Proton Conductivity Research Articles

Room-Temperature Superprotonic Conductivity beyond 10-1 S cm-1 in a Co(II) Coordination Polymer.

An efficient design of crystalline solid-state proton conductors (SSPCs) is crucial for the progress of clean energy applications. Developing such materials to make them work at room temperature with a conductivity of ≥10-1 S cm-1 is of significant interest in terms of technical and commercial aspects. Utilizing the recently highlighted "coordinated-water-driven proton conduction" approach, herein, we have rationally synthesized two highly stable and scalable 1D Co(II) coordination polymers (CPs) as SSPCs, PCM-2 {[Co(bpy)(H2O)2(NO3)2]·H2O}n and PCM-3 {[Co2(bpy)2(SO4)2(H2O)6].4H2O}n, with distinct alignments in coordinated water and coordinated oxo-anions (nitrate and sulfate, respectively). The acidity of the metal-bound water molecules in PCM-2 is further enhanced through cooperative long-range continuous H bonds with coordinated Brønsted basic nitrates (proton acceptors), leading to ultrahigh superprotonic conductivities even at 25 °C (1.03 × 10-1 S cm-1 under 95% RH), and reached a maximum of 2.99 × 10-1 S cm-1 at 85 °C (95% RH). The conductivity at 25 °C is even higher than that of commercial Nafion 117 (6.74 × 10-2 S cm-1 at 100% RH). The absence of such an H-bonding interaction in PCM-3 (closed loops) resulted in a lesser conductivity of 5.87 × 10-5 S cm-1 (95% RH, 85 °C). PCM-2 represents the first example of SSPC exhibiting conductivity in the order 10-1 S cm-1 at ambient temperature (25 °C) with excellent recyclability.

Square-planar Tetranuclear Cluster-based Alkaline Earth Metal-organic Frameworks with Enhanced Proton Conductivity.

Alkaline earth (AE) metal complexes have garnered significant interest in various functional fields due to their nontoxicity, low density, and low cost. However, there is a lack of systematic investigation into the structural characteristics and physical properties of AE-metal-organic frameworks (MOFs). In this research, we synthesized isostructural MOFs consisting of AE4(μ4-Cl) clusters bridged by benzo-(1,2;3,4;5,6)-tris(thiophene-2'-carboxylic acid) (BTTC3-) ligands. The resulting structure forms a truncated octahedral cage denoted as [AE4(m4-Cl)]6(BTTC)8, which further linked to a porous three-dimensional framework. Among the investigated AE ions (Ca, Sr, and Ba), the Ca4-MOF demonstrated good chemical stability in water compared to Sr4-MOF and Ba4-MOF. The N2 adsorption and solid-state UV-vis-NIR absorption behaviors were evaluated for all AE4-MOFs, showing similar trends among the different metal ions. Additionally, the proton conduction study revealed that the Ca4-MOF exhibited ultra-high proton conductivity, reaching 3.52×10-2 S cm-1 at 343 K and 98 % RH. Notably, the introduction of LiCl via guest exchange resulted in an improved proton conduction of up to 6.36×10-2 S cm-1 under similar conditions in the modified LiCl@Ca4-MOF. The findings shed light on the regulation of physical properties and proton conductivity of AE-MOFs, providing valuable insights for their potential applications in various fields.

Enhancing Performance and Stability of High-Temperature Proton Exchange Membranes through Multiwalled Carbon Nanotube Incorporation into Self-Cross-Linked Fluorenone-Containing Polybenzimidazole.

Addressing critical challenges in enhancing the oxidative stability and proton conductivity of high-temperature proton exchange membranes (HT-PEMs) is pivotal for their commercial viability. This study uncovers the significant capacity of multiwalled carbon nanotubes (MWNTs) to absorb a substantial amount of phosphoric acid (PA). The investigation focuses on incorporating long-range ordered hollow MWNTs into self-cross-linked fluorenone-containing polybenzimidazole (FPBI) membranes. The absorbed PA within MWNTs and FPBI forms dense PA networks within the membrane, effectively enhancing the proton conductivity. Moreover, the exceptional inertness of MWNTs plays a vital role in reinforcing the oxidation resistance of the composite membranes. The proton conductivity of the 1.5% CNT-FPBI membrane is measured at 0.0817 S cm-1 at 160 °C. Under anhydrous conditions at the same temperature, the power density of the 1.5% CNT-FPBI membrane reaches 831.3 mW cm-2. Notably, the power density remains stable even after 200 h of oxidation testing and 250 h of operational stability in a single cell. The achieved power density and long-term stability of the 1.5% CNT-FPBI membrane surpass the recently reported results. This study introduces a straightforward approach for the systematic design of high-performance and robust composite HT-PEMs for fuel cells.

Tailoring porous structure in non-ionic polymer membranes using multiple templates for low-cost iron-lead single-flow batteries

Porous ion-selective membranes are promising alternatives for the expensive perfluorosulfonic acid membranes in redox flow batteries. In this work, novel non-ionic porous polyvinylidene fluoride-hexafluoro propylene membranes are designed for iron-lead single-flow batteries. The membranes are prepared using a multiple template approach, involving simultaneously using polyethylene glycol and dibutyl phthalate (DBP) as pore-forming templates. Their porous structure is finely tuned by adjusting the ratio of the two templates. As a result, dual-porous membranes bearing both macro and micropores are obtained. The H3520 membrane with modified porous structure attains a high proton conductivity of 43.5 mS·cm-1 and a relatively low ferric ion diffusion constant (8.61 × 10-8 cm2·min-1) and demonstrates the best balance between these performance-determining parameters (selectivity 5.04 × 105 S·min·cm-3, higher than that of the N115 membrane). Besides, performance tests of the iron-lead single-flow single cells equipped with the dual-porous membranes show a high energy efficiency, exceeding 87.2% at its rated current density, and outstanding cycling stability over 200 charge-discharge cycles. Altogether, the mixed template method presents a promising strategy to prepare high-performance and low-cost non-ionic membranes for redox flow batteries.

In situ growth of covalent organic framework on graphene oxide nanosheet enable proton-selective transport in flow battery membrane

Perfluorosulfonic acid (PFSA) is the most widely used membrane material for all-vanadium redox flow batteries (VRFB). However, severe vanadium ion permeation of PFSA membranes remains to be solved. In this work, a series of PFSA-based composite membranes are prepared by introducing two-dimensional continuous covalent organic framework (COF) to achieve enhanced performance. Two dimensional continuous Schiff base network-type COFs (GO/SNW) are synthesized by using the two-dimensional multi-functionalized surface of graphene oxide (GO) as a reaction site. Compared to the original form of agglomerated particles, two-dimensional continuous structure obtained a larger vanadium resistance area. Comparing to conventional PFSA membranes, the special pores of COF have a size sieving mechanism for selectively proton transfer, leading to simultaneously enhancement of proton conductivity and vanadium barrier property. VRFB assembled with PFSA-GO/SNW-7 showed high Coulombic efficiency (CE: 97.47%–98.18 % VS PFSA: 80.73%–91.92 %) and energy efficiency (EE: 93.04%–85.71 % VS PFSA: 77.53%–81.78 %) at 40–120 mA cm−2. In addition, there is no significant decrease in the efficiency of battery assembled with PFSA-GO/SNW-7 after 800 cycle (than 650 h) tests. This work provides a new direction in the design of fillers for mixed matrix membranes.

Vitrification-enabled enhancement of proton conductivity in hydrogen-bonded organic frameworks

Hydrogen-bonded organic frameworks (HOFs) are versatile materials with potential applications in proton conduction. Traditional approaches involve incorporating humidity control to address grain boundary challenges for proton conduction. This study finds vitrification as an alternative strategy to eliminate grain boundary effect in HOFs by rapidly melt quenching the kinetically stable HOF-SXU-8 to glassy state HOF-g. Notably, a remarkable enhancement in proton conductivity without humidity was achieved after vitrification, from 1.31 × 10−7 S cm−1 to 5.62× 10−2 S cm−1 at 100 °C. Long term stability test showed negligible performance degradation, and even at 30 °C, the proton conductivity remained at high level of 1.2 × 10−2 S cm−1. Molecule dynamics (MD) simulations and X-ray total scattering experiments reveal the HOF-g system is consisted of three kinds of clusters, i.e., 1,5-Naphthalenedisulfonic acid (1,5-NSA) anion clusters, N,N-dimethylformamide (DMF) molecule clusters, and H+-H2O clusters. In which, the H+ plays an important role to bridge these clusters and the high conductivity is mainly related to the H+ on H3O+. These findings provide valuable insights for optimizing HOFs, enabling efficient proton conduction, and advancing energy conversion and storage devices.

The characteristics of high temperature polymer electrolyte membranes for fuel cell based on 2-pyridene based polybenzimidazole blended with poly(vinyl-phosphonic acid)

The present study has focused on exploring new 2-pyridine-bridge-based polybenzimidazole (2-Py-PBIs) based materials for various energy-related uses in proton exchange membrane fuel cells (PEMFC). An electrochemical device, which transforms chemical energy into electrical energy, is known as fuel cell. Using solution polymerization with polyphosphoric acid as a solvent, a series of 2-Py-PBIs were synthesised from the 4,4'-([2,4′-bipyridine]-2′,6′-diyl)bis (benzene-1,2-diamine). 2-Pyridine bridge Polybenzimidazoles are cross-linked with poly (vinylphosphonic acid), which helps us to improve membrane properties like mechanical properties and proton conductivities. FT-IR was used to characterize chemical structure, Ubbelohde viscometer was employed to determine the inherent viscosity. Additionally investigated were the oxidative stability, swelling ratio, ion exchange capability, and water uptake for 2-Py-PBIs. Thermogravimetric analysis is used to evaluate thermal stability. The obtained 2-Py-PBIs membranes were thermally stable and mechanically strong when compared with conventional polybenzimidazole-based membranes. The 2-Py-PBIs:PVPA membranes showed proton conductivity between 0.10 µS/m to 4.65 µS/m.

Cellulose nanofiber-connected covalent organic framework nanosheets composite membrane for proton conduction

Covalent organic framework (COF) nanosheets have been considered as promising materials for proton exchange membranes (PEM) due to their orderly, adjustable pores and relatively improved membrane forming properties. Here, we introduced the one-dimensional sulfonated bacterial cellulose nanofibers (SBCNF), originating from coconut and binding TpBd-2SO3H nanosheets to prepare a series of SBCNF/TpBd-2SO3H composite membranes. The composite membranes present a typical layered structure due to the presence of SBCNF. Moreover, extensive hydrogen bond network is formed between the embedded TpBd-2SO3H nanosheets and SBCNF, which is beneficial for improving the proton conductivity and mechanical strength of the membrane. As a result, the composite membrane achieved a proton conductivity of 147.5 mS/cm at 80 °C, 100 %RH and a highest tensile strength of 88.49 MPa.

The effect of nitrogen positive sites on the proton conductivity and acid stability of polybenzimidazole-based proton exchange membranes

High-temperature proton exchange membranes (HT-PEMs) based on amino-type polybenzimidazole (AmPBI) and double-bonded ionic liquids (ILs) are prepared. To prevent leakage of ILs, three kinds of polymeric ionic liquids (PILs) with different nitrogen positive sites are synthesized through in-situ free radical polymerization, and then the AmPBI-PIL membranes are prepared. The ion pairs (N+ - H2PO4−) formed after treatment with KOH and PA have a good effect on both proton conductivity and PA retention. After acid doping, the nitrogen positive sites in the PILs form ion pairs with PA, which serves as a jumping site for protons and promotes proton transport. The excellent proton conductivity and PA remaining of the AmPBI-PIL membranes are noteworthy. In particular, the proton conductivity of AmPBI-CTDTr is as high as 184.9 mS cm−1 at 180 °C, and the acid reservation is 83 % at 160 °C after 240 h. AmPBI-CTDTr has a 550.9 mW cm−2 peak power density when it is anhydrous at 160 °C.

High-performance proton exchange membrane employing water-insoluble hybrid formed by chemically bonding phosphotungstic acid with polydopamine

Heteropolyacids can retain water in a proton exchange membrane to increase proton conductivity at high temperatures and low humidity; however, their high solubility in water leads to leaching, which limits their further application. Herein, we used phosphotungstic acid (HPW) and polydopamine (PDA) particles to prepare a water-insoluble PDA/HPW hybrid (PDW) via hydrothermal reaction. The amino groups of PDA in PDW chemically bonded to HPW and acted as an anchor for HPW. The proton conductivity of the sulfonated poly(ether ether ketone) (SPEEK) composite membrane containing 15wt% PDW (SPEEK/PDW-15) in liquid water was 0.052 S⸱cm–1 at 25 ℃, which was 63% higher than that of the SPEEK control membrane (0.032 S⸱cm–1). The SPEEK/PDW-15 composite membrane also showed stable proton conductivity during 80 days of testing while immersed in water.

Fast proton conductors for low humidity: hydrophilic sulfonated and phosphonated polysilsesquioxanes with Al-O-P crosslinks.

Proton-conducting polysilsesquioxane oligomers with core-shell structures consisting of hydrophilic silica-rich cores surrounded by an organic layer with sulfonic and phosphonic acid groups were synthesized. They were crosslinked by mixing with phosphoric acid and aluminum ions to form a hydrophilic Al-O-P framework. The resulting polymers were clear, uniform, flexible, and exhibited a high proton conductivity above 100 °C in non-humidified low-humidity air (∼22 mS cm-1 at 120 °C and ∼1%RH) because of their high sulfonic acid concentration and high water retention capability.

Tailored Porous Ferrocene-Based Metal-Organic Frameworks as High-Performance Proton Conductors.

Although crystalline metal-organic frameworks (MOFs) have gained a great deal of interest in the field of proton conduction in recent years, the low stability and poor proton conductivity (σ) of some MOFs have hindered their future applications. As a result, resolving the issues listed above must be prioritized. Due to their exceptional structural stability, MOFs with ferrocene groups that exhibit particular physical and chemical properties have drawn a lot of attention. This study describes the effective preparation of a set of three-dimensional ferrocene-based MOFs, MIL-53-FcDC-Al/Ga and CAU-43, containing both main group metals and 1,1'-ferrocene dicarboxylic acid (H2FcDC). Multiple measurements, including powder X-ray diffraction (PXRD), infrared (IR), and scanning electron microscopy (SEM), confirmed that the addition of ferrocene groups enhanced the thermal, water, and acid-base stabilities of the three MOFs. Consequently, their proton-conductive behaviors were meticulously measured utilizing the AC impedance approach, and their best proton conductivities are 5.20 × 10-3, 2.31 × 10-3, and 1.72 × 10-4 S/cm at 100 °C/98% relative humidity (RH), respectively. Excitingly, MIL-53-FcDC-Al/Ga demonstrated an extraordinarily ultrahigh σ of above 10-4 S·cm-1 under 30 °C/98% RH. Using data from structural analysis, PXRD, SEM, thermogravimetry (TG), and activation energy, their proton transport mechanisms were thoroughly examined. The fact that these MOFs are notably easy to assemble, inexpensive, toxin-free, and stable will increase the range of practical uses for them.

Tetramethyl poly(aryl ether ketone) modified by DABCO cationic polymer for high temperature proton exchange membrane fuel cells

Rationally constructing proton transport channel within high temperature proton exchange membranes (HT-PEMs) plays a critical role in lowering the mass transfer resistance and thus improving the performance of HT-PEM fuel cells (HT-PEMFCs). We herein designed a microphase-separated structure to promote proton transmitting by incorporating 1,4-Diazabicyclo[2.2.2]octane (DABCO) cationic polymer into tetramethyl poly(aryl ether ketone) (TMPAEK). The flexible and cationic segments afforded a polarity difference from TMPAEK, resulting in easier phosphoric acid adsorption. High proton conductivity of 135 mS cm−1 was obtained under anhydrous conditions at 150 °C. Besides, the hydrophilic domains that containing N-heterocycle could stabilize phosphoric acid through hydrogen bonding interactions, resulting in high phosphoric acid retention of ∼80 % after 288 h test. A Peak power density of 496 mW cm−2 was achieved in non-humidified H2/O2 without back pressure at 140 °C, which was higher than that of m-PBI under the same conditions. This work not only paved a way to tailor the ion conductivity of membrane, but also provided a highly competitive membrane for HT-PEMFCs.

Sulfo ethyl cellulose/Nafion composite for high‐temperature proton exchange membrane

AbstractThis study investigated the potential enhancement of proton conductivity in Nafion membranes through the incorporation of sulfo ethyl cellulose (SEC) at varying weight ratios (5 and 10 wt.%). Results indicated that increasing the weight ratio of SEC led to improvements in water absorption, activation energy, and proton conductivity within the composite membranes. Specifically, the composite membrane exhibited a significant increase in proton conductivity, reaching up to 170 mS cm−1, in contrast to the pristine Nafion membrane which recorded 40.08 mS cm−1, particularly at temperatures exceeding 120°C. At the sub‐molecular level, Fourier transfer inferred spectroscopy (FTIR) analysis of Nafion/SEC membranes unveiled cross‐linking interactions occurring between the sulfo acid groups of Nafion chains and the hydroxyls within the SEC matrix. Moreover, X‐ray diffraction (XRD) findings of the composite membranes were instrumental in identifying crystalline phases, orientation, and structural features. The results indicated variations in atomic radius and alterations in lattice parameters at the nanoscale, induced by heightened surface forces resulting from the inclusion of SEC in the Nafion matrix. This phenomenon leads to a reduction in crystallite size, accompanied by an increase in peak broadening and surface area within the composite membranes. Such changes signify a clear interaction between SEC and Nafion, as confirmed by both scanning electron microscopy and thermal gravimetry analyses. Taken together, these findings strongly indicate that the cross‐linked composite membranes utilizing SEC‐Nafion hold significant promise as proton exchange membranes.

MoS2/graphene dispersed 2‐acrylamide‐2‐methyl propane sulfonic acid grafted polyarylene ether of di‐phenylenedi‐acetal high temperature‐proton exchange membrane fuel cell application

AbstractA polyaryleneether has been synthesized from bis‐(4‐cholorophenyl)di‐acetal (DPDA) monomer with bisphenol A and allyl bisphenol‐A. The copolymer was then functionalized with 2‐acrylamide‐2‐methyl propane sulfonic acid through radical grafting (SPAE/DPDA). The successfully synthesized SPAE/DPDA polymer was validated by using FTIR and NMR. Secondly, a composite nanostructure of MoS2/GNS nanosheet has been prepared and characterized using PXRD, FE‐SEM, and HR‐TEM. The composite membrane casted with SPAE/DPDA and varying weight percentage of 1%, 2%, 3%, 5%, 7%, and 10% MoS2/GNS nanosheet, has been characterized for ion exchange capacity (IEC), water stability (WU), swelling properties (SR), oxidative stability, and proton conductivity (PC).The MoS2/GNS dispersed SPAE/DPDA polymer nanocomposites membrane showed a chemical degradation of 22.56% and proton conductivity (PC) of 2.5 × 10−2 S/cm at 110°C. The results show that these membranes have high proton conductivity and can be used in proton exchange membrane fuel cells (HT‐PEMFCs).

An amperometric high-temperature ammonia sensor based on a BaCo0.4Fe0.4Zr0.1Y0.1O3-δ triple conductor

Selective catalytic reduction (SCR) utilizing urea hydrolysis to generate ammonia (NH3) is the most efficient technology to reduce the emission of nitrogen oxides (NOx). NH3 detection is crucial in the closed-loop feedback system for the precise urea injection. In this work, a high-temperature NH3 sensor using a BaZr0.8Y0.2O3-δ (BZY) proton conductor as the electrolyte and a BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) H+/e–/O2– triple conductor as the sensing electrode (SE) is reported. The effect of the micromorphology of the BCFZY SE on the sensing performance is investigated by varying the sintering temperature of SE. The sensor shows high sensitivity to NH3 with response currents of 0.39, 1.31, 3.03, and 1.81 μA/ppm at 350, 400, 450, and 500 °C, respectively. Furthermore, the sensor shows excellent selectivity and repeatability. This work demonstrates that the BCFZY based sensor has great potential for the high-temperature NH3 detection.

Electrolytic Performance of Sodium Alginate-Poly Vinyl Alcohol Matrix with Ammonium Bromide for Proton Conduction: Applications in Electrochemical Systems

Polymer blend electrolytes based on poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared using the solution casting method. These electrolytes were doped with varying amounts of ammonium bromide (NH4Br). The compatibility of NH4Br with PVA:NaAlg polymers was examined through X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) studies. The FTIR assessment confirmed the formation of a complex between PVA:NaAlg and the added salt, as evidenced by modifications and reductions in the intensity of FTIR bands related to functional groups. The conductivity and dielectric behavior of the samples were analyzed using AC impedance spectroscopy. The sample with 20wt.% of added salt exhibited a higher ionic conductivity of 1.661×10-5 Scm-1. Activation energy and relaxation time were estimated, and dielectric studies revealed a non-Debye nature. The conduction mechanism was best described by the correlated overlapping large polaron tunneling model (OLPT). The highest conducting sample was found to be suitable for electrochemical devices, as demonstrated by transference number (TNM), cyclic volumetric (CV), and linear sweep voltammetry (LSV) analyses. This high-conductivity sample can be employed in electrochemical devices such as EDLC. The cyclic voltammetry (CV) curve exhibited a nearly rectangular shape with non-faradaic peaks. GCD(Galvanostatic charge-discharge) analysis yielded specific capacitance, power density, and energy density values of 125.01 Fg-1, 1037 WKg-1, and 14.06 WhKg-1 respectively. These results indicate that polymer electrolytes show great promise as electrolytes in proton-conducting electrochemical devices.

Proton conductance and regulation of proton/potassium fluxes in Escherichia coli FhlA-lacking cells during fermentation of mixed carbon sources

Escherichia coli uptake potassium ions with the coupling of proton efflux and energy utilization via proton FOF1-ATPase. In this study contribution of formate hydrogen lyase (FHL) complexes in the proton/potassium fluxes and the formation of proton conductance (CMH+) were investigated using fhlA mutant strain. The proton flux rate (JH+) decreased in fhlA by ∼ 25% and ∼ 70% during the utilization of glucose and glycerol, respectively, at 20 h suggesting H+ transport via or through FHL complexes. The decrease in JK+ in fhlA by ∼ 40% proposed the interaction between FHL and Trk secondary transport system during mixed carbon fermentation. Moreover, the usage of N,N’-dicyclohexylcarbodiimide (DCCD) demonstrated the mediation of FOF1-ATPase in this interaction. CMH+ was 13.4 nmol min−1 mV-1 in WT at 20 h, which decreased by 20% in fhlA. Taken together, FHL complexes have a significant contribution to the modulation of H+/ K+ fluxes and the CMH+ for efficient energy transduction and regulation of the proton motive force during mixed carbon sources fermentation.

Self-healing sulfonated poly(ether ether ketone)/polyvinyl alcohol membrane reinforced with sulfonated silica for direct methanol fuel cell

Nafion, the predominant choice for polymer electrolyte membranes (PEMs) in direct methanol fuel cells (DMFCs), excels in proton conductivity but is plagued by elevated methanol permeability and sustained performance degradation. To address these issues, this study aims to synthesize a self-healable composite membrane composed of sulfonated poly (ether ether ketone), polyvinyl alcohol, and sulfonated silica (S/PVA/S–SiO2). The composite membrane with 3 wt% S–SiO2 demonstrates the highest proton conductivity, thanks to its improved water absorption and increased proton transfer sites. Compared to pure SPEEK, the composite membrane has a 20% lower methanol permeability. With its enhanced selectivity, the S/PVA/S–SiO2 membrane produces a power density of 3.64 mW cm−2 at 26.67 mA cm−2. Furthermore, by virtue of reversible hydrogen bonding, the composite membrane shows exceptional self-healing capabilities, restoring its methanol-blocking function by 83.6%. These results highlight that the S/PVA/S–SiO2 membrane holds promise for DMFC applications.

Tetra-Ln3+-Implanted Tellurotungstates Covalently Modified by dl-Malic Acid: Proton Conduction and Photochromic Properties.

Three unique dl-malic acid covalently modified tetra-Ln3+-implanted tellurotungstates [H2(CH3)2]9NaH9[Ln4(H2O)14W6O13(OH)5(Mal)2(B-α-TeW9O33)4]·48H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3); H3Mal = dl-malic acid] were fabricated by reacting Na2TeO3, Na2WO4·2H2O, Mal, and LnCl3·6H2O with dimethylamine hydrochloride in an aqueous solution. The most prominent architectural feature of these compounds is the covalent connection mode of an organic ligand and a polyoxometallate backbone, which is relatively rare in the realm of polyoxotungstates. The tetrameric polyanion can be deemed as four [TeW9O33]8- fragments fused together via an intriguing hexanuclearity [W6O13(OH)5(Mal)2Ln4(H2O)14]13+ cluster. Impedance measurements manifest that all three complexes display splendid proton conduction properties, with an exceptional conductivity for 2 up to 2.48 × 10-2 S·cm-1 under 85 °C and 95% relative humidity. Moreover, compounds 1 and 3 exhibited fast reversible photochromic properties with allochroic half-life periods t1/2 of 1.046 and 0.544 min, respectively.