MIMo 132 -5 exhibits an enhanced proton conductivity of 75 mS cm -1 at 80 °C, which is 82.9% higher than pristine SPAEKS membrane. Additionally, this membrane is suitable for application in proton exchange membrane fuel cells, and a maximum power density of 266.2 mW cm -2 can be achieved at 80 °C, which far exceeds that of pristine SPAEKS membrane (54.6 mW cm -2 ). This work demonstrates that polyoxometalate-based clusters can serve as excellent proton conduction sites, opening up the choice of proton conduction carriers in hybrid membrane design and providing a novel idea to manufacture high-performance PEMs., (© 2024 Wiley‐VCH GmbH.)

In recent years, ceramic cells based on high proton conductivity have attracted much attention and can be employed for hydrogen production and electricity generation, especially at low temperatures. Nevertheless, attaining a high power output and durability is challenging, especially at low operational temperatures. In this regard, we design semiconductor heterostructure SFT-ZnO (SrFe 0.3 TiO 3 -ZnO) materials to function as an electrolyte for fuel cell and electrolysis applications. Using this approach, the functional semiconductor heterostructure can deliver a better power output and high ionic and proton conductivity at low operational temperatures. The prepared cell in fuel cell mode has demonstrated excellent performance of 700 mW cm -2 and proton performance of 540 mW cm -2 at the low temperature of 520 °C, suggesting dominant proton conduction. Further, the prepared cell delivers exceptional current densities of 1.18 and 0.38 A cm -2 (at 1.6 and 1.3 V, respectively) at 520 °C in the electrolysis mode. Our electrochemical cell is stable in fuel and electrolysis mode at a low temperature of 500 °C.

Imidazole molecules entrapped in porous materials can exhibit high and stable proton conductivity suitable for elevated temperature (>373 K) fuel cell applications. In this study, new anhydrous proton conductors based on imidazole and mesoporous KIT-6 were prepared. To explore the impact of the acidic nature of the porous matrix on proton conduction, a series of KIT-6 materials with varying Si/Al ratios and pure silica materials were synthesized. These materials were additionally modified with cerium atoms to enhance their Brønsted acidity. TPD-NH 3 and esterification model reaction confirmed that incorporating aluminum into the silica framework and subsequent modification with cerium atoms generated additional acidic sites. UV-Vis and XPS identified the presence of Ce 3+ and Ce 4+ in the KIT-6 materials, indicating that high-temperature treatment after cerium introduction may lead to partial cerium incorporation into the framework. EIS studies demonstrated that dispersing imidazole within the KIT-6 matrices resulted in composites showing high proton conductivity over a wide temperature range (300-393 K). The presence of weak acidic centers, particularly Brønsted sites, was found to be beneficial for achieving high conductivity. Cerium-modified composites exhibited conductivity surpassing that of molten imidazole, with the highest conductivity (1.13 × 10 -3 S/cm at 393 K) recorded under anhydrous conditions for Ce-KIT-6. Furthermore, all tested composites maintained high stability over multiple heating and cooling cycles.

In this paper, we successfully synthesize phosphoric acid functionalized graphene oxide (PGO) based on acid modification of graphene oxide. The composite membrane is further prepared by adding PGO into sulfonated poly(aryl ether ketone sulfone) containing carboxyl groups matrix (C-SPAEKS). The PGO as well as the composite membranes were characterized by a series of tests. The prepared composite proton exchange membranes (PEMs) have good mechanical and electrochemical properties. Compared to the C-SPAEKS membrane, the best composite membrane has a tensile strength of 40.7 MPa while exhibiting superior proton conductivity (110.17 mS cm -1 at 80 °C). In addition, the open-circuit voltage and power density of C-SPAEKS@1% PGO are 0.918 V and 792.17 mW cm -2 , respectively. Compared with C-SPAEKS (0.867 V and 166 mW cm -2 ), it can be seen that our work has a certain effect on the improvement of the single cell performance. The above results demonstrate that the functionalized graphene oxide has greatly improved the electrochemical performance and even the overall performance of PEMs.

Metal organic frameworks (MOFs) constructed with bismuth metal have not been widely reported, especially multifunctional Bi-MOFs. Therefore, developing multifunctional MOFs is of great significance due to the increasing requirements of materials. In this work, a 3D Bi-MOF (Bi-TCPE) with multifunctionality was successfully constructed, demonstrating high thermal stability, water stability, a porous structure, and strong blue fluorescence emission. We evaluated the properties of Bi-TCPE in detecting anions (S 2- , Cr 2 O 7 2- , and CrO 4 2- ) in aqueous solution, along with the rapid visual detection of H 2 S gas and proton conduction. In terms of anion detection, Bi-TCPE achieved the rapid detection of trace S 2- in aqueous solutions, while the K sv value was 1.224 × 10 4 M -1 with a limit of detection (LOD) value of 1.93 μM through titration experiments. Furthermore, Bi-TCPE could sensitively detect Cr 2 O 7 2- and CrO 4 2- , with K sv values of 1.144 × 10 4 S gas. Finally, we evaluated the proton conductivity of Bi-TCPE, and the experimental results showed that the proton conductivity of Bi-TCPE reached 4.77 × 10 4 M -1 , respectively, while LOD reached 2.07 and 2.18 μM. Subsequently, we conducted H 2 S gas detection experiments, and the results indicated that Bi-TCPE could selectively detect H 2 S gas at extremely low concentrations (2.08 ppm) and with a fast response time (<10 s). We also observed significant color changes under both UV light and sunlight. Therefore, we developed a H 2 S detection test paper for the rapid visual detection of H 2 S gas. Finally, we evaluated the proton conductivity of Bi-TCPE, and the experimental results showed that the proton conductivity of Bi-TCPE reached 4.77 × 10 -2 S·cm -1 at 98% RH and 90 °C, achieving an excellent value for unmodified and encapsulated MOFs. In addition, Bi-TCPE showed high stability in proton conduction experiments (it remained stable after 21 consecutive days of testing and 12 cycles of testing), demonstrating relatively high application value. These results indicate that Bi-TCPE is a multifunctional MOF material with great application potential.

In this study, polymer-coated anisotropic inorganic nanowires dispersed in PBI matrix were introduced to construct 1D proton conducting channels within PBI. Ionic-liquid and solvothermal methods were used for the synthesis of ZrO 2 and W 18 O 49 NWs, which were coated with PVPA and PDDA polymers to increase their proton conductivity. Our results showed that, prepared membranes have amorphous nature due to the dominating presence of PBI. SEM analysis revealed the average thickness of membrane of about 36 µm. TG/DTA analysis detected lower weight loss of W 18 O 49 NWs (total 2.8%) compared to ZrO 2 NWs (18%). Proton conductivity analysis showed that, PDDA/W 18 O 49 NWs possess relatively 4 times higher proton conductivity (4 × 10 -4  Scm -1 ) compared to PDDA/ZrO 2 NWs (1 × 10 -4  Scm -1 ) at 80 ℃. In addition, PDDA-coated W 18 O 49 NWs dispersed PBI membranes showed the highest fuel cell current density (1.2 A/cm 2 ) and power density (215 mW/cm 2 ) at 150 ℃ after 24 h which is nearly 2.5 times higher than pure PBI membrane. In addition, they exhibited the lowest in-situ proton resistance of about (0.47 Ω) compared with that of pure PBI membrane (0.8 Ω). Our results are introducing new concepts towards the development of thin and efficient polymer electrolyte membranes for PEM fuel cells., (© 2024. The Author(s).)

High-temperature polymer-electrolyte membrane fuel cells (HT-PEMFCs) are a very important type of fuel cells since they operate at 150-200 °C, making it possible to use hydrogen contaminated with CO. However, the need to improve the stability and other properties of gas-diffusion electrodes still impedes their distribution. Self-supporting anodes based on carbon nanofibers (CNF) are prepared using the electrospinning method from a polyacrylonitrile solution containing zirconium salt, followed by pyrolysis. After the deposition of Pt nanoparticles on the CNF surface, the composite anodes are obtained. A new self-phosphorylating polybenzimidazole of the 6F family is applied to the Pt/CNF surface to improve the triple-phase boundary, gas transport, and proton conductivity of the anode. This polymer coating ensures a continuous interface between the anode and proton-conducting membrane. The polymer is investigated using CO 2 adsorption, TGA, DTA, FTIR, GPC, and gas permeability measurements. The anodes are studied using SEM, HAADF STEM, and CV. The operation of the membrane-electrode assembly in the H 2 /air HT-PEMFC shows that the application of the new PBI of the 6F family with good gas permeability as a coating for the CNF anodes results in an enhancement of HT-PEMFC performance, reaching 500 mW/cm 2 at 1.3 A/cm 2 (at 180 °C), compared with the previously studied PBI-O-PhT-P polymer.

Proton conductors are essential functional materials with a wide variety of potential applications in energy storage and conversion. In order to address the issues of low proton conductivity and poor stability in conventional proton conductors, a simple and valid ion-exchange method was proposed in this study for the introduction of stable and ultrahigh proton conductivity in layered rare earth hydroxides (LRHs). Test analyses by solid-state nuclear magnetic resonance, Fourier transform infrared spectroscopy, and powder X-ray diffraction revealed that the exchange of H 2 PO 4 - not only does not disrupt the layered structure of LRHs, but also creates more active proton sites and channels necessary for proton transport, thereby creating a high-performance proton conductor (LRH-H 2 ). By utilizing this ion-exchange method, the proton conductivity of LRHs can be significantly enhanced from a low level to an ultrahigh level (>10 4 - ). By utilizing this ion-exchange method, the proton conductivity of LRHs can be significantly enhanced from a low level to an ultrahigh level (>10 -2 S·cm -1 ), while maintaining excellent long-term stability. Moreover, through methodically manipulating the guest ions and molecules housed within the interlayers of LRHs, a comprehensive explanation has been presented regarding the proficient mechanism of proton conduction in LRH-H 2 PO 4 - . As a result, this investigation presents a feasible and available approach for advancing proton conductor.

Biological macromolecules exhibit emergent functions through hierarchical self-assembly, a concept that is extended to design artificial supramolecular assemblies. Here, the first example of breaking the common parallel arrangement of capsule-shaped zirconium coordination cages is reported by constructing the hierarchical porous framework ZrR-1. ZrR-1 adopts a quaternary structure resembling protein and contains 12-connected chloride clusters, representing the highest connectivity for zirconium-based cages reported thus far. Compared to the parallel framework ZrR-2, ZrR-1 demonstrated enhanced stability in acidic aqueous solutions and a tenfold increase in BET surface area (879 m 2  g -1 ). ZrR-1 also exhibits excellent proton conductivity, reaching 1.31 × 10 -2 S·cm -1 at 353 K and 98% relative humidity, with a low activation energy of 0.143 eV. This finding provides insights into controlling the hierarchical self-assembly of metal-organic cages to discover superstructures with emergent properties., (© 2024 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Proton exchange membranes are an essential component of proton-exchange membrane fuel cells (PEMFC). Their performance is directly related to the development of ionic channel networks through hydration. Current sensing atomic force microscopy (CSAFM) can map the local conductance and morphology of a sample surface with sub-nano resolution simultaneously by applying a bias voltage between the conducting tip and sample holder. In this study, the ionic channel network variation of Nafion by hydration has been quantitatively characterized based on the basic principles of electrodynamics and CSAFM. A nano-sized PEMFC has been created using a Pt-coated tip of CSAFM and one side Pt-coated Nafion, and studied under different relative humidity (RH) conditions. The results have been systematically analyzed. First, the morphology of PEMFC under each RH has been studied using line profile and surface roughness. Second, the CSAFM image has been analyzed statistically through the peak value and full-width half-maximum of the histograms. Third, the number of protons moving through the ionic channel network (NPMI) has been derived and used to understand ionic channel network variation by hydration. This study develops a quantitative method to comprehend variations in the ionic channel network by calculating the movement of protons into the ionic channel network based on CSAFM images. To verify the method, a comparison is made between the NPMI and the changes in proton conductivity under different RH conditions and it reveals a good agreement. This developed method can offer a quantitative approach for characterizing the morphological structure of PEM. Also, it can provide a quantitative tool for interpretating CSAFM images.

Metal-organic frameworks and supramolecular metal-organic frameworks (SMOFs) exhibit great potential for a broad range of applications taking advantage of the high surface area and pore sizes and tunable chemistry. In particular, metalloporphyrin-based MOFs and SMOFs are becoming of great importance in many fields due to the bioessential functions of these macrocycles that are being mimicked. On the other hand, during the last years, proton-conducting materials have aroused much interest, and those presenting high conductivity values are potential candidates to play a key role in some solid-state electrochemical devices such as batteries and fuel cells. In this way, using metalloporphyrins as building units we have obtained a new crystalline material with formula [H(bipy)] 2 [(MnTPPS)(H 2 O) 2 ]·2bipy·14H 2 O, where bipy is 4,4'-bipyidine and TPPS 4- is the meso -tetra(4-sulfonatephenyl) porphyrin. The crystal structure shows a zig-zag water chain along the [100] direction located between the sulfonate groups of the porphyrin. Taking into account those structural features, the compound was tested for proton conduction by complex electrochemical impedance spectroscopy (EIS). The as-obtained conductivity is 1 × 10 -2 S·cm -1 at 40 °C and 98% relative humidity, which is a remarkably high value.

The incorporation of cerium-zinc bimetallic oxide (CeZnO x ) nanostructures in sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) membranes holds promise in an enhanced and durable fuel cell performance. This investigation delves into the durability and efficiency of SPPO membranes intercalated with CeZnO x nanostructures by varying the filler loading of 1, 2, and 3% (w/w). The successful synthesis of CeZnO x nanostructures by the alkali-aided deposition method is confirmed by wide-angle X-ray diffraction spectroscopy (WAXS), Raman spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analyses. CeZnO x @SPPO nanocomposite membranes are fabricated using a solution casting method. The intricate interplay of interfacial adhesion and coupling configuration between three-dimensional CeZnO x and sulfonic moieties of the SPPO backbone yields an enhancement in the bound water content within the proton exchange membranes (PEMs). This constructs simultaneously an extensive hydrogen bonding network intertwined with the proton transport channels, thereby elevating the proton conductivity ( K m ). The orchestrated reversible redox cycling involving Ce 3+ /Ce 4+ enhances the quenching of aggressive radicals, aided by Zn 2+ , promoting oxygen deficiency and Ce 3+ concentration. This synergistic efficacy ultimately translates into composite PEMs characterized by a mere 4% mass loss and a nominal 6% decrease in K m after rigorous exposure to Fenton's solution. Remarkably, an improved power density of 403.2 mW/cm 2 and a maximum current density of 1260.6 mA/cm 2 were achieved with 2% loading of CeZnO x (SPZ-2) at 75 °C and 100% RH. The fuel cell performance of SPZ-2 is 74% higher than its corresponding pristine SPPO membrane.

Crystalline triazine-based covalent organic frameworks (COFs) are aromatic nitrogen-rich porous materials. COFs typically show high thermal/chemical stability, and are promising for energy applications, but often require harsh synthesis conditions and suffer from low crystallinity. In this work, we propose an environmentally friendly route for the synthesis of crystalline COFs from CO 2 molecules as a precursor. The mass ratio of CO 2 conversion into COFs formula unit reaches 46.3 %. The synthesis consists of two steps; preparation of 1,4-piperazinedicarboxaldehyde from CO 2 and piperazine, and condensation of the dicarboxaldehyde and melamine to construct the framework. The CO 2 -derived COF has a 3-fold interpenetrated structure of 2D layers determined by powder X-ray diffraction, high-resolution transmission electron microscopy, and select-area electron diffraction. The structure shows a high Brunauer-Emmett-Teller surface area of 945 m 2  g -1 and high stability against strong acid (6 M HCl), base (6 M NaOH), and boiling water over 24 hours. Post-modification of the framework with oxone has been demonstrated to modulate hydrophilicity, and it exhibits proton conductivity of 2.5×10 -2  S cm -1 at 85 °C, 95 % of relative humidity., (© 2023 Wiley-VCH GmbH.)

The present work concerns proton-conducting composites obtained by replacing the water molecules present in aluminophosphate and silicoaluminophosphate AFI-type molecular sieves (AlPO-5 and SAPO-5) with azole molecules (imidazole or 1,2,4-triazole). Both the introduction of azoles and the generation of Brønsted acid centers by isomorphous substitution in aluminophosphate materials were aimed at improving the proton conductivity of the materials and its stability. In the presented study, AlPO-5 and several SAPO-5 materials differing in silicon content were synthesized. The obtained porous matrices were studied using PXRD, low-temperature nitrogen sorption, TPD-NH 3 , FTIR, and SEM. The proton conductivity of composites was measured using impedance spectroscopy. The results show that the increase in silicon content of the porous matrices is accompanied by an increase in their acidity. However, this does not translate into an increase in the conductivity of the azole composites. Triazole composites show lower conductivity and significantly higher activation energies than imidazole composites; however, most triazole composites show much higher stability. The different conductivity values for imidazole and triazole composites may be due to differences in chemical properties of the azoles.

In this study, we aimed to design and research proton-conducting membranes based on Aquivion ® -type material that had been modified with detonation nanodiamonds (particle size 4-5 nm, 0.25-5.0 wt. %). These nanodiamonds carried different functional groups (H, OH, COOH, F) that provided the hydrophilicity of the diamond surface with positive or negative potential, or that strengthened the hydrophobicity of the diamonds. These variations in diamond properties allowed us to find ways to improve the composite structure so as to achieve better ion conductivity. For this purpose, we prepared three series of membrane films by first casting solutions of perfluorinated Aquivion ® -type copolymers with short side chains mixed with diamonds dispersed on solid substrates. Then, we removed the solvent and the membranes were structurally stabilized during thermal treatment and transformed into their final form with -SO 3 H ionic groups. We found that the diamonds with a hydrogen-saturated surface, with a positive charge in aqueous media, contributed to the increase in proton conductivity of membranes to a greater rate. Meanwhile, a more developed conducting diamond-copolymer interface was formed due to electrostatic attraction to the sulfonic acid groups of the copolymer than in the case of diamonds grafted with negatively charged carboxyls, similar to sulfonic groups of the copolymer. The modification of membranes with fluorinated diamonds led to a 5-fold decrease in the conductivity of the composite, even when only a fraction of diamonds of 1 wt. % were used, which was explained by the disruption in the connectivity of ion channels during the interaction of such diamonds mainly with fluorocarbon chains of the copolymer. We discussed the specifics of the mechanism of conductivity in composites with various diamonds in connection with structural data obtained in neutron scattering experiments on dry membranes, as well as ideas about the formation of cylindrical micelles with central ion channels and shells composed of hydrophobic copolymer chains. Finally, the characteristics of the network of ion channels in the composites were found depending on the type and amount of introduced diamonds, and correlations between the structure and conductivity of the membranes were established.

In this investigation, we systematically explored the intricate relationship between the structural attributes of polyvinyl alcohol (PVA) membranes and their multifaceted properties relevant to fuel cell applications, encompassing diverse crosslinking conditions. Employing the solution casting technique, we fabricated crosslinked PVA membranes by utilizing phosphoric acid (PA) as the crosslinking agent, modulating the crosslinking temperature across a range of values. This comprehensive approach aimed to optimize the selection of crosslinking parameters for the advancement of crosslinked polymer materials tailored for fuel cell contexts. A series of meticulously tailored crosslinked PVA membranes were synthesized, each varying in PBTCA content (5-30 wt.%) to establish a systematic framework for elucidating chemical interactions, morphological transformations, and physicochemical attributes pertinent to fuel cell utilization. The manipulation of crosslinking agent concentration and crosslinking temperature engendered a discernible impact on the crosslinking degree, leading to a concomitant reduction in crystallinity. Time-resolved attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) was harnessed to evaluate the dynamics of liquid water adsorption and ionomer swelling kinetics within the array of fabricated PVA films. Notably, the diffusion of water within the PVA membranes adhered faithfully to Fick's law, with discernible sensitivity to the crosslinking conditions being implemented. Within the evaluated membranes, proton conductivities exhibited a span of between 10 -3 and 10 -2 S/cm, while methanol permeabilities ranged from 10 -8 to 10 -7 cm 2 /s. A remarkable revelation surfaced during the course of this study, as it became evident that the structural attributes and properties of the PVA films, under the influence of distinct crosslinking conditions, underwent coherent modifications. These changes were intrinsically linked to alterations in crosslinking degree and crystallinity, reinforcing the interdependence of these parameters in shaping the characteristics of PVA films intended for diverse fuel cell applications.

The purpose of this study is to identify the steps involved in fabricating silica/chitosan composite membranes and their suitability for fuel cell applications. It also intends to identify the physical characteristics of chitosan composite membranes, including their degree of water absorption, proton conductivity, methanol permeability, and functional groups. In this investigation, composite membranes were fabricated using the solution casting method with a chitosan content of 5 g and silica dosage variations of 2% and 4% while stirring at a constant speed for 2 h. According to the findings, the analysis of composite membranes produced chitosan membranes that were successfully modified with silica. The optimum membrane was found to be 4% s-SiO 2 from the Sol-gel method with the composite membrane's optimal condition of 0.234 cm/s proton conductivity, water uptake of 56.21%, and reduced methanol permeability of 0.99 × 10 -7 cm 2 /s in the first 30 min and 3.31 × 10 -7 in the last 150 min. Maintaining lower water uptake capacity at higher silica content is still a challenge that needs to be addressed. In conclusion, the fabricated membranes showed exceptional results in terms of proton conductivity and methanol permeability.

Solid-state proton conductors based on the use of metal-organic framework (MOF) materials as proton exchange membranes are being investigated as alternatives to the current state of the art. This study reports a new family of proton conductors based on MIL-101 and protic ionic liquid polymers (PILPs) containing different anions. By first installing protic ionic liquid (PIL) monomers inside the hierarchical pores of a highly stable MOF, MIL-101, then carrying out polymerization in situ, a series of PILP@MIL-101 composites was synthesized. The resulting PILP@MIL-101 composites not only maintain the nanoporous cavities and water stability of MIL-101, but the intertwined PILPs provide a number of opportunities for much-improved proton transport compared to MIL-101. The PILP@MIL-101 composite with HSO 4 - anions shows superprotonic conductivity (6.3 × 10 -2  S cm -1 ) at 85 °C and 98% relative humidity. The mechanism of proton conduction is proposed. In addition, the structures of the PIL monomers were determined by single crystal X-ray analysis, which reveals many strong hydrogen bonding interactions with O/NH···O distances below 2.6 Å., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

In this study, blended perfluorinated sulfonic acid (PFSA) ionomers with equivalent weights (EWs, g/mol) of ~1000, 980, and 830 are prepared. Catalyst layers (CLs), using blended PFSA ionomers, with different side chain lengths and EWs are investigated and compared to CLs using single ionomers. The ion exchange capacity results confirm that blended ionomers have the target EWs. As a result, blended ionomers exhibit higher ion conductivity than single ionomers at all temperatures due to the higher water uptake of the blended ionomers. This implies that blended ionomers have a bulk structure to form a competent free volume compared to single ionomers. Blended ionomers with short side chains and low EWs can help reduce the activation energy in proton conduction due to enhanced hydrophobic and hydrophilic segregation. In addition, when using the blended ionomer, the CLs form a more porous microstructure to help reduce the resistance of oxygen transport and contributes to lower mass transfer loss. This effect is proven in fuel cell operations at not a lower temperature (70 °C) and full humidification (100%) but at an elevated temperature (80 °C) and lower relative humidity (50 and 75%). Blended ionomer-based CLs with a higher water uptake and porous CL structure result in improved fuel cell performance with better mass transport than single ionomer-based CLs.

The performance of a polymer electrolyte fuel cell can be enhanced by improving the proton conductivity of the catalyst layer, where the oxygen reduction reaction generates electrochemical power. Protons are conducted through the ionomer coatings on catalyst-supporting carbon particles, which form porous structures that facilitate oxygen diffusion during the reaction within the catalyst layer. Therefore, while a higher ionomer content in the catalyst layer is favorable, the proton conductivity is additionally governed by the type of carbon support. As the influence of the ionomer distribution is not fully understood, we introduce a novel proton conductivity model for use in simulating catalyst layers with various amounts of ionomers and different carbon types. This proton conductivity model considers that several ionomers occur as thin films with drastically suppressed proton conductivities. Although evaluating the thin-film ionomer fraction is challenging, proton-conducting ion clusters in thick-film ionomers have been detected by characterizing the catalyst layers via small-angle neutron scattering. Our model reveals that reducing the fraction of the thin-film ionomer or avoiding factors that suppress its proton conduction improves the performance of the catalyst layer.

Chitosan (CS), a promising potential biopolymer with exquisite biocompatibility, economic viability, hydrophilicity, and chemical modifications, has drawn interest as an alternative material for proton exchange membrane (PEM) fabrication. However, CS in its original form exhibited low proton conductivity and mechanical stability, restricting its usage in PEM development. In this work, chitosan was functionalized (sulfonic acid (-SO 3 H) groups)) to enhance proton conductivity. The sulfonated chitosan (sCS) was blended with polyvinylidene fluoride (PVDF) polymer, along with the incorporation of functionalized SiO 2 (-OH groups), for fabricating chitosan-based composite proton exchange membranes to enhance microbial fuel cell (MFC) performances. The results show that adding functionalized inorganic fillers (fSiO 2 ) into the membrane enhances the mechanical, thermal, and anti-biofouling behavior. From the results, the PVDF/sCS/fSiO 2 composite membrane exhibited enhanced proton conductivity 1.0644 × 10 -2 S cm -1 at room temperature and increased IEC and mechanical and chemical stability. Furthermore, this study presents a revolutionary way to generate environmentally friendly natural polymer-based membrane materials for developing PEM candidates for enhanced MFC performances in generating bioelectricity and wastewater treatment.

Introduction of mechanical flexibility into proton-conducting coordination polymers (CPs) is in high demand for future protonic applications such as fuel cells and hydrogen sensors. Although such mechanical properties have been primarily investigated in one-dimensional (1D) CPs, in this study, we successfully fabricated highly flexible free-standing CP membranes with a high surface-to-volume ratio, which is beneficial for enhanced performance in the aforementioned applications. We fabricated a layered CP, Cu 2 (NiTCPP) (H 4 (H 2 TCPP); 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin), in which a two-dimensional (2D) square grid sheet composed of tetradentate nickel porphyrins and paddlewheel-type copper dimers was connected to each other by weak van der Waals forces. The mechanical flexibility was evaluated by bending and tensile tests. The flexural and Young's moduli of the membrane were significantly higher than those of conventional Nafion membranes. Electrochemical impedance spectroscopy analysis revealed that the in-plane proton conductivity of the membrane was maintained even under applied bending stress. Because the X-ray diffraction analysis indicates that the proton-conducting pathway through the hydrogen bonding network remains intact during the bending operation, our present study provides a promising strategy for the fabrication of new and advanced 2D CPs without using substrates or additional polymers for protonic devices., (© 2023 Wiley-VCH Verlag GmbH.)

Polymer ion-exchange membranes are featured in a variety of modern technologies including separation, concentration and purification of gases and liquids, chemical and electrochemical synthesis, and hydrogen power generation. In addition to transport properties, the strength, elasticity, and chemical stability of such materials are important characteristics for practical applications. Perfluorosulfonic acid (PFSA) membranes are characterized by an optimal combination of these properties. Today, one of the most well-known practical applications of PFSA membranes is the development of fuel cells. Some disadvantages of PFSA membranes, such as low conductivity at low humidity and high temperature limit their application. The approaches to optimization of properties are modification of commercial PFSA membranes and polymers by incorporation of different additive or pretreatment. This review summarizes the approaches to their modification, which will allow the creation of materials with a different set of functional properties, differing in ion transport (first of all proton conductivity) and selectivity, based on commercially available samples. These approaches include the use of different treatment techniques as well as the creation of hybrid materials containing dopant nanoparticles. Modification of the intrapore space of the membrane was shown to be a way of targeting the key functional properties of the membranes.

2D materials that can provide long-range ordered channels in thin-film form are highly desirable for proton exchange membranes (PEMs). Covalent organic framework nanosheets (CONs) are promising 2D materials possessing intrinsic porosity and high processability. However, the potential of CONs in PEMs is limited by loose sheet stacking and interfacial grain boundary, which lead to unsatisfied mechanical property and discontinuous conduction pathway. Herein, chitosan (CS), a natural polymer with rich NH 2 groups, is designed as the linker of dual-sulfonate CONs (CON-2(SO 3 H)) to obtain CON-2(SO 3 H)-based membrane. Ultrathin CON-2(SO 3 H) with high crystallinity and large lateral size is synthesized at water-octanoic acid interface. The high flexibility of CS chains and their electrostatic interactions with SO 3 H groups of CON-2(SO 3 H) enable effective connection of CON-2(SO 3 H), thus endowing membrane dense structure and exceptional stability. The stacked CON-2(SO 3 H) constructs regular hydrophilic nanochannels containing high-density SO 3 H groups, and the electrostatic interactions between CON-2(SO 3 H) and CS form interfacial acid-base pairs transfer channels. Consequently, CON-2(SO 3 H)@CS membrane simultaneously achieves superior proton conductivity of 353 mS cm -1 (under 80 °C hydrated condition) and tensile strength of 95 MPa. This work highlights the advantages of proton-conducting porous CON-2(SO 3 H) in advanced PEMs and paves a way in fabricating robust CON-based membranes for various applications., (© 2023 Wiley-VCH GmbH.)

Aquivion ® -type perfluorosulfonic acid membranes with a polytetrafluoroethylene backbone and short side chains with sulfonic acid groups at the ends have great prospects for operating in hydrogen fuel cells. To improve the conducting properties of membranes, various types of nanofillers can be used. We prepared compositional Aquivion ® -type membranes with embedded detonation nanodiamond particles. Nanodiamonds were chemically modified with sulfonic acid groups to increase the entire amount of ionogenic groups involved in the proton conductivity mechanism in compositional membranes. We demonstrated the rise of proton conductivity at 0.5-2 wt.% of sulfonated nanodiamonds in membranes, which was accompanied by good mechanical properties. The basic structural elements, conducting channels in membranes, were not destroyed in the presence of nanodiamonds, as follows from small-angle neutron scattering data. The prepared compositional membranes can be used in hydrogen fuel cells to achieve improved performance.

Blend proton exchange membranes (BPEMs) were prepared by blending sulfonated poly(aryl ether nitrile) (SPAEN) with phosphorylated poly(vinylbenzyl chloride) (PPVBC) and named as SPM-x%, where x refers to the proportion of PPVBC to the weight of SPAEN. The chemical complexation interaction between the phosphoric acid and sulfonic acid groups in the PPVBC-SPAEN system resulted in BPEMs with reduced water uptake and enhanced mechanical properties compared to SPAEN proton exchange membranes. Furthermore, the flame retardancy of the PPVBC improved the thermal stability of the BPEMs. Despite a decrease in ion exchange capacity, the proton conductivity of the BPEMs in the through-plane direction was significantly enhanced due to the introduction of phosphoric acid groups, especially in low relative humidity (RH) environments. The measured proton conductivity of SPM-8% was 147, 98, and 28 mS cm -1 under 95%, 70%, and 50% RH, respectively, which is higher than that of the unmodified SPAEN membrane and other SPM-x% membranes. Additionally, the morphology and anisotropy of the membrane proton conductivities were analyzed and discussed. Overall, the results indicated that PPVBC doping can effectively enhance the mechanical and electrochemical properties of SPAEN membranes.

The development of nanocomposite membranes based on hydrocarbon polymers is emerging as one of the most promising strategies for overcoming the performance, cost, and safety limitations of Nafion, which is the current benchmark in proton exchange membranes for fuel cell applications. Among the various nanocomposite membranes, those based on sulfonated polysulfone (sPSU) and Layered Double Hydroxides (LDHs) hold promise regarding their successful utilization in practical applications due to their interesting electrochemical performance. This study aims to elucidate the effect of LDH introduction on the internal arrangement of water molecules in the hydrophilic clusters of sPSU and on its proton transport properties. Swelling tests, NMR characterization, and Electrochemical Impedance Spectroscopy (EIS) investigation allowed us to demonstrate that LDH platelets act as physical crosslinkers between -SO 3 H groups of adjacent polymer chains. This increases dimensional stability while simultaneously creating continuous paths for proton conduction. This feature, combined with its impressive water retention capability, allows sPSU to yield a proton conductivity of ca. 4 mS cm -1 at 90 °C and 20% RH.

A 2D-to-2D (2D: two-dimensional) structural transformation accompanying significant bond rearrangement and coordination environment change is demonstrated in a coordination polymer (CP) comprised of copper(II) ions and terephthalate (BDC 2- ) ligands for the first time. When immersed in water, a free-standing membrane of 2D Cu(BDC)(DMF) (Cu-1; DMF: N,N-dimethylformamide) transforms into 2D Cu(BDC)(H 2 O) 2 (Cu-2) while maintaining its highly oriented layered structure. In the 2D sheet, paddlewheel-type Cu II dimers coordinated with four bidentate BDC ligands in a square-planar array in Cu-1 were released to form uniform aqua-bridged Cu II chains, which are cross-linked with each other by unidentate BDC ligands, in Cu-2. The present facile approach to implement the 2D-to-2D transformation accompanied by bond rearrangement, which is characteristic of CPs, leads to a marked increase in in-plane magnetic susceptibility and proton conductivity. In situ experiments in support of theoretical calculations unveiled the energy diagram that governs the unique structural transformation., (© 2023 Wiley-VCH GmbH.)

Hydrogen-bonded organic frameworks (HOFs) are ordered supramolecular solid structures, however, nothing much explored as centimetre-scale self-standing films. The fabrication of such crystals comprising self-supported films is challenging due to the limited flexibility and interaction of the crystals, and therefore studies on two-dimensional macrostructures of HOFs are limited to external supports. Herein, we introduce a novel chemical gradient strategy to fabricate a crystal-deposited HOF film on an in situ-formed covalent organic polymer film (Tam-Bdca-CGHOF). The fabricated film showed versatility in chemical bonding along its thickness from covalent to hydrogen-bonded network. The kinetic-controlled Tam-Bdca-CGHOF showed enhanced proton conductivity (8.3×10 -5  S cm -1 ) compared to its rapid kinetic analogue, Tam-Bdca-COP (2.1×10 -5  S cm -1 ), which signifies the advantage of bonding-engineering in the same system., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

SrZrO 3 -based perovskites are promising proton-conducting membranes for use in fuel and electrolysis cells, sensors, hydrogen separators, etc., because they combine good proton conductivity with excellent chemical stability. In the present research, the effect of Lu-doping on microstructure, phase composition, and electrical conductivity of SrZr 1-x LuxO 3-δ (x = 0-0.10) was investigated via X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy and impedance spectroscopy. Dense ceramic samples were obtained by the solution combustion synthesis and possessed an orthorhombic perovskite-type structure. The solubility limit of Lu was revealed to lie between x = 0.03 and 0.05. The conductivity of SrZr 1-x Lu x O 3-δ increases strongly with the addition of Lu at x < 0.05 and just slightly changes at x > 0.05. The rise of the water vapor partial pressure results in an increase in the conductivity of SrZr 1-x LuxO 3-δ ceramics, which confirms their hydration ability and significant contribution of protonic defects to the charge transfer. The highest conductivity was achieved at x = 0.10 (10 mS cm -1 at 700 °C, wet air, pH 2 O = 0.61 kPa). The conductivity behavior was discussed in terms of the defect formation model, taking into account the improvement in ceramic sintering at high lutetium concentrations.

A sulfonated poly(ethersulfone) (SPES)-metal-organic framework (MOF) film with excellent proton conductivity was synthesized by anchoring UiO-66-NH 2 to the main chain of the aromatic polymer through the Hinsberg reaction. The chemical bond was formed between the amino group in MOFs and the -SO 2 Cl group in chlorosulfonated poly(ethersulfones) to conduct protons in the proton channel of the membrane, making the membrane have excellent proton conductivity. UiO-66-NH 2 is successfully prepared as a result of the consistency of the experimental and simulated powder X-ray diffraction (PXRD) patterns of MOFs. The existence of absorption peaks of characteristic functional groups in Fourier transform infrared (FTIR) spectra proved the successful preparation of SPES, PES-SO 2 Cl, and a composite film. The results of the AC impedance test indicate that the composite film with a 3% mass fraction has the best proton conductivity of 0.215 S·cm -1 , which is 6.2 times higher than that of the blended film without a chemical bond at 98% RH and 353 K. To our knowledge, there are rarely any reports on the preparation of a composite membrane by directly linking MOFs and the membrane matrix with chemical bonds. This work provides a good way to synthesize the highly conductive proton exchange film.

The study is devoted to one of the important problems of hydrogen energy-the comparative analysis and creation of novel highly conductive and durable medium-temperature proton membranes based on cesium dihydrogen phosphate and fluoropolymers. The proton conductivity, structural characteristics and mechanical properties of (1 - x)CsH 2 PO 4 -x fluoropolymer electrolytes (x-mass fraction, x = 0-0.3) have been investigated and analyzed. UPTFE and PVDF-based polymers (F2M, F42, and SKF26) with high thermal stability and mechanical properties have been chosen as polymer additives. The used fluoropolymers are shown to be chemical inert matrices for CsH 2 PO 4 . According to the XRD data, a monoclinic CsH 2 PO 4 (P2 1 /m) phase was retained in all of the polymer electrolytes studied. Highly conductive and mechanically strong composite membranes with thicknesses of ~50-100 μm were obtained for the soluble fluoropolymers (F2M, F42, and SKF26). The size and shape of CsH 2 PO 4 particles and their distribution have been shown to significantly affect proton conductivity and the mechanical properties of the membranes. The thin-film polymer systems with uniform distributions of salt particles (up to ~300 nm) were produced via the use of different methods. The best results were achieved via the pretreatment of the suspension in a bead mill. The ability of the membranes to resist plastic deformation increases with the growth of the polymer content in comparison with the pure CsH 2 PO 4 , and the values of the mechanical strength characteristics are comparable to the best low-temperature polymer membranes. The proton-conducting membranes (1 - x)CsH 2 PO 4 -x fluoropolymer with the optimal combination of the conductivity and mechanical and hydrophobic properties are promising for use in solid acid fuel cells and other medium-temperature electrochemical devices.

Development of new materials capable of conducting protons in the absence of water is crucial for improving the performance, reducing the cost, and extending the operating conditions for proton exchange membrane fuel cells. We present detailed atomistic simulations showing that graphanol (hydroxylated graphane) will conduct protons anhydrously with very low diffusion barriers. We developed a deep learning potential (DP) for graphanol that has near-density functional theory accuracy but requires a very small fraction of the computational cost. We used our DP to calculate proton self-diffusion coefficients as a function of temperature, to estimate the overall barrier to proton diffusion, and to characterize the impact of thermal fluctuations as a function of system size. We propose and test a detailed mechanism for proton conduction on the surface of graphanol. We show that protons can rapidly hop along Grotthuss chains containing several hydroxyl groups aligned such that hydrogen bonds allow for conduction of protons forward and backward along the chain without hydroxyl group rotation. Long-range proton transport only takes place as new Grotthuss chains are formed by rotation of one or more hydroxyl groups in the chain. Thus, the overall diffusion barrier consists of a convolution of the intrinsic proton hopping barrier and the intrinsic hydroxyl rotation barrier. Our results provide a set of design rules for developing new anhydrous proton conducting membranes with even lower diffusion barriers.

Sulfonated polyether ether ketone (SPEEK) has been widely investigated in proton exchange membrane fuel cells (PEMFCs) due to its excellent thermal stability, chemical stability, and low cost compared with Nafion. However, excessive degree of sulfonation will easily lead to the decrease in thermal stabilities and mechanical properties of SPEEK membranes, which limits the enhancement of proton conductivity. In this work, a series of Schiff-base networks (SNWs) with different contents are in situ synthesized in the SPEEK membrane by a Schiff-base co-condensation reaction, and then, the composite membranes are soaked in sulfonic acid for further improvement of proton conductivity. The highest doping amount of the SNW filler in SPEEK can reach 20 wt %. High loading and low leaching rate of H 2 SO 4 are easily achieved owing to the similar size between sulfuric acid molecules and micropores in SNW. Moreover, abundant amino and imine groups in SNW networks contribute to the anchoring of H 2 SO 4 into the pores by acid-base interactions. The proton conductivity of the SPEEK/S-SNW-15 composite membrane can reach 115.53 mS cm -1 at 80 °C and 100% RH. Meanwhile, the composite membrane also exhibits satisfied stability and mechanical property.

The development of phosphorylated polybenzimidazoles (PBI) for high-temperature polymer-electrolyte membrane (HT-PEM) fuel cells is a challenge and can lead to a significant increase in the efficiency and long-term operability of fuel cells of this type. In this work, high molecular weight film-forming pre-polymers based on N 1 , N 5 -bis(3-methoxyphenyl)-1,2,4,5-benzenetetramine and [1,1'-biphenyl]-4,4'-dicarbonyl dichloride were obtained by polyamidation at room temperature for the first time. During thermal cyclization at 330-370 °C, such polyamides form N -methoxyphenyl substituted polybenzimidazoles for use as a proton-conducting membrane after doping by phosphoric acid for H 2 /air HT-PEM fuel cells. During operation in a membrane electrode assembly at 160-180 °C, PBI self-phosphorylation occurs due to the substitution of methoxy-groups. As a result, proton conductivity increases sharply, reaching 100 mS/cm. At the same time, the current-voltage characteristics of the fuel cell significantly exceed the power indicators of the commercial BASF Celtec ® P1000 MEA. The achieved peak power is 680 mW/cm 2 at 180 °C. The developed approach to the creation of effective self-phosphorylating PBI membranes can significantly reduce their cost and ensure the environmental friendliness of their production.

Recently, it was reported that chitin and chitosan exhibited high-proton conductivity and function as an electrolyte in fuel cells. In particular, it is noteworthy that proton conductivity in the hydrated chitin becomes 30 times higher than that in the hydrated chitosan. Since higher proton conductivity is necessary for the fuel cell electrolyte, it is significantly important to clarify the key factor for the realization of higher proton conduction from a microscopic viewpoint for the future development of fuel cells. Therefore, we have measured proton dynamics in the hydrated chitin using quasi-elastic neutron scattering (QENS) from the microscopic viewpoint and compared the proton conduction mechanism between hydrated chitin and chitosan. QENS results exhibited that a part of hydrogen atoms and hydration water in chitin are mobile even at 238 K, and the mobile hydrogen atoms and their diffusion increase with increasing temperature. It was found that the diffusion constant of mobile protons is two times larger and that the residence time is two times faster in chitin than that in chitosan. In addition, it is revealed from the experimental results that the transition process of dissociable hydrogen atoms between chitin and chitosan is different. To realize proton conduction in the hydrated chitosan, the hydrogen atoms of the hydronium ions (H 3 O + ) should be transferred to another hydration water. By contrast, in hydrated chitin, the hydrogen atoms can transfer directly to the proton acceptors of neighboring chitin. It is deduced that higher proton conductivity in the hydrated chitin compared with that in the hydrated chitosan is yielded by the difference of diffusion constant and the residence time by hydrogen-atom dynamics and the location and number of proton acceptors.

The composite polymer electrolytes (1-x)CsH 2 PO 4 -xF-2M (x = 0-0.3) have been first synthesized and their electrotransport, structural, and mechanical properties were investigated in detail by impedance, FTIR spectroscopy, electron microscopy, and X-ray diffraction methods. The structure of CsH 2 PO 4 (P2 1 /m) with salt dispersion is retained in the polymer electrolytes. The FTIR and PXRD data are consistent, showing no chemical interaction between the components in the polymer systems, but the salt dispersion is due to a weak interface interaction. The close to uniform distribution of the particles and their agglomerates is observed. The obtained polymer composites are suitable for making thin highly conductive films (60-100 μm) with high mechanical strength. The proton conductivity of the polymer membranes up to x = 0.05-0.1 is close to the pure salt. The further polymers addition up to x = 0.25 results in a significant decrease in the superproton conductivity due to the percolation effect. Despite a decrease, the conductivity values at 180-250 °C remain high enough to enable the use of (1-x)CsH 2 PO 4 -xF-2M as a proton membrane in the intermediate temperature range.

Understanding the ionic structure and charge transport on proton exchange membranes (PEMs) is crucial for their characterization and development. Electrostatic force microscopy (EFM) is one of the best tools for studying the ionic structure and charge transport on PEMs. In using EFM to study PEMs, an analytical approximation model is required for the interoperation of the EFM signal. In this study, we quantitatively analyzed recast Nafion and silica-Nafion composite membranes using the derived mathematical approximation model. The study was conducted in several steps. In the first step, the mathematical approximation model was derived using the principles of electromagnetism and EFM and the chemical structure of PEM. In the second step, the phase map and charge distribution map on the PEM were simultaneously derived using atomic force microscopy. In the final step, the charge distribution maps of the membranes were characterized using the model. There are several remarkable results in this study. First, the model was accurately derived as two independent terms. Each term shows the electrostatic force due to the induced charge of the dielectric surface and the free charge on the surface. Second, the local dielectric property and surface charge are numerically calculated on the membranes, and the calculation results are approximately valid compared with those in other studies.

In recent years, light-responsive molecules have been incorporated in metal-organic frameworks (MOFs) to fabricate light-responsive intelligent devices, where reversible isomerization of the guest molecules in the nanopores is crucial. However, how to design a porous environment of MOFs to achieve a reversible isomerization remains unknown until now. In this work, donor-acceptor Stenhouse adducts (DASAs), a new kind of visible light responsive compound, were confined in the nanopores of different MOFs to study their isomerization upon visible-light irradiation/mild heating. We found that the polarity of the pore environment is the key to control the reversibility of isomerization of such guest molecules. Under the guidance of this principle, MIL-53(Al) was screened to investigate the proton conductivity and switching performance of the DASA-confined MOF. The proton conductance was up to 0.013 S cm -1 at 80 °C and 98 % RH, and at least 30 switching cycles were achieved thanks to the Grotthuss-type mechanism and the low polarity of MIL-53(Al) pore environment., (© 2023 Wiley-VCH GmbH.)

Two ionic hydrogen-bonded organic frameworks (iHOF-10, iHOF-11) were prepared using 1,1'-diamino-4,4'-bipyridine diiodide (Dbpy ⋅ 2I) and tetrakis(4-sulfophenyl)ethylene (H 4 TPE). With increasing RH and temperature, water molecules induce single crystal to single crystal (SCSC) transformation of iHOF-10, resulting in the formation of iHOF-11. At 90 °C, 98 % RH, the proton conductivity of iHOF-11 (7.03×10 -3  S cm -1 ) is 2.09 times higher than iHOF-10 (3.37×10 -3  S cm -1 ). At 50 °C, 98 % RH, iHOF-11 (9.49×10 -4  S cm -1 ) is 19.06 times higher than iHOF-10 (4.98×10 -5  S cm -1 ). The proton conductivity shows water molecules enter the crystal and induce crystal transformation and reorganization of the hydrogen bonding structure, thus increasing the proton conductivity and stability., (© 2023 Wiley-VCH GmbH.)

Ionic conduction in highly designable and porous metal-organic frameworks has been explored through the introduction of various ionic species (H + , OH - , Li + , etc.) using post-synthetic modification such as acid, salt, or ionic liquid incorporation. Here, we report on high ionic conductivity (σ>10 -2  S cm -1 ) in a two-dimensionally (2D)-layered Ti-dobdc (Ti 2 (Hdobdc) 2 (H 2 dobdc), H 4 dobdc: 2,5-dihydroxyterephthalic acid) via LiX (X=Cl, Br, I) intercalation using mechanical mixing. The anionic species in lithium halide strongly affect the ionic conductivity and durability of conductivity. Solid-state pulsed-field gradient nuclear magnetic resonance (PFG NMR ) verified the high mobility of H + and Li + ions in the temperature range of 300-400 K. In particular, the insertion of Li salts improved the H + mobility above 373 K owing to strong binding with H 2 O. Furthermore, the continuous increase in Li + mobility with temperature contributed to the retention of the overall high ionic conductivity at high temperatures., (© 2023 Wiley-VCH GmbH.)

Both proton exchange membrane fuel cells and uranium-based nuclear techniques represent two green and advanced energies. However, both of them still face some intractable scientific and industrial problems. For the former, established proton-conduction materials always suffer one or another defect such as low proton conductivity, high activation energy, bad durability, or just small-scale product; while for the later, there still lacks available adsorbent to selectively recover of UO 2 2+ from concentrated nitric acid (>1 M) during the spent fuel reprocessing due to the deactivation of the adsorption site or the decomposition of adsorbent under such rigorous conditions. It is found that the above two issues can be well solved by the construction of sulfonic-pendent vinylene-linked covalent organic frameworks (COFs), since these COFs contain abundant sulfonic units for both intrinsic proton conduction and UO 2 2+ capture through strong coordination fixation and vinylene linkage that enhances the stability up to 12 M nitric acid (one of the best materials surviving in 12 M HNO 3 )., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The development of solid-state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen-based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH 5 (PO 4 ) 3 (ZP3), which exhibits record-high proton conductivity of 0.5-3.1×10 -2  S cm -1 in the range 25-110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25-110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)