Excellent Proton Conductivity Research Articles

Sandwich structure engineering for constructing proton exchange membranes with excellent stability and proton conductivity

Sandwich structure engineering for constructing proton exchange membranes with excellent stability and proton conductivity

A {Ru(C6H6)}-Containing Isopolymolybdate with Good Photocatalytic Activity for Oxidative Coupling of Amines, and Proton Conduction Properties.

We present a nonclassical {Ru(C6H6)}-containing isopolymolybdate Cs8K2Na2H4{[(C6H6)Ru]6Mo24O86}·35H2O (1) via one-pot reaction. The crystallographic characterization of compound 1 revealed that it contains an unusual {Mo24O86} cluster together with six {Ru(C6H6)} groups, having the largest number of {Ru(C6H6)} groups within the field of {Ru(C6H6)}-containing polyoxometalates. Results showed that compound 1 displayed excellent proton conductivity (9.8 × 10-3 S cm-1) at 90 °C and 95% relative humidity. Based on the calculation result of activation energy, which was more than 0.4 eV (1.47 eV), it was determined that the proton conduction process for compound 1 was in accordance with the Vehicle mechanism. More interestingly, compound 1 was exploited as a catalyst to achieve the heterogeneous oxidative coupling of amines and realized a high yield (98.9%) toward N-benzylidenebenzylamine under ambient temperature and visible light irradiation (>400 nm) and O2 atmosphere.

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.

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.

Advances in the Application of Sulfonated Poly(Ether Ether Ketone) (SPEEK) and Its Organic Composite Membranes for Proton Exchange Membrane Fuel Cells (PEMFCs)

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.

Non-Noble-Metal-Based Electrocatalysts for Acidic Oxygen Evolution Reaction: Recent Progress, Challenges, and Perspectives.

The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO2 reduction, nitrogen fixation, and metal-air batteries. Among various water electrolysis techniques, proton exchange membrane (PEM)-based water electrolysis devices offer numerous advantages, including high current densities, exceptional chemical stability, excellent proton conductivity, and high-purity H2. Nevertheless, the prohibitive cost associated with Ir/Ru-based OER electrocatalysts poses a significant barrier to the broad-scale application of PEM-based water splitting. Consequently, it is crucial to advance the development of non-noble metal OER catalysis substance with high acid-activity and stability, thereby fostering their widespread integration into PEM water electrolyzers (PEMWEs). In this review, a comprehensive analysis of the acidic OER mechanism, encompassing the adsorbate evolution mechanism (AEM), lattice oxygen mechanism (LOM) and oxide path mechanism (OPM) is offered. Subsequently, a systematic summary of recently reported noble-metal-free catalysts including transition metal-based, carbon-based and other types of catalysts is provided. Additionally, a comprehensive compilation of in situ/operando characterization techniques is provided, serving as invaluable tools for furnishing experimental evidence to comprehend the catalytic mechanism. Finally, the present challenges and future research directions concerning precious-metal-free acidic OER are comprehensively summarized and discussed in this review.

A manganese doping deficient cerium base metal organic framework as radical scavenger for highly-durable proton exchange membrane water electrolysis

Eliminating hydrogen peroxide and free radicals from electrochemical reactions is crucial for mitigating chemical degradation and improving the durability of proton exchange membranes (PEMs). Herein, we prepare a metal–organic framework containing manganese and cerium ions that possesses oxygen vacancy defects and amino functional groups. The prepared Ce4MnBDC-NH2 acts as a catalyst for H2O2 decomposition and as a free radical scavenger, and it is incorporated into a perfluorosulfonic acid (PFSA) ionomer matrix. Featuring large pore volume, high porosity, and abundant amino groups, the Ce4MnBDC-NH2 is locked in a PEM. The obtained Ce4Mn-NH2BDC@PFSA composite membrane exhibits high dimensional stability, excellent proton conductivity and low high-frequency impedance, yielding a proton conductivity of up to 137 mS cm–1 and superior water electrolysis performance of up to 1.83 V at 3.0 A cm–2. Moreover, the obtained Ce4Mn-NH2BDC@PFSA membrane experiences lower weight loss during the Fenton reaction, a low fluoride-ion release rate, and excellent stability in high current density durability testing: its decay rate is only 5.2 μV h–1, which is lower than that of CeO2@PFSA and Nafion 117 membranes. This work provides a promising method to prepare efficient free radical scavengers for steady-state PEM water electrolysis.

Perfluoroalkyl Functionalized Superhydrophobic Covalent Organic Frameworks for Excellent Oil-Water Membrane Separation and Anhydrous Proton Conduction.

Rapid economic development has led to oil pollution and energy shortage. Membrane separation has attracted much attention due to its simplicity and efficiency in oil-water-separation. The development of membrane materials with enhanced separation properties is essential to improve the separation-efficiency. Proton exchange membrane fuel cells (PEMFCs) are expected to replace conventional engines due to their high-power-conversion rates and other favorable properties. Anhydrous-proton-conductingmaterials are vital components of PEMFCs. However, developing stable proton-conducting materials that exhibit high conductivity at varying temperatures remains challenging. Herein, two covalent organic frameworks (COFs) with long-side-chains are synthesized, and their corresponding COF@SSN membranes. Both membranes can effectively separate oil-water mixtures and water-in-oil emulsions. The TFPT-AF membrane achieves a maximum oil-flux of 6.05×105g h-1 m-2 with an oil-water separation efficiency of above 99%, which is almost unchanged after 20 consecutive uses. COF@H3PO4 doped with different ratios of H3PO4 is prepared, the results show that the perfluorocarbon-chain system has excellent anhydrous proton conductivity, achieving an ultra-high proton-conductivityof 3.98×10-1Scm-1 at 125°C. This study lays the foundation for tailor-made-functionalization of COF through pre-engineering and surface-modification, highlighting the great potential of COFs for oil-water separation and anhydrous-proton-conductivity.

Construction of wide-temperature-range proton exchange membrane by regulating proton transfer channels based on phosphate-functionalized carbon nanotubes

Phosphoric acid (PA) doped polybenzimidazole (PBI) high-temperature proton exchange membrane is favored because it can achieve faster proton transfer at 180 °C without additional humidification. However, the PA-PBI membrane is faced with slow PA proton conduction kinetics below 100 °C, and failing rapid start-up of fuel cells. Herein, carbon nanotubes functionalized with phosphate groups (P-CNT) and sulfonated poly [2,2'-(p-hydroxydibenzene)-5,5′-benzimidazole] (SOPBI) composite membranes are prepared as proton exchange membranes with wide temperature range (40–180 °C). Based on the regulation of monophosphate and bisphosphate groups on P-CNT, the bisphosphate group can strengthen the vehicular mechanism of proton transport by accelerating the formation and diffusion of H3O+ at low temperature/high humidity, and the Grotthuss mechanism of proton transport by constructing dense hydrogen bond network at high temperature/low humidity. The 2P-CNT(6 %)/SOPBI composite membrane shows excellent proton conductivity (131.8 mS cm−1 at 80 °C/90%RH, 170.5 mS cm−1 at 180 °C/0%RH) and peak power density (378 mW cm−2 at 80 °C/100 % RH, 531 mW cm−2 at 160 °C/0 % RH) under wide temperature conditions, surpassing SOPBI membrane and other composite membranes. Furthermore, the 2P-CNT(6 %)/SOPBI composite membrane exhibits high proton conduction and fuel cell stability at both 80 °C/100 % RH and 160 °C/0 % RH.

High H2O-Assisted Proton Conduction in One Highly Stable Sr(II)-Organic Framework Constructed by Tetrazole-Based Imidazole Dicarboxylic Acid.

Solid electrolyte materials with high structural stability and excellent proton conductivity (σ) have long been a popular and challenging research topic in the fuel cell field. This problem can be addressed because of the crystalline metal-organic frameworks' (MOFs') high structural stability, adjustable framework composition, and dense H-bonded networks. Herein, one highly stable Sr(II) MOF, {[Sr(H2tmidc)2(H2O)3]·4H2O}n (1) (H3tmidc = 2-(1H-tetrazolium-1-methylene)-1H-imidazole-4,5-dicarboxylic acid) was successfully fabricated, which was structurally characterized by single-crystal X-ray diffraction and electrochemically examined by the AC impedance determination. The results demonstrated that the σ of the compound manifested a positive dependence on temperature and humidity, and the optimal proton conductivity is as high as 1.22 × 10-2 S/cm under 100 °C and 98% relative humidity, which is at the forefront of reported MOFs with ultrahigh σ. The analysis of the proton conduction mechanism reveals that numerous tetrazolium groups, carboxyl groups, coordination, and crystallization water molecules in the framework are responsible for the high efficiency of proton transport. This work offers a fresh perspective on how to create novel crystalline proton conductive materials.

Highly sulfonated poly ether ether ketone chelated with Cu2+ as a proton exchange membrane at sub-zero temperatures

Improving the proton conductivity (σ) of proton exchange membranes at low temperatures is very important for expanding their application areas. Here, sulfonated poly ether ether ketone (SPEEK) membranes were prepared with different sulfonation degrees, and its maximum ion exchange capacity is 3.15 mmol/g for 10 h at 60 °C. Highly sulfonated SPEEK membrane exhibits ultra-high water uptake and excellent proton conductivity of 0.074 S/cm at −25 °C due to its abundant −SO3H. Nevertheless, its high swelling ratio and low mechanical strength are not conducive to the practical application of the membrane. Luckily, by employing the chelation of Cu2+ with −SO3− on the SPEEK chain, Cu2+-coordinated SPEEK membranes were prepared, and they not only retain high −SO3H content but also possess robust mechanical properties and good dimensional stability compared to pristine SPEEK membrane. Meanwhile, the σ of the SPEEK-Cu membrane reaches 0.054 S/cm at −25 °C, and its fuel cell maximum power (Wmax) reaches 0.42 W/cm2 at −10 °C, demonstrating superior low-temperature performance in comparison to other reported materials. Particularly, water states in the prepared membranes are quantified by low-temperature differential scanning calorimetry. Because much more water bound to the plentiful −SO3H and Cu2+ inside the membrane endows it with anti-freezing performance, the decay of the σ and the Wmax for the SPEEK-Cu membrane is retarded at sub-zero temperatures. It is envisioned that composite membranes comprising metal ions such as Cu2+-SPEEK have a high potential for sub-zero fuel cell applications.

Preparation and study on H–MoS2/SLS modified SPI@SPEEK blend proton exchange membrane with balanced proton conductivity and stability

Proton exchange membranes (PEMs) are the core components of fuel cells, and research has long focused on how to balance their proton conductivity and durability. In this work, a series of homogeneous blend of sulfonated polyimide (SPI) and sulfonated polyether ether ketone (SPEEK) hybrid membranes with were constructed refined with sulfonated MoS2 (H–MoS2) and sodium lignosulfonate (SLS). The results showed that the tensile strength of the films was enhanced by 39.4% (67.84 MPa) compared to the base film. The composite films incorporating 1 wt% H-MoS2 and 2 wt% SLS has excellent proton conductivity, which can reach 50.24 mS/cm at 80°C and 100% humidity. The embed hybrid structure constructed by H–MoS2 and SLS, which not only effectively solves the limitations of the proton transport channel of traditional polymer materials, but also provides abundant proton transport sites, which provides a new strategy for preparing high-performance PEM.

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.

Double cross-linked 3D layered PBI proton exchange membranes for stable fuel cell performance above 200 °C

Phosphoric acid doped proton exchange membranes often experience performance degradation above 200 °C due to membrane creeping and phosphoric acid evaporation, migration, dehydration, and condensation. To address these issues, here we present gel-state polybenzimidazole membranes with double cross-linked three-dimensional layered structures via a polyphosphoric acid sol-gel process, enabling stable operation above 200 °C. These membranes, featuring proton-conducting cross-linking phosphate bridges and branched polybenzimidazole networks, effectively anchor and retain phosphoric acid molecules, prevent 96% of its dehydration and condensation, improve creep resistance, and maintain excellent proton conductivity stability. The resulting membrane, with superior through-plane proton conductivity of 0.348 S cm−1, delivers outstanding peak power densities ranging from 1.20–1.48 W cm−2 in fuel cells operated at 200-240 °C and a low voltage decay rate of only 0.27 mV h−1 over a 250-hour period at 220 °C, opening up possibilities for their direct integration with methanol steam reforming systems.

Hybrid Membrane of Sulfonated Poly(aryl ether ketone sulfone) Modified by Molybdenum Clusters with Enhanced Proton Conductivity.

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-{Mo132} into SPAEKS are obtained. Excellent hydrophilic properties of 2MeIm-{Mo132} 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-2MIMo132-5 exhibits an enhanced proton conductivity of 75mScm-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 266.2mWcm-2 can be achieved at 80°C, which far exceeds that of pristine SPAEKS membrane (54.6mWcm-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.

High ion exchange capacity perfluorosulfonic acid resine proton exchange membrane for high temperature applications in polymer electrolyte fuel cells

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) have attract much attention from academic and industry, which can improve the catalyst activity, reduce Pt loading, enhance CO tolerance, and simplify water and heat management. High-temperature proton exchange membrane (HT-PEM) is the key component for HT-PEMFCs. Here, we provide an investigation of newly developed HT-PEM to evaluate its properties and performances in fuel cells above 90 °C. The HT-PEM exhibits an excellent proton conductivity of 136.1 mS cm−1 at 90 °C and 95% RH, and remarkable power density of 0.95 Wcm−2 at 105 °C and 80% RH. The stability and durability of HT-PEM are studied with varied testing methods. After the continuous operation at open circuit voltage (OCV) for 500 h and continuous dry-wet circulation for 20000 cycles at 90 °C, negligible change of OCV and hydrogen permeation current density are recorded, indicating good chemical and mechanical stability for HT-PEM. The improved property and performance originate from the new PFSA base material and improved morphology, in which the larger ionic clusters and continuous proton-transfer channels contribute to the superior performance, and the high glass transition temperature (Tg∼132 °C) induces good stability.

A multifunctional Eu-MOF with multi-color and proton conduction switching and its anti-counterfeiting applications

Lanthanide metal-organic frameworks (Ln-MOFs) have exhibited remarkable capabilities in color change, luminescence, proton conduction through the strategic modification of metal nodes, organic ligands and channels or pores. By modifying the electron-deficient bipyridinium to contain carboxylic acid moieties and coordinating them with the luninescent Eu3+ ion, a unique and versatile Eu-MOF has been synthesized. Under UV light conditions, the complex shows an obvious color change from colorless to blue, which is due to the formation of viologen radicals after photoinduced electron transfer (PIET) process. As we all know, the changed color is caused by the alteration of absorption intensity, ultimately impacting its luminescence as well. Thus, the bright and strong red fluorescence of this complex is quenched upon continuous UV light irradiation, which may be attributed to intramolecular energy transfer from the excited state of the europium ion to the colored state of the CV ligand. Based on the control of multiple colors of the complex, the designed encryption model can realize multiple anti-counterfeiting of real numbers. In addition, the conductivity of this compound increases significantly after UV illumination, showing excellent photo-modulated proton conductivity. In short, our work has proposed a multifunctional bipyridinium-based Ln-MOF with photochromism, photo-switchable photoluminescence and proton conduction, which offers valuable insights for the creation of versatile switchable materials based on MOFs.

Improving the proton conductivity of HKUST‐1 by hole expansion and ionic liquid introduction

As a new type of proton conductor, metal–organic frameworks (MOFs) have attracted much attention because of their superior properties over conventional materials, such as the modifiability of framework, reversibility of coordination bond, high specific surface area, and porosity. It is predicted that the proton conductivities of MOFs can be improved by hole expansion and ionic liquid introduction. In this work, HKUST‐1 and LP‐HKUST‐1 were prepared, which were filled with different proportions of N‐methylimidazole triflate (MIM‐CF3SO3) to prepare composite materials MIM‐CF3SO3@HKUST‐1‐100% and MIM‐CF3SO3@LP‐HKUST‐1‐x (x = 25%, 50%, 75% and 100%). A total of seven kinds of materials were synthesized. The proton conductivities of all the materials at 75% RH were tested from 303 to 353 K. In this environment, MIM‐CF3SO3@LP‐HKUST‐1‐100% shows excellent proton conductivity (σ = 0.341 S·cm−1 at 353 K, 75% relatively humidity [RH]), being 7060 times that of HKUST‐1, and reaches the peak value of MOF family in recent years. Then, the conductivities of parts of the materials were tested in extreme environments, such as in high‐humidity environment (303–353 K, 100% RH), high‐temperature environment (373–423 K, N2 atmosphere), and low‐temperature environment (253–283 K, 75% RH). The results show that under all conditions above, the proton conductivity of MIM‐CF3SO3@LP‐HKUST‐1‐100% is the best, up to 0.341 S·cm−1 at 353 K and 75% RH, 0.179 S·cm−1 at 353 K and 100% RH, 1.31 × 10−3 S·cm−1 at 283 K and 75% RH, and 2.31 × 10−4 S·cm−1 at 423 K and N2 atmosphere, indicating that proton conductivity of HKUST‐1 is improved by hole expansion and ionic liquid introduction. Finally, the stability test showed that MIM‐CF3SO3@LP‐HKUST‐1‐100% was stable in all environments above. Moreover, the conductive mechanism of HKUST‐1 before and after introduction of ionic liquids was also discussed, providing a theoretical basis for the enhancement of proton conductivities of MOFs using ionic liquid introduction and hole expansion.

Assessment of polybenzimidazole/MOF composite membranes for the improvement of high-temperature PEM fuel cell performance

This study aims to determine the most effective utilization of ZIF-8 type metal-organic framework (MOF) doped polybenzimidazole (PBI) composite membrane in high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) and investigate how ZIF-8 filler affects performance. ZIF-8 particles were prepared by solvothermal method and added to the PBI polymer using a weight percentage varying from 1 to 5 %. XRD, BET, and TEM examined the prepared ZIF-8. Composite membrane properties were investigated by XRD, SEM analysis, proton conductivity measurements, acid doping, and acid stripping tests. The HT-PEMFC performances of the membranes were carried out using Hydrogen and dry air at 150–180. The highest performance was acquired with the composite ZIF8/PBI-2 membrane as 0.432 W/cm2 at 170 °C. The obtained result is explained by easier proton transfer over ZIF-8's enlarged tunnel network. This study proposes a promising strategy to use ZIF-8 to prepare a PBI composite membrane with excellent proton conductivity, acid doping, and low acid leaching for HT-PEMFC application. The current study's findings can support future research on PBI/MOF-based composite membranes for HT-PEMFC applications.

Hierarchical Self-Assembly of Capsule-Shaped Zirconium Coordination Cages with Quaternary Structure.

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 (879m2 g-1 ). ZrR-1 also exhibits excellent proton conductivity, reaching 1.31×10-2 S·cm-1 at 353K and 98% relative humidity, with a low activation energy of 0.143eV. This finding provides insights into controlling the hierarchical self-assembly of metal-organic cages to discover superstructures with emergent properties.