Proton Conductance Pathway Research Articles

Preparation of high temperature proton exchange membrane through covalent organic framework doped polyvinylidene fluoride nanofibers

Covalent organic framework (COF) exhibits the great potential to promote proton conduction under low relative humidity for proton exchange membranes (PEMs). In this research, quick and stable proton conduction has been achieved since the prepared COF and polyvinylidene fluoride (PVDF) nanofibers are believed to constitute successive proton conduction channels. The PVDF-COF nanofibers membrane is prepared through the in-situ growth of COF along PVDF nanofibers. The fine compatibility can drive the stable combination of COF with the PVDF nanofibers in PVDF-COF nanofibers. Most importantly, the fibrous PVDF nanofibers accelerate proton conduction through confining the proton conduction pathways. Additionally, ionic liquids of 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-butyl-3-methylimidazole hexafluorophosphate (BmimPF6) as proton conduction carriers have been introduced to accelerate proton conduction in the prepared PVDF-COF/BmimCl/PA and PVDF-COF/BmimPF6/PA membranes. Phosphoric acid (PA) molecules are combined by COF and ionic liquid cations with the formation of intermolecular hydrogen bonds. As a result, the PVDF-COF/BmimPF6/PA membrane exhibits the proton conductivity of (1.81 ± 0.07) × 10−1 S/cm at 160 °C. The long-term proton conductivity stability is determined, deriving from the proton conductivities of 1.77×10−2 S/cm at 80 °C and 1.42×10−2 S/cm at 110 °C in the 400 h non-stop measurement. The single fuel cell equipped with the PVDF-COF/BmimPF6/PA membrane represents the open circuit voltage of 0.927 V and the peak power density of 178.8 mW/cm2 at 100 °C, 0.907 V and 326.5 mW/cm2 at 120 °C.

Rational Tuning the Proton Conductivity and Stability of Hydrogen-Bonded Organic Frameworks.

In the development of proton conductors, it is crucial to regulate proton conduction pathways and enhance structural stability. In this study, we designed and constructed three hydrogen-bonded organic frameworks (HOFs), namely, NKM-HOF-9, NKM-HOF-10, and NKM-HOF-11, with different dimensional hydrogen-bonding pathways using 4,4'-sulfonyldibenzoic acid and various bases. They are cost-effective and easy to synthesize, allowing for their large-scale production at room temperature. By purposefully altering the ammonium ions, we achieved enhancements in the conductivity and stability of these HOFs. Proton conductivity studies at different humidities and temperatures revealed that at 85 °C and 98% relative humidity, the proton conductivity of NKM-HOF-10 reached 1.7 × 10-3 S cm-1, surpassing that of NKM-HOF-9 by 1 order of magnitude. This improvement was accomplished by increasing the number of proton donors from the base, which resulted in a transition of the hydrogen bond network from discontinuous to continuous, thereby enhancing the proton conduction performance. Moreover, stability tests showed that raising the base's pKa could improve the stability of these frameworks. NKM-HOF-11, which features the highest pKa, demonstrated superior stability by maintaining its structural integrity even at 450 °C.

Proton Conducting Metal-Organic Frameworks (MOFs) via Post Synthetic Transmetallation and Water Induced Structural Transformations.

Post Synthetic Modification (PSM) of Metal-Organic Frameworks (MOFs) is a crucial strategy for developing new MOFs with enhanced functional properties compared to their parent one. PSM can be accomplished through various methods:1) modification of organic linkers; 2) exchange of metal ions or nodes; and 3) inclusion or exchange of solvent/guest molecules. Herein, PSM of bimetallic and monometallic MOFs containing biphenyl dinitro-tetra-carboxylates (NCA) are demonstrated. The tetra carboxylate NCA, produces monometallic Cd-MOF-1 and Cu-MOF-1 and bimetallic CoZn-MOF in solvothermal reactions with the corresponding metal salts. The CoZn-MOF undergoes post-synthetic transmetallation with Cd(NO3)2 and Cu(NO3)2 in aqueous solution to yield Cd-MOF-2 and Cu-MOF-2, respectively. Additionally, green crystals of Cu-MOF-1 found to undergo a single-crystal-to-single-crystal (SCSC) transformation to blue crystals of Cu-MOF-3 upon dipped into water at room temperature. These MOFs demonstrate notable proton conductivities ranging from 10-3 to 10-4 S cm-1 under variable temperatures and humidity levels. Among them, Cu-MOF-3 achieves the highest proton conductivity of 1.36×10-3 S cm-1 at 90 °C and 98 % relative humidity, attributed to its continuous and extensive hydrogen bonding network, which provides effective proton conduction pathways within the MOF. This work highlights a convenient strategy for designing proton-conducting MOFs via post-synthetic modification.

Tuning Proton Conduction by Staggered Arrays of Polar Preyssler-Type Oxoclusters.

Polyoxometalates (POMs), anionic nanosized oxoclusters that can be considered as fragments of metal oxides, have been extensively studied for their diverse composition and structure, showing promise in various fields such as catalysis and electronics. Proton conduction, relevant to catalysis and electronics, has attracted interest in materials chemistry, and POM anions are advantageous in terms of their proton carrier density and mobility. Recently, polar POMs have attracted attention for their unique ferroelectric behaviors, yet they have been little studied with regard to proton conduction, as their polarity has generally been believed to have a negative impact. Here, we propose that polar POMs can be used to align polar proton carriers, such as H2O and polymers, to construct efficient proton-conducting pathways. In this study, we present ionic crystals composed of polar Preyssler-type POMs ([Xn+(H2O)P5W30O110](15-n)-, Xn+ = Ca2+, Eu3+) and K+ exhibiting ultrahigh proton conductivity surpassing 10-2 S cm-1, which is required for practical applications. In contrast, ionic crystals with nonpolar Preyssler-type POMs show an order of magnitude lower proton conductivity. Structural and spectroscopic studies combined with theoretical calculations reveal that proton carriers align with the aid of staggered arrays of polar POMs, forming a hydrogen-bonding network favorable for proton conduction. This study integrates molecular chemistry by the design of POMs and solid-state chemistry by exploring long-range proton conduction mechanisms, offering novel insights for future materials design.

Prominent Intrinsic Proton Conduction in Two Robust Zr/Hf Metal-Organic Frameworks Assembled by Bithiophene Dicarboxylate.

To date, developing crystalline proton-conductive metal-organic frameworks (MOFs) with an inherent excellent proton-conducting ability and structural stability has been a critical priority in addressing the technologies required for sustainable development and energy storage. Bearing this in mind, a multifunctional organic ligand, 3,4-dimethylthiophene[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), was employed to generate two exceptionally stable three-dimensional porous Zr/Hf MOFs, [Zr6O4(OH)4(DTD)6]·5DMF·H2O (Zr-DTD) and [Hf6O4(OH)4(DTD)6]·4DMF·H2O (Hf-DTD), using solvothermal means. The presence of Zr6 or Hf6 nodes, strong Zr/Hf-O bonds, the electrical influence of the methyl group, and the steric effect of the thiophene unit all contribute to their structural stability throughout a wide pH range as well as in water. Their proton conductivity was fully examined at various relative humidities (RHs) and temperatures. Creating intricate and rich H-bonded networks between the guest water molecules, coordination solvent molecules, thiophene-S, -COOH, and -OH units within the framework assisted proton transfer. As a result, both MOFs manifest the maximum proton conductivity of 0.67 × 10-2 and 4.85 × 10-3 S·cm-1 under 98% RH/100 °C, making them the top-performing proton-conductive Zr/Hf-MOFs. Finally, by combining structural characteristics and activation energies, potential proton conduction pathways for the two MOFs were identified.

Energetics of the H-Bond Network in Exiguobacterium sibiricum Rhodopsin.

Exiguobacterium sibiricum rhodopsin (ESR) functions as a light-driven proton pump utilizing Lys96 for proton uptake and maintaining its activity over a wide pH range. Using a combination of methodologies including the linear Poisson-Boltzmann equation and a quantum mechanical/molecular mechanical approach with a polarizable continuum model, we explore the microscopic mechanisms underlying its pumping activity. Lys96, the primary proton uptake site, remains deprotonated owing to the loss of solvation in the ESR protein environment. Asp85, serving as a proton acceptor group for Lys96, does not form a low-barrier H-bond with His57. Instead, deprotonated Asp85 forms a salt-bridge with protonated His57, and the proton is predominantly located at the His57 moiety. Glu214, the only acidic residue at the end of the H-bond network exhibits a pKa value of ∼6, slightly elevated due to solvation loss. It seems likely that the H-bond network [Asp85···His57···H2O···Glu214] serves as a proton-conducting pathway toward the protein bulk surface.

Tunnel-Structured Phosphate Exhibiting High Proton Conductivity and Thermal Stability over a Wide Intermediate Temperature Range.

For the practical application of fuel cells in vehicles, it is a challenge to develop a proton solid electrolyte that coexhibits thermal stability and high proton conductivity at wide intermediate temperatures. Here, we report on the tunnel structured phosphate KNi1-xH2x(PO3)3·yH2O, which exhibits high proton conductivity at room temperature up to 500 °C, with the conductivity value reaching 1.7 × 10-2 S cm-1 at 275 °C for x = 0.18. This material, composed of the smallest cations that form the tunnel framework with face-shared (KO6) and (NiO6) chains and PO4 tetrahedral chains, retained the rigid framework up to 600 °C. Two oxygen sites of water molecules located adjacent to each other along the PO4 tetrahedral chains in the tunnel provided the proton conduction pathway. The sample maintained a conductivity of 5.0 × 10-3 S cm-1 for 10 h at 150 °C while changing the measurement atmosphere to a N2 gas flow, a 4% H2-96% Ar gas flow, and an O2 gas flow. The conductivity value at x = 0.18 obtained from the DC measurement was in the order of 10-6 S cm-1, close to the instrument's measurement limit. These results demonstrate that tunnel phosphate has potential as a proton solid electrolyte for next-generation fuel cells.

Constructing sandwich-like microstructure based on multi-nanofibers to accelerate proton conduction at subzero temperature

The well-ordered microstructure has been demonstrated to accelerate the proton conduction process through reducing proton conduction resistance. In this research, the proton exchange membranes (PEMs) with sandwich-like microstructure have been constructed based on Kevlar nanofibers and bifunctional nanofibers of chitosan (CS) with polyvinyl alcohol (PVA). The CS/PVA bifunctional nanofibers (CPNF) layer has been prepared with electrospinning process, which is stably adhered to the Kevlar nanofibers layer owing to compatible interfacial property. The fine structure stability without layer separation is achieved even with phosphoric acid (PA) molecules doping in the prepared PA doped composite membranes. The fibrous microstructure accelerats proton conduction through regulating proton conduction pathways. The objective of accelerating proton conduction at subzero temperature has been realized, reflecting in high and stable proton conductivities. For instance, the (Kevlar/CPNF/Kevlar)/PA membrane exhibits proton conductivities of 9.75 × 10−3 S/cm at −30 °C and 8.22 × 10−2 S/cm at 30 °C. Most importantly, the fine proton conductivity stability is identified by the results of the cycle test and long-term test. Specifically, the proton conductivities are respectively 8.62 × 10−3 S/cm at −30 °C and 8.07 × 10−2 S/cm at 30 °C after a five heating/cooling cycle process. The proton conductivities remain 2.97 × 10−2 S/cm at −25 °C and 7.19 × 10−2 S/cm at 30 °C after a 1032 h non-stop test. Additionally, the single proton exchange membrane fuel cell with the (Kevlar/CPNF/Kevlar)/PA membrane exhibits the peak power densities of 279.5 mW/cm2 at 100 °C and 352.7 mW/cm2 at 130 °C.

Constructing amino-functionalized flower-shaped ZnO@Al2O3 nanofibers composite membrane (ZANFs/SPSF) with hierarchical proton conductive pathways and excellent methanol resistance

Traditional nanofiber-hybrid proton exchange membranes (PEMs) are limited in their further application due to differences in proton conductivity between vertical and horizontal orientations. In this study, we design and synthesize a novel type aminated flower-shaped ZnO@Al2O3 nanofibers and then filling its three-dimensional interstices with sulfonated polysulfone (SPSF) to obtain a nanofiber composite proton exchange membrane (ZANFs/SPSF). The Al2O3 nanofibers provide long-range and stable proton transport nanochannels in plane, while the flower-shaped ZnO on its surface provide additional vertical transport channels for protons. This combination of 1D and 2D conductive pathways forms a typical 3D hierarchical proton conductive configuration, optimizing the proton transfer pathway. Specifically, the amino groups (-N-H) on the nanofibers surface not only form acid-base pairs with sulfonic acid groups (-SO3H), providing a rich hydrogen bonding network for proton hopping, but also have a similar structure to the polyether sulfone groups (–SO2–NH-), which significantly improves the compatibility between the nanofibers and SPSF. Additionally, the flower-like pleated surface of the nanofibers has a high contact area with the SPSF, providing more proton hopping sites, improving the utilization efficiency of proton carriers, and also resulting in a more stable structure. Moreover, the crosslinked network of nanofibers serves as a barrier to further inhibit methanol permeation. The ZANFs/SPSF exhibits excellent parallel proton conductivity of 348 mS cm−1 at 80 °C and 100% RH, which is 2.7 times higher than that of SPSF under the same conditions, and achieves a peak power density of 405.7 mW cm−2. This approach presents a unique perspective for the preparation of high-performance PEMs for methanol fuel cells.

Maximizing the Potential of Electrically Conductive MOFs.

ConspectusElectrically conductive metal-organic frameworks (EC-MOFs) have emerged as a compelling class of materials, drawing increasing attention due to their unique properties facilitating charge transport within porous structures. The synergy between electrical conductivity and porosity has opened a wide range of applications, including electrocatalysis, energy storage, chemiresistive sensing, and electronic devices that have been underexplored for their insulating counterparts. Despite these promising prospects, a prevalent challenge arises from the predominant adoption of two-dimensional (2D) structures by most EC-MOFs. These 2D frameworks often show modest surface areas and short interlayer distances, hindering molecular accessibility, which deviates from the inherent characteristics of conventional MOFs. Furthermore, the quest for efficient charge transport imposes design constraints, leading to a restricted selection of functional building blocks. Additionally, there is a lack of established functionalization methods within EC-MOFs, limiting their functional diversity. Thus, these challenges have impeded EC-MOFs from reaching their full potential.In this Account, we summarize and discuss our group's efforts aimed at enhancing molecular accessibility and deploying the functional diversity of EC-MOFs. Our focus on enhancing molecular accessibility involves several strategies. First, we employed macrocyclic ligands with intrinsic pockets as the building blocks for EC-MOFs. The integrated intrinsic pockets in the frameworks supplement surface areas and additional pores to enhance molecular accessibility. The resulting macrocyclic ligand-based EC-MOFs exhibit exceptionally high surface areas and confer advantages in electrochemical performances. Second, our efforts extend to addressing the structural limitations, frequently associated with EC-MOFs' 2D structures. Through the pillar insertion strategy, we transformed a 2D EC-MOF platform into a three-dimensional (3D) structure, thereby achieving higher porosity and enhanced molecular accessibility. In pursuing functional diversity, we have delved into molecular-level tuning of EC-MOF building blocks. We demonstrated that electron-rich alkyne-based pockets in the macrocyclic ligands can host transition metals and alkali ions, enabling ion selectivity and showcasing diverse use of EC-MOFs. We utilized a postsynthetic approach to further functionalize metal nodes on the molecular level within an EC-MOF framework, introducing a proton-conducting pathway while preserving its electrical conductivity.We aspire for this Account to provide practical insights and strategies to surmount structural and functional diversity limitations in the realm of EC-MOFs. By integrating enhanced molecular accessibility and diverse functionality, our endeavor to propel the utility of these materials will inspire further rational development for future EC-MOFs and unlock their full potential.

A Rheo-Impedance investigation on the interparticle interactions in the catalyst ink and its impact on electrode network formation in a proton exchange membrane fuel cell

The performance of a proton exchange membrane fuel cell is highly dependent on the microstructure of the catalyst layer. The catalyst layer consists of a network of platinum supported by carbon particles mixed with an ion-conductive ionomer. Optimum coverage of ionomer on catalyst is essential in providing proton conductive pathways while maintaining minimal oxygen transport resistance. Considering that most of the catalyst and ionomer interactions occur as a result of ink formulation and evolution during the high-shear coating process, a new methodology involving a combination of ink flow properties and electrochemical impedance spectroscopy is introduced to study interparticle interactions in catalyst ink. Five ink samples with ionomer-to-carbon ratios ranging from 0 to 1 are used to investigate the interplay between ionomer and catalyst. The flow and impedance properties of the ink are measured simultaneously to investigate the agglomerate characteristics and the percolation of conductive catalyst in the catalyst ink, while fixing the carbon to solvent ratio. This study successfully demonstrate the effectiveness of the newly developed characterization tools, which can be used for evaluating new materials and processing parameters. The insights gained from this study can be applied to optimize the triple-phase-boundaries and form efficient electrode structure with low Pt loading to enhance overall fuel cell performance.

Electrospinning-assisted construction of rapid proton conduction channels in halloysite nanotube-encapsulated ionic liquid-embedded sulfonated poly(ether ether ketone) proton exchange membranes

The most fatal drawback of traditional sulfonated polymer proton-exchange membranes (PEMs) is their heavy dependence on water molecules to conduct protons, which causes a sharp decrease in their proton conductivity in low-humidity environments. Here, composite membranes were fabricated by electrostatically spinning halloysite nanotube-encapsulated ionic-liquids (IL@HNTs) incorporated into sulfonated poly(ether ether ketone) (SPEEK) (SPEEK/IL@HNTs). Using electrospinning, one-dimensional IL@HNTs ionogels with good water absorption were axially and uniformly aligned along the fiber filament direction. This formed long-range uninterrupted proton conduction pathways that greatly improved the proton conductivity of the composite membrane under various humidity environments. The axially-aligned structure facilitated crystallization, which improved the mechanical properties and thermal stability of the composite membrane. The SPEEK/6IL@HNTs membrane exhibited a through-plane proton conductivity of 139.2 mS cm−1 at 90 °C/98 % RH, representing a significant increase compared with the intrinsic SPEEK membrane. The SPEEK/6IL@HNTs membrane demonstrated a maximum power density of 732 mW cm−2, which exceeded that of the Nafion115 membrane (328 mW cm−2) by a factor of 2.2. It exhibited a single-cell performance equivalent to that of the Nafion212 membrane (723 mW cm−2), demonstrating that this provides a feasible approach to operating fuel cells in low-humidity environments without additional humidification.

Improved performance of lanthanide-doped UIO-66/Nafion hybrid proton exchange membrane for water electrolyzer

Incorporating metal-organic frameworks (MOFs) especially the ones with protic functional groups into proton exchange membrane (PEM) can effectively improve its proton conductivity. Lanthanide MOFs (Ln-MOFs) have been recognized as more potential candidates exhibiting proton dissociation capability. However, the performance of PEM upon integrating Ln-MOFs in water electrolyzer has yet to be investigated. In this study, Nafion composites with different loadings of lanthanide Ce-UiO-66 were prepared, characterized and tested by comparing with the non-lanthanide Zr-UiO-66. It was revealed that the proton conductivity of Ce-UiO-66/Nafion composite membrane was higher than pristine Nafion and Zr-UiO-66/Nafion membrane, which was attributed to the fact that the Ce-UiO-66 doping contributed to the construction of the hydrogen-bonded network to enhance the proton conductivity. At 3 wt% Ce-UiO-66 doping, the proton conductivity of the composite membrane can reach 124.45 mS/cm, which is significantly improved by 17 % compared with Zr-UiO-66/Nafion. Such a trend is mainly contributed by the lower proton affinity and proton transfer capability of Ce atoms in Ce-UiO-66, and the higher number of water molecules around Ce atoms favors the reduced tortuosity of the proton conduction pathway in membranes. Single electrolytic cell tests demonstrated the enhancement of electrolysis efficiency upon Ce-UiO-66 doping was improved from 58.77 % to 65.37 % at a current density of 2 A cm−2.

Water-mediated exsolution of nanoparticles in alkali metal-doped perovskite structured triple-conducting oxygen electrocatalysts for reversible cells

Doping monovalent alkali metals with high basicity into barium containing perovskite materials facilitates high proton conduction pathways through the exsolution of barium oxides at humidified air conditions, boosting oxygen reactions activities.

High anhydrous proton conductivity and a smart proton transportation approach of a sulfate coordination polymer.

We successfully synthesized a one-dimensional cobalt sulfate coordinating polymer, whose simple hydrogen bond web structure facilitated the analysis of the proton transfer process. At 175 °C, without humidity, the conductivity is 0.0311 S cm-1, which exceeds those of most of the organic inorganic hybrid materials under anhydrous conditions (world record rank 8). Based on its crystal structure and theoretical calculations, the subversive proton conduction pathway was inferred clearly. We, for the first time, found that the proton smartly chose the path with a lower energy barrier but not the one with short distance to transport avoiding short circuit.

Membrane potential generation by cytochrome <i>bd</i>

This treatise gives an overview of current thinking on the mechanism of generation of a transmembrane electric potential difference (Δψ) during the catalytic cycle of a bd-type triheme terminal quinol oxidase. It is assumed that the main contribution to the Δψ formation is made by the movement of H+ across the membrane along the intraprotein hydrophilic proton-conducting pathway from the cytoplasm to the active site for oxygen reduction of this bacterial enzyme.

A novel proton exchange membrane with long-range ordered proton transport pathways through modulation of interfacial interactions via amino-functionalized polyhedral oligomeric silsesquioxane-grafted graphene oxide

Nano octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) was grafted into graphene oxide (GO) via covalent bonding to synthesize OA-POSS-g-GO. A novel SP/OA-POSS-g-GO proton exchange membrane was prepared by adding sulfonated poly (ether ether ketone) (SPEEK, SP). OA-POSS was well dispersed on GO to form an ordered acid-base pair with SPEEK, which facilitated the construction of continuous ion channels. GO as a carrier facilitated the construction of long-range proton conduction pathways in the membrane. The strong interactions between OA-POSS and SPEEK along with the synergistic effect of GO modulate the size of ionic clusters and increased the bound water ratio within the membrane. The conductivity of the SP/OA-POSS-g-GO-2 membrane (80 °C, 95% RH) reached 0.2096 S⋅cm−1, which was 1.7 times higher than that of the SPEEK membrane (0.1265 S⋅cm−1). The conductivity of the SP/OA-POSS-g-GO-2 membrane increased at 100 °C and 40% RH, while that of the SPEEK membrane decreased with the temperature increased above 80 °C. The maximum power density of the single cell assembled from the composite membrane reached 305.8 mW⋅cm−2 at 80 °C and 95% RH, which was 1.4 and 1.3 times higher than that of the SPEEK and Nafion 117 membrane, respectively.

Proton Conduction in Gly-X (X = Ser, Ser-Gly-Ser) and GS50.

In recent years, the use of biomaterials has been required from the viewpoint of biocompatibility of electronic devices. In this study, the proton conductivity of Glycyl-L-serine (Gly-Ser) was investigated to clarify the relationship between hydration and proton conduction in peptides. From the crystal and conductivity data, it was inferred that the proton conductivity in hydrated Gly-Ser crystals is caused by the cleavage and rearrangement of hydrogen bonds between hydration shells formed by hydrogen bonds between amino acids and water molecules. Moreover, a staircase-like change in proton conduction with hydration was observed at n = 0.3 and 0.5. These results indicate that proton transport in Gly-Ser is realized by hydration water. In addition, we also found that hydration of GSGS and GS50 can achieve proton conduction of Gly-Ser tetrameric GSGS and GS50 containing repeating sequences. The proton conductivity at n = 0.3 is due to percolation by the formation of proton-conducting pathways. In addition to these results, we found that proton conductivity at GS50 is realized by the diffusion constant of 3.21 × 10-8 cm2/s at GS50.

Contribution of zeolitic imidazolate framework-8 in improving the performance of polymer electrolyte membrane for direct methanol fuel cell

Introducing ZIF-8 into the PES-cSMM membranes played a pivotal role in the development of proton-conducting pathways and an effective methanol barrier. We employed dry-wet phase inversion techniques to fabricate PES-cSMM, finding that a 3 wt% cSMM content yielded optimal results. The resulting PES-cSMM exhibits impressive performance, with a 38% higher selectivity and a 95% greater methanol barrier compared to Nafion® 117. The imidazole-N-H linker in the terminal PES-cSMM/ZIF-8 promotes proton transport through a hydrogen bond chain, while the hydrophobic backbone acts as an effective methanol filter. As a result, PES-cSMM/ZIF-8 boasts a 13-fold higher water uptake than Nafion® 117 and achieves a 99% improvement in methanol sieving performance, a highly promising breakthrough for DMFC systems. Proton conductivity for the PES-cSMM/ZIF-8 immersion membrane reaches 19.5 × 10-3 Scm-1, comparable to Nafion® 117, which is 20.4 × 10-3 Scm-1. The structural flexibility of ZIF-8 within PES-cSMM facilitates efficient proton conduction, while the ZIF-8 cage acts as a robust methanol barrier. Computational analysis revealed covalent bonding within the PES-cSMM system. We characterized the chemical interactions in PES-cSMM/ZIF-8 using topology analysis, specifically the Atom in Molecules/Non-covalent analysis (AIM/NCI) technique.

Generation of Membrane Potential by Cytochrome bd.

An overview of current notions on the mechanism of generation of a transmembrane electric potential difference (Δψ) during the catalytic cycle of a bd-type triheme terminal quinol oxidase is presented in this work. It is suggested that the main contribution to Δψ formation is made by the movement of H+ across the membrane along the intra-protein hydrophilic proton-conducting pathway from the cytoplasm to the active site for oxygen reduction of this bacterial enzyme.