High Proton Conductivity Research Articles

High Proton Conductivity of Sulfonate-amine Ionic HOFs and Enhancement of SPEEK Composite Membranes.

Hydrogen-bonded organic frameworks (HOFs) are crystalline materials assembled by intermolecular hydrogen-bonding interactions, and their hydrogen-bonding structures are effective pathways for proton transport. Herein, we synthesize iHOF-45 using 4,4'-diaminodiphenylmethane and 1,3,6,8-pyrenetetrasulfonicacid sodium salt with 2D hydrogen-bonding networks. The stability of ionic HOFs (iHOFs) can be enhanced by introducing ionic bonds in addition to hydrogen-bonding forces. Thermal analyses demonstrated that iHOF-45 exhibited excellent thermal stability up to 332 °C. The proton conductivity of iHOF-45 was evaluated, demonstrating a notable increase with rising temperature and RH. At 100 °C and 98 % RH, the conductivity reached 5.25×10-3 S cm-1. The activation energy (Ea) of iHOF-45 was calculated to be 0.281 eV for 98 % RH, and the proton conduction was attributed to the Grotthuss mechanism, whereby the protons were transported in 2D hydrogen-bonding networks. Moreover, iHOF-45 was doped into SPEEK to prepare composite membranes, the proton conductivity of the 15 % iHOF-45/SPEEK membrane reached 9.52×10-2 S cm-1 at 80 °C and 98 % RH, representing a 45.1 % increase over that of the SPEEK. This suggests that doping enhances the proton conductivity of SPEEK and providing a reference for the development of high proton conductivity materials.

Construction and Comparative Research of Two MOFs Proton Conducting Materials Containing Nitro Groups.

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.

Design of Functional Gyroid Minimal Surfaces Transporting Proton Based Solely on Surface Hopping Conduction Mechanism.

Surface proton hopping conduction (SPHC) mechanisms is an important proton conduction mechanism in conventional polymer electrolytes, along with the Grotthuss and vehicle mechanisms. Due to the small diffusion coefficient of protons in the SPHC mechanism, few studies have focused on the SPHC mechanism. Recently, it has been found that a dense alignment of SO3 - groups significantly lowers the activation energy in the SPHC mechanism, enabling fast proton conduction. In this study, a series of polymerizable amphiphilic-zwitterions is prepared, forming bicontinuous cubic liquid-crystalline assemblies with gyroid symmetry in the presence of suitable amounts of bis(trifluoromethanesulfonyl) imide (HTf2N) and water. In situ polymerization of these compounds yields gyroid-nanostructured polymer films, as confirmed by synchrotron small-angle X-ray scattering experiments. The high proton conductivity of the films on the order of 10-2 S cm-1 at 40 °C and relative humidity of 90% is based solely on the SPHC mechanism.

Proton direct transport channels incorporated with protonated porphyrin hyper-crosslinked structures for high proton conductivity HT-PEMs

The trade-off between the mechanical properties and proton conductivity of phosphoric acid (PA)-doped polybenzimidazole (PBI) membranes presents a significant challenge to their development and practical application as high-temperature proton exchange membranes (HT-PEMs). In this study, we prepared hyper-crosslinked poly[2,2′-(p-oxydiphenylene)-5,5′-benzimidazole] (OPBI) membranes with porphyrins (TBPP) containing a substantial amount of halogen. The combination of the protonation effect of porphyrin and the support of the hyper-crosslinked structure results in TBPP-OPBI crosslinked membranes exhibiting excellent mechanical strength and proton conductivity at high PA doping levels (ADLs). In particular, the TBPP-15-OPBI crosslinked membrane exhibits high proton conductivity of 244 mS cm−1 at 180 °C, which is 3.64 times greater than that observed in the OPBI membrane. The H2/air fuel cells based on the TBPP-15-OPBI crosslinked membranes exhibit a peak power density of 521.1 mW cm−2 at 160 °C without humidification and back pressure, as well as excellent durability (over 100 h). Thus, this work provides a straightforward and feasible structural design approach to comprehensively enhance the performance of PA-PBI proton exchange membranes.

Y, Yb, and Gd tri-doping on B-site of Ba(Zr, Ce)O3-δ with improved proton conduction performance

Perovskite-type proton conducting electrolytes are garnering significant attention due to its key role in protonic ceramic electrochemical cells (PCEC) and its application in hydrogen sensors (HS) used for metal melt measurements. Developing high proton conduction perovskite materials with good chemical stability is always a worldwide research focus. In this paper, Y, Yb and Gd triple-doping on B-site of BaCeO3-BaZrO3 solid solution were carried out to investigate the effect of gadolinium doping on the performance of protonic conducting electrolytes. BaZr0.1Ce0.7(Y0.5Yb0.5)0.2-xGdxO3-δ (x = 0, 0.1, 0.15 and 0.2), which were also referred as BZCYYbGdx (x = 0, 10, 15 and 20), were synthesized by solid-state reaction at 1600 °C for 10 h. It is found that BZCYYbGd15 has the highest proton conductivity and proton transfer number among the four prepared materials. The proton mobility of BZCYYbGd15 is 4.06 × 10−6 cm2/(Vꞏs) at 800 °C, which increases with an increased temperature. Its proton transfer number is higher than 0.9 at 500 °C under the atmosphere of PH2O = 0.018 atm. A moderate doping of gadolinium increases the temperature threshold for proton conduction. Proton, oxygen vacancy, electron hole and total conductivity activation energies of BZCYYbGd15 under the wet atmosphere are found to be 0.74, 1.58, 1.41 and 0.92 eV, respectively. Furthermore, the chemical stability of pellets is improved after gadolinium doping. This study provides a reference value for future research on high proton conduction electrolytes.

Polyoxometalates-based metal-organic frameworks with conjugated acid-base pairs for proton supercapacitors

The design and construction of electrode materials with high specific capacity and excellent cycling stability represents a crucial and challenging for the development of supercapacitors. Polyoxometalates (POMs)-based metal–organic frameworks, which are obtained via self-assembling of POMs and organic ligands, showcase high redox capability and stability and are suitable for electrode materials of supercapacitor with high specific capacity and high stability. Three new Dawson-type POM-based metal–organic frameworks (POMOFs), [(Cu3(MPT)2(H2O)3)[P2W18O62]]·12H2O (CUST-831), [(Cu3(MPTD)2(H2O)7)[P2W18O62]]·6H2O (CUST-832) and [(Co2(HMPTZ)2(H2O)4)[P2W18O62]]·9H2O (CUST-833) have been successfully synthesized under hydrothermal conditions via tuning nitrogen heterocycles-based organic ligands. All three Dawson-type POMOFs exhibited impressive specific capacitance values of 225, 305, and 430F g−1, respectively, at a current density of 1 A g−1. The theoretical calculations and experiments indicated that the enhanced performance of CUST-833 is attributed to its higher proton conductivity. The two uncoordinated N atoms on the organic ligand in CUST-833 form a “conjugated acid-base pair” that facilitates rapid proton transport. This work provides new insights into the design and synthesis of proton-conducting materials based on POMs in their crystalline state for supercapacitors.

Highly flexible SCOF proton exchange membrane reinforced with PTFE to enhance fuel cell power density

Sulfonated covalent organic frameworks (SCOFs) facilitate rapid proton conduction through densely ordered sulfonic acid groups, however, the brittleness of COFs self-supporting membranes often makes potential difficulty in fuel cell assembly and limits their power density. Herein, a highly flexible SCOF proton exchange membrane is developed through in-situ growth of a continuous BD(SO3H)2-COF microphase within porous PTFE networks. The strong hydrogen bonding between PTFE and BD(SO3H)2-COF contributes to the defect-free morphology of the BD(SO3H)2/PTFE membrane. The reinforce of PTFE network makes the membrane extremely high flexibility, achieving an elongation at break of 124.4% even with a remarkably high SCOF mass proportion of 90 wt.% (BD(SO3H)2/PTFE-0.9). This allows the membrane to be folded repeatedly, even in dry state. The swelling ratio in water at 80 °C is effectively restricted to 8.6%, even with a high ion exchange capacity of 3.6 mmol g-1 and a water uptake of 68.2%. The densely ordered sulfonic acid groups in continuous BD(SO3H)2-COF microphase contribute to a high proton conductivity up to 249.2 mSꞏcm-1 at 80°C, approximately 1.5 folds that of Nafion 212. As a result, the BD(SO3H)2/PTFE-0.9 membrane achieves a fuel cell power density of 1195.3 mWꞏcm-2 at 80°C, along with a high open circuit voltage of 1.01 V, surpassing the-state-of-the-art COF-based proton exchange membranes. This work provides a novel strategy to fabricate COFs into flexible and size scalable membranes, enhancing the performance of fuel cells.

Potential of kaolin as filler in Nafion composite membranes for PEM fuel cells

Nafion is one of the polymer materials used as a polymer exchange membrane (PEM) in fuel cells due to its high proton conductivity, chemical stability, and fuel cell performance. However, Nafion membranes still have notable disadvantages, such as decreased proton conductivity at high temperatures and low humidity. One of the methods applied to overcome these limitations is to add inorganic compounds to the Nafion matrix. In this study, kaolin, a hygroscopic clay, was incorporated into Nafion for the first time to enhance proton conductivity of the membrane. Kaolin-doped composite membranes (5 %, 10 %, and 15 % kaolin by weight) were produced through the solution casting method and analyzed using various characterization techniques. The synthesized membranes exhibited significantly higher water uptake, lower swelling, higher proton conductivity, and better mechanical properties compared to recast Nafion. Among all composite membranes, Nafion-Kaolin-15 demonstrated a proton conductivity of 0.330 S/cm, which is a remarkable enhancement of 1.43 times compared to recast Nafion. These findings revealed the potential of kaolin-doped Nafion membranes for future applications in PEMFCs.

Anisotropic membrane with high proton conductivity sustaining upon dehydration.

In fuel cells and electrolyzers, suboptimal proton conductivity and its dramatic drop at low humidity remain major drawbacks in proton exchange membranes (PEMs), including current benchmark Nafion. Sustained through-plane (TP) alignment of nanochannels was proposed as a remedy but proved challenging. We report an anisotropic composite PEM, mimicking the water-conductive composite structure of bamboo that meets this challenge. Micro- and nanoscale alignment of conductive pathways is achieved by in-plane thermal compression of a mat composed of co-electrospun Nafion and poly(vinylidene fluoride) (PVDF) nanofibers stabilizing the alignment. This translates to pronounced TP-enhanced proton conductivity, twice that of pure Nafion at high humidity, 13 times larger at low humidity, and 10 times larger water diffusivity. This remarkable improvement is elucidated by molecular dynamics simulations, which indicate that stronger nanochannels alignment upon dehydration compensates for reduced water content. The presented approach paves the way to overcoming the major drawbacks of ionomers and advancing the development of next-generation membranes for energy applications.

Convenient Aqueous‐Phase Synthesis of Covalent Organic Frameworks for Anhydrous Proton Conduction

Covalent organic frameworks (COFs) as a kind of emerging materials has been widely concerned. Developing and recovering new COF materials is of great importance for anhydrous proton conduction, most of the synthesis methods are not organic solvent phase or convenient enough, which would inevitably lead to solvent waste and increase environmental burden. Herein, a method of COF synthesis in aqueous phase is developed, which is used for nonpolluting and sustainable fabrication. Benefits from the suitable channels and stability of HCOF‐1, the composite material H3PO4@HCOF‐1 exhibit high proton conductivity (1.29 × 10−4 S cm−1) at 413 K and the crystallinity of HCOF‐1 is maintained well after measurements. This work broadens the scope of COF synthesis and promotes the development of anhydrous proton conduction.

Exploring the Potential of Cold Sintering for Proton-Conducting Ceramics: A Review.

Proton-conducting ceramic materials have emerged as effective candidates for improving the performance of solid oxide cells (SOCs) and electrolyzers (SOEs) at intermediate temperatures. BaCeO3 and BaZrO3 perovskites doped with rare-earth elements such as Y2O3 (BCZY) are well known for their high proton conductivity, low operating temperature, and chemical stability, which lead to SOCs' improved performance. However, the high sintering temperature and extended processing time needed to obtain dense BCZY-type electrolytes (typically > 1350 °C) to be used as SOC electrolytes can cause severe barium evaporation, altering the stoichiometry of the system and consequently reducing the performance of the final device. The cold sintering process (CSP) is a novel sintering technique that allows a drastic reduction in the sintering temperature needed to obtain dense ceramics. Using the CSP, materials can be sintered in a short time using an appropriate amount of a liquid phase at temperatures < 300 °C under a few hundred MPa of uniaxial pressure. For these reasons, cold sintering is considered one of the most promising ways to obtain ceramic proton conductors in mild conditions. This review aims to collect novel insights into the application of the CSP with a focus on BCZY-type materials, highlighting the opportunities and challenges and giving a vision of future trends and perspectives.

Synthesis of {AlMo14O44}-Based Supramolecular Structures with High Proton Conductivity.

Polyoxometalates (POMs) are esteemed for their remarkable stability and exceptionally high proton conductivity, rendering them ripe for extensive exploration owing to their research significance. Herein, we synthesized two bimolybdenum-capped {AlMoVI8MoV6O44} cluster-based coordination polymers through a solvothermal method. Single-crystal X-ray diffraction analysis elucidates that H[(H2bimb)3(AlMoVI8MoV6O44)] [bimb = 1,4-bis(imidazole-1-ylmethyl)benzene, compound 1] is the POMs-organic supramolecular structure. The introduction of zinc ions into the reaction environment facilitated the connection of initially dispersed ligands, which yielded the well-ordered structure H3[Zn2(bimb)4(AlMoVI8MoV6O44)]·4H2O (compound 2) with a layer distance of 11.8 Å. The proton conductivities (σ) of two compounds were measured under conditions of 85 °C and 98% relative humidity (RH), resulting in values of 3.89 × 10-2 and 4.76 × 10-2 S·cm-1, respectively. This study presents a novel approach to fabricating POMs as proton conductors through structural design and manufacturing adjustments.

Sulfonamide-Sulfonimide Copolymers as Novel, Fluorine-Lean Type of Proton Exchange Membranes for Fuel Cell Application.

In this work, a novel type of fluorine-lean proton exchange membranes is presented, using sulfonamide-sulfonimide functional groups for ion conduction. These groups are constructed on a polystyrene backbone for simple and cost-efficient usage as well as rapid scalability. The polymer is further tailored by adjusting the sulfonamide functionality with various end-groups, namely pentafluorophenyl, 4-fluorophenyl, butyl and octyl groups. These groups affect the pKa, leading to pKa values of 5.7 for the pentafluorophenyl substitution and pKa 10.5 for the alkyl chain. The glass transition temperature of the sulfonamide homopolymers can be reduced from Tg=151 °C (Pentafluorophenyl) to 49 °C (Octyl), making the ionomer more flexible at room temperature. The combination of the non-swelling sulfonamide further mitigates the high water uptake of the sulfonimide while maintaining the nominal ion exchange capacity. This combination leads to extremely high proton conductivities with up to σ=283 mS cm-1 at room temperature, which is clearly outperforming Nafion and approaches values for acid doped systems. This approach can pave the way to a novel type of ion conducting class in proton exchange membrane fuel cells.

Quaternized poly(aryl imidazolium) containing bulky binaphthyl group as proton exchange membrane for high-temperature fuel cells

The low power output and high phosphoric acid (PA) leakage are the main constraints restricting the commercialization of PA-doped high-temperature proton exchange membranes (HT-PEMs). Ionized imidazoles have been shown to be an effective strategy to improve PA retention, however, less research has been conducted on the fractional free volume (FFV) of the backbone of the main chain on PA loss. Herein, novel imidazolium ions polymer (PQBN-4-IM) material with bulky binaphthyl (BN) group was prepared as PA-doped HT-PEM using a one-step superoxid acid catalyzed polycondensation and subsequent methylation process. The rigidity and hydrophobicity of the BN group promote PQBN-4-IM PEM to produce more obvious microphase separation morphology and large FFV, which is beneficial for forming better ion transport channels and excellent PA interaction. Notably, the PA-doped PQBN-4-IM (PQBN-4-IM/PA) membrane has the highest proton conductivity (90.26 mS cm−1, 180 ℃) and peak power density (PPD) (802.5 mW cm−2, 180 ℃) than PQTP-4-IM/PA and m-PBI/PA HT-PEMs. Moreover, the PQBN-4-IM/PA membrane has higher PA retention at 80 ℃/40 % relative humidity (RH), 40 ℃/60 % RH, or immersed in water due to enhancement on ion-pair interactions by microstructure. Under the accelerated stress test (AST) of the fuel cell (FC), the PQBN-4-IM/PA membrane loses only 12.22 % of PPD after 200 cycles at 80 ℃, which exhibits higher PPD retention than that of the PQBP-4-IM/PA (70.23 %), PQTP-4-IM/PA (74.36 %) and m-PBI/PA (65.25 %) membranes, and shows excellent durability of cell performance for more than 1000 h without significant voltage decay at 160 °C. Thus, the outstanding performance suggests that the microstructure and morphology of imidazolium ions polymer membranes significantly influence proton conductivity, performance, and the durability of a cell.

A 2D open framework zinc phosphate and its high proton conductance properties at medium and low temperature

A 2D open-framework zinc phosphate [C3N2H12][Zn2(HPO4)3] (1) was synthesized by solvothermal method. The inorganic anion layer is constructed from Zn2P2O12 cluster units and the interlayer spaces are filled by the diprotonated DAP molecules. The resultant compound had high purity and thermal stability by PXRD and TG analysis. This compound exhibited strongly temperature and humidity dependent proton conductivity, and its highest proton conductivity achieves 2.36 × 10−2 S.cm−1 at 100 %RH and 333 K. Moreover, the important effect of the dense hydrogen bond network in elevating the proton conductivity was explored through comparing the structure and proton conduction behavior between 1 and [C3N2H12][Zn(HPO4)2] (2), which synthesized via the same hydrothermal reaction process, and only a slight difference in the amount of DAP.

Mechanism underlying anion-sieving in poly(ionic liquid)-based membrane: Effective acid recovery from engineering waste

Anion exchange membranes (AEMs) are promising for recovering acid from different engineering effluent due to their lower energy consumption, positive environmental impact, and potential for providing clean water resources. Utilizing the diffusion dialysis (DD) process, AEMs effectively retain metal ions while selectively allowing fast proton permeation. Achieving high hydrophilicity, proton conductivity, and ion exchange capacity through exact control of polymeric structure and chemical composition is crucial for enhancing the efficiency of the acid recovery process. This study presents the findings on the impact of novel Poly(ionic liquid) on cellulose acetate-based AEMs for acid recovery through DD application. In this study, interconnected nanochannel AEMs with high acid permeability are engineered using a straightforward blending technique. Poly(3-butyl-1-vinylimidazolium bromide-co-methyl methacrylate-co-styrene) (poly([BVIM]-[Br]–co–MMA-co-Styrene, PIL) is blended with cellulose acetate to achieve ionic crosslinking, resulting in a mechanically stable membrane. The dosage of PIL within the membrane matrix plays a vital role in determining the prepared membranes' physicochemical properties and ion exchange capabilities, which exhibit excellent thermal stability. Remarkably, the optimal AEM (7.5 % PILM) exhibits a high acid dialysis coefficient (UH+) of 1.05 m/h and a separation factor (S) of 802, outperforming previously reported state-of-the-art AEMs and commercial membranes. These findings indicate that the prepared AEMs are highly effective for acid recovery through DD. Notably, our work stands out by introducing new AEMs with superior acid dialysis performance and selectivity.

Two birds with one stone: A ferrocene-based zirconium(IV)-organic framework nanosheet denoting intrinsic high proton conductivity and acting as a fine dopant to chitosan-based composite membranes

Recently, it was demonstrated that employing metal-organic frameworks (MOFs) with prominent proton conductivity (σ) as fillers with organic substrates such as chitosan (CS) or Nafion is an effective approach for preparing composite membranes (CMs) with outstanding functionalities. Inspired by this, one extremely stable Zr(IV)-MOF (namely Zr-FDC) with a nanosheet structure produced by 1,1′-ferrocene dicarboxylic acid (H2FDA) was successfully manufactured in this research and subsequently used as a filler to synthesize a series of CS-based CMs via casting method. The alternating current (AC) impedance determinations manifested that both Zr-FDC and the related CS-based CMs (CS/MOF-x; x = 2, 4, 6, 8 being the mass percentage of Zr-MOF in the CM) showed ultrahigh σ values, indicating the structural advantages of the Zr-MOF. Further research verified that when the MOF doping quantity is 4 %, the CM's (CS/MOF-4) σ is the greatest, being 2.22 × 10−2 S/cm, which is boosted by nearly tenfold at 100 °C and 98 % relative humidity (RH) compared to the original MOF (3.2 × 10−3 S/cm). Furthermore, the CM exhibits superior thermal stability and tensile resistance. Finally, considering the structural features of the MOF and CS, activation energy data, and other determinations, we thoroughly theorized the proton conduction process within the MOF framework and CMs, referencing the subsequent proton exchange membrane design.

Proton Conduction via Water and Ammonia Coordinated Metal Cationic Species in MOF and MHOF Platforms.

Although metal-organic frameworks (MOFs) and metalo hydrogen-bonded organic frameworks (MHOFs) are designed as promising solid-state proton conductors by incorporating various protonic species intrinsically or extrinsically, design and development of such materials by employing the concept of proton conduction through coordinated polar protic solvent is largely unexplored. Herein, we have constructed two proton-conducting materials having different solvent coordinated metal cationic species: In-H2O-MOF, ({[In(H2O)6][In3(Pzdc)6]·15H2O}n; H2Pzdc: pyrazine-2,3-dicarboxylic acid) with coordinated water molecules from hexaaquaindium cationic species, and MHOF-4, ([{Co(NH3)6}2(2,6-NDS)2(H2O)2]n; 2,6-H2NDS: 2,6-naphthalenedisulfonic acid) with coordinated ammonia from hexaammoniacobalt cationic species. Interestingly, higher proton conductivity was achieved for In-H2O-MOF (1.5 × 10-5 S cm-1) than MHOF-4 (6.3 × 10-6 S cm-1) under the extreme conditions (80 ºC and 95% RH), which could be attributed to enhanced acidity of coordinated water molecules having much lower pKa value than that of coordinated ammonia. Greater charge polarization on hydrogen atoms of In3+-coordinated water molecules than that of Co2+-coordinated ammonia led to the high conductivity of In-H2O-MOF, as evident by quantum chemical studies. Such a comparative study on metal-coordinated protic polar solvents in achieving proton conduction in crystalline solids is yet to be made.

Bio-metal organic framework functionalized nanofibers as efficient proton-conducting for proton exchange membrane

A membrane with a low methanol permeability and high proton conductivity (σp) is essential for the effective operation of a direct methanol-based fuel cell. Herein, a bio-metal organic framework was prepared with natural α-amino acids as ligands and then combined with hydrolyzed polyacrylonitrile (PAN) nanofibers (AA-MOF@PAN). The resulting nanocomposite membranes were subsequently integrated into a Nafion matrix (AA-MOF@PAN/Nafion). The –NH2 groups on AA-MOF@PAN interact with –SO3H groups on Nafion, forming long-range acid-base pairs along the interface between the matrix and nanofibers. This interaction creates abundant proton-conducting sites for proton exchange membrane. Notably, the AA-MOF@PAN-4h/Nafion membrane demonstrated an exceptional proton conductivity (σp) of 0.25 S cm−1 and a higher power density of 117.61 mW cm−2 compared to the recast Nafion membrane. This study offers valuable insights into the three-dimensional ordered design of a natural α-amino acids as a proton transfer sites and highlighting their potential applications in proton exchange membranes.

Conjugated acid-base pairs in Keggin-type polyoxometalate-based metal-organic frameworks enhance proton conduction

To achieve high proton conductivities, it is pivotal to design and select appropriate functional organic ligands for constructing polyoxometalate-based metal–organic frameworks (POMOFs). In this work, the effects of functional groups upon the molecular electrostatic potentials and pKa of two organic ligands (4-abpt, theoretical pKa value of 25.13; Hdpt, theoretical pKa value of 9.24) are first investigated by theoretical calculations. And then, two new proton-conductive decorated POMOFs, {[Cu(4-abpt)2(H2O)][Cu(4-abpt)(H2O)][SiW12O40]}·6H2O (CUST-875) and {[Cu(Hdpt)(H2O)2] [Cu(Hdpt)][SiW12O40]}·2H2O (CUST-876), have been designed and obtained via hydrothermal method. Besides, their proton conduction performances and influencing factors also have been investigated in more details. It is found that more water molecules adsorption and the conjugated acid-base pairs played substantial roles in proton conduction. As a consequence, the three-dimensional framework CUST-875, composed of the higher theoretical pKa value organic ligand 4-abpt, exhibited a higher proton conductivity of 1.07 × 10−4 S cm−1 at 95 °C and 98 % relative humidity (RH), surpassing that of CUST-876 by three orders of magnitude. Additionally, CUST-875 possesses the ability to degrade H2O2, which readily generates during charging and discharging of battery and has adverse effects on the battery life. This work contributes new insights into the high efficiency preparation and structure–property relationships of new polyoxometalate (POM)-based crystalline proton conducting materials with relatively high intrinsic proton conductivities.