Proton Conductivities of Graphene Oxide Nanosheets: Single,Multilayer, and Modified Nanosheets

Proton conductivities of layered solid electrolytes can be improved by minimizing strain along the conduction path. It is shown that the conductivities (σ) of multilayer graphene oxide (GO) films (assembled by the drop‐cast method) are larger than those of single‐layer GO (prepared by either the drop‐cast or the Langmuir‐Blodgett (LB) method). At 60 % relative humidity (RH), the σ value increases from 1×10^?6 S cm^?1 in single‐layer GO to 1×10^?4 and 4×10^?4 S cm^?1 for 60 and 200 nm thick multilayer films, respectively. A sudden decrease in conductivity was observed for with ethylenediamine (EDA) modified GO (enGO), which is due to the blocking of epoxy groups. This experiment confirmed that the epoxide groups are the major contributor to the efficient proton transport. Because of a gradual improvement of the conduction path and an increase in the water content, σ values increase with the thickness of the multilayer films. The reported methods might be applicable to the optimization of the proton conductivity in other layered solid electrolytes.     

Superprotonic Conductivity of a UiO‐66 Framework Functionalized with Sulfonic Acid Groups by Facile Postsynthetic Oxidation

Facile postsynthetic oxidation of the thiol‐laced UiO‐66‐type framework UiO‐66(SH)₂ enabled the generation of UiO‐66(SO₃H)₂ with sulfonic acid groups covalently linked to the backbone of the system. The oxidized material exhibited a superprotonic conductivity of 8.4×10^?2 S cm^?1 at 80 °C and 90 % relative humidity, and long‐term stability of the conductivity was observed. This level of conductivity exceeds that of any proton‐conducting MOF reported to date and is equivalent to the conductivity of the most effective known electrolyte, Nafion.     

Preparation of Proton Conductive Inorganic-Organic Hybrid Films Using Epoxycyclohexylethyltrimethoxysilane and Orthophosphoric Acid

Proton conductive inorganic-organic hybrid films, which show high proton conductivity at temperatures higher than 100°C with low humidification, have been prepared from epoxycyclohexylethyltrimethoxysilane (EHTMS), 3-glycidoxypropyltrimethoxysilane, and orthophosphoric acid by the sol-gel method. Self-supporting, flexible, and brownish transparent films with a thickness ranging from 150 to 300 μm were obtained. Differential thermal analyses and thermogravimetric measurements revealed that the films were stable up to about 200°C. Ionic conductivity of the films increased with an increase in the content of phosphoric acid in the films. The films with a molar ratio of P/Si = 1.75 retained a high conductivity of about 6 × 10^?4 S cm^?1 even after holding for 150 h under 0.7% relative humidity at 130°C. The conductivity of the films increased with an increase in the relative humidity and was about 1 × 10^?2 S cm^?1 under 20% relative humidity at 130°C.     

Guest‐Assisted Proton Conduction in the Sulfonic Mesoporous MIL‐101 MOF

Post‐synthesis modification of MIL‐101(Cr)‐NO₂ was explored in order to decorate the organic backbone by propyl‐sulfonic groups, with the aim to incorporate mobile and acidic protons for solid‐state proton electrolyte applications. The resulting solid switched from insulating towards proton superconductive behavior under humidity, while the conductivity recorded at 363 K and 95 % relative humidity reached 4.8×10^?3 S cm^?1. Propitiously, the impregnation of the material by strong acidic molecules (H₂SO₄) further boosted the proton conductivity performances up to the remarkable σ value of 1.3×10^?1 S cm^?1 at 363 K/95 % RH, which reaches the performances of the best proton conductive MOF reported so far.     

Water‐Stable Homochiral Cluster Organic Frameworks Built by Two Kinds of Large Tetrahedral Cluster Units

Compared with metal organic frameworks (MOFs), the proton conductivity of cluster organic frameworks has been less studied. Herein, two supertetrahedral cluster organic frameworks (SCOFs) have been made that show two‐fold interpenetrated networks built by trivalent lanthanide tetrahedral clusters and monovalent cuprous T₃‐supertetrahedral clusters. The structure analysis, second harmonic generation signals, and solid‐state circular dichroism spectroscopy consistently reveal the chirality of these SCOFs. Remarkably, the water‐stable SCOFs show a high proton conductivity value of 1.4×10^?3 S cm^?1 at 80 °C and 95 % RH (relative humidity).     

Studies on sulfonic acid functionalized hollow silica spheres/Nafion® composite proton exchange membranes

In this work, sulfonic acid functionalized hollow silica spheres (SAFHSS)/Nafion® composite membranes were prepared by a recasting procedure. The influences of temperature on water uptake, swelling degree, and proton conductivity of the composite membranes were studied. In comparison with the pure recast Nafion® membrane, it was found that water uptake of composite membranes increased with increasing SAFHSS loading at all temperature studied. The swelling degree of SAFHSS/Nafion® composite membranes with 10～15 wt % SAFHSS loading was lower than that of the pure recast Nafion® at all temperatures in the study. The proton conductivity of SAFHSS/Nafion® composite membranes was constantly higher than that of the pure recast Nafion® at all temperatures (50～130 °C). In a range from 50 to 130 °C, the highest conductivity of composite membranes was obtained when 10 wt % SAFHSS was loaded. The maximum conductivity reached 0.1 S cm^?1 at 100% relative humidity and 100 °C, even the temperature reached to 130 °C, the conductivity of the composite membranes with 10 wt % SAFHSS was still as high as 4.4 × 10^?2 S cm^?1 at 100% relative humidity, whereas the conductivity of the pure recast Nafion® was only 2.2 × 10^?3 S cm^?1. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2647–2655, 2009     

Polycarboxylate‐Templated Coordination Polymers: Role of Templates for Superprotonic Conductivities of up to 10−1 S cm−1

Three coordination polymers (CPs) have been synthesized based on a [Co(bpy)(H₂O)₄]²⁺ chain (bpy=4,4′‐bipyridine) by a template approach. The frameworks are neutralized by different templated polycarboxylate anions (furan di‐carboxylate (fdc) in Co‐fdc, benzene tri‐carboxylate (btc) in Co‐tri and benzene tetra‐carboxylate (btec) in Co‐tetra). These templates with different degrees of protonation and ionic carrier concentration played significant role on crystal packing as well as formation of well‐directed H‐bonded networks which made these CPs perform well in proton conduction (PC). The PC value reaches to 1.49×10^?1 S cm^?1 under 80 °C and 98 % relative humidity (R.H.) for Co‐tri, which is the highest among CPs/MOFs/COFs and is an example of conductivity in the order of 10^?1 S cm^?1. Co‐tri and Co‐tetra are excellent proton conductors at mild temperature (40 °C) and 98 % R.H. (conductivities up to 2.92×10^?2 and 1.38×10^?2 S cm^?1, respectively).     

Proton Conductivities of Graphene Oxide Nanosheets: Single,Multilayer, and Modified Nanosheets

Proton conductivities of layered solid electrolytes can be improved by minimizing strain along the conduction path. It is shown that the conductivities (σ) of multilayer graphene oxide (GO) films (assembled by the drop‐cast method) are larger than those of single‐layer GO (prepared by either the drop‐cast or the Langmuir‐Blodgett (LB) method). At 60 % relative humidity (RH), the σ value increases from 1×10⁻⁶ S cm⁻¹ in single‐layer GO to 1×10⁻⁴ and 4×10⁻⁴ S cm⁻¹ for 60 and 200 nm thick multilayer films, respectively. A sudden decrease in conductivity was observed for with ethylenediamine (EDA) modified GO (enGO), which is due to the blocking of epoxy groups. This experiment confirmed that the epoxide groups are the major contributor to the efficient proton transport. Because of a gradual improvement of the conduction path and an increase in the water content, σ values increase with the thickness of the multilayer films. The reported methods might be applicable to the optimization of the proton conductivity in other layered solid electrolytes.     

Proton Transport in a Highly Conductive Porous Zirconium‐Based Metal–Organic Framework: Molecular Insight

The water stable UiO‐66(Zr)‐(CO₂H)₂ MOF exhibits a superprotonic conductivity of 2.3×10^?3 S cm^?1 at 90 °C and 95 % relative humidity. Quasi‐elastic neutron scattering measurements combined with aMS‐EVB3 molecular dynamics simulations were able to probe individually the dynamics of both confined protons and water molecules and to further reveal that the proton transport is assisted by the formation of a hydrogen‐bonded water network that spans from the tetrahedral to the octahedral cages of this MOF. This is the first joint experimental/modeling study that unambiguously elucidates the proton‐conduction mechanism at the molecular level in a highly conductive MOF.     

Solvent‐Vapor‐Induced Reversible Single‐Crystal‐to‐Single‐Crystal Transformation of a Triphosphaazatriangulene‐Based Metal–Organic Framework

A triphosphaazatriangulene (H₃L) was synthesized through an intramolecular triple phospha‐Friedel–Crafts reaction. The H₃L triangulene contains three phosphinate groups and an extended π‐conjugated framework, which enables the stimuli‐responsive reversible transformation of [Cu(HL)(DMSO)?(MeOH)]_n, a 3D‐MOF that exhibits reversible sorption characteristics, into (H₃L?0.5 [Cu₂(OH)₄?6 H₂O] ?4 H₂O), a 1D‐columnar assembled proton‐conducting material. The hydrophilic nature of the latter resulted in a proton conductivity of 5.5×10^?3 S cm^?1 at 95 % relative humidity and 60 °C.     

Structural modification of chitosan biopolymer as a novel polyelectrolyte membrane for green power generation

In the present study, a series of bioresource polyelectrolytes based on chitosan were synthesized and assessed for applicability in direct methanol fuel cells (DMFCs). A binary cross‐linking agent (sulfosuccinic acid/glutaraldehyde) was used for the structural modification of chitosan and membranes comprising various amounts of sulfosuccinic acid (0, 8, 12, and 16 wt% SSA/wt chitosan) were prepared. It was found that by increasing the sulfonate groups' content up to 16 wt%, proton conductivity and methanol permeability properties reach the values of 0.0452 S cm^?1 and 9.6 × 10^?7 cm² sec^?1, respectively. Based on the membrane selectivity evaluation and activation energy measurements of proton conduction, the optimum composition of cross‐linking agent was determined. The optimum composition resulted in a relatively high proton conductivity of 0.0452 S cm^?1 and a low methanol permeability of 9.6 × 10^?7 cm² sec^?1. Moreover, the optimum proton exchange membrane exhibited selectivity value of 47,100 in comparison with the corresponding value of 40,500 for Nafion® 117. The fabricated membranes showed acceptable oxidative and hydrolytic stability. Furthermore, single cell DMFC performance test revealed a power density of 17 mW cm^?2 at 30°C and 41 mW cm^?2 at 60°C in a 2 M methanol feed. Hence, prepared proton‐conducting bioresource ionomers could have promising potential in the field of green power generation as a low cost and biodegradable polyelectrolyte. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton‐exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2′‐bis(p‐aminophenoxy)‐1,1′‐binaphthyl‐6,6′‐disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30–80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film‐forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945–0.161 S/cm) at 20–80 °C in liquid water. The membranes exhibited methanol permeability from 9 × 10^?8 to 5 × 10^?7 cm²/s at 20 °C, which was much lower than that of Nafion (2 × 10^?6cm²/s). The copolymers were thermally stable up to 300 °C. The sulfonated polyimide copolymers with 30–60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 222–231, 2007     

Polybenzimidazoles tethered with N‐phenyl 1,2,4‐triazole units as polymer electrolytes for fuel cells

Polybenzimidazole (PBI) polymers tethered with N‐phenyl 1,2,4‐triazole (NPT) groups were prepared from a newly synthesized aromatic diacid, 3′‐(4‐phenyl‐4H‐1,2,4‐triazole‐3,5‐diyl) dibenzoic acid (PTDBA). The obtained polymers show superior thermal and chemical stability and good solubility in many aprotic solvents. The inherent viscosities of all polymers were around 1 dL/g. They exhibit high thermal stability with initial decomposition temperature ranging from 515 to 530 °C, high glass transition temperature ranging from 375 to 410 °C, and good mechanical properties with tensile stress in the range of 66–98 MPa and modulus 1897–2600 MPa. XRD analysis indicates that these polymers are amorphous in nature. Physicochemical properties such as water and phosphoric acid‐uptake, oxidative stability, and proton conductivity of membranes of these polymers have also been determined. The proton conductivity ranged from 4.7 × 10^?3 to 1.8 × 10^?2 S cm^?1 at 175 °C in dry conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2289–2303, 2009     

Cost‐Effective,High‐Performance Porous‐Organic‐Polymer Conductors Functionalized with Sulfonic Acid Groups by Direct Postsynthetic Substitution

We demonstrate the facile microwave‐assisted synthesis of a porous organic framework 1 and the sulfonated solid ( 1S ) through postsubstitution. Remarkably, the conductivity of 1S showed an approximately 300‐fold enhancement at 30 °C as compared to that of 1 , and reached 7.72×10^?2 S cm^?1 at 80 °C and 90 % relative humidity. The superprotonic conductivity exceeds that observed for any conductive porous organic polymer reported to date. This material, which is cost‐effective and scalable for mass production, also revealed long‐term performance over more than 3 months without conductivity decay.     

Synthesis and properties of novel sulfonated (co)polyimides bearing sulfonated aromatic pendant groups for PEFC applications

Novel sulfonated diamines bearing aromatic pendant groups, namely, 3,5‐diamino‐3′‐sulfo‐4′‐(4‐sulfophenoxy) benzophenone (DASSPB) and 3,5‐diamino‐3′‐sulfo‐4′‐(2,4‐disulfophenoxy) benzophenone (DASDSPB), were successfully synthesized. Novel side‐chain‐type sulfonated (co)polyimides (SPIs) were synthesized from these two diamines, 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTDA) and nonsulfonated diamines such as 4,4′‐bis(3‐aminophenoxy) phenyl sulfone (BAPPS). Tough and transparent membranes of SPIs with ion exchange capacity of 1.5–2.9 meq g^?1 were prepared. They showed good solubility and high thermal stability up to 300 °C. They showed isotropic membrane swelling in water, which was different from the main‐chain‐type and sulfoalkoxy‐based side‐chain‐type SPIs. The relative humidity (RH) and temperature dependence of proton conductivity were examined. At low RH, the novel SPI membranes showed much higher conductivity than the sulfoalkoxy‐based SPIs. They showed comparable or even higher proton conductivity than Nafion 112 in water at 60 °C (>0.10 S cm^?1). The membrane of NTDA‐DASDSPB/BAPPS (1/1)‐s displayed reasonably high proton conductivities of 0.05 and 0.30 S cm^?1 at 50 and 100% RH, respectively, at 120 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2862–2872, 2006     

Lewis Acid Guests in a {P8W48} Archetypal Polyoxotungstate Host: Enhanced Proton Conductivity via Metal‐Oxo Cluster within Cluster Assemblies

Complexes made by hosts that completely surround their guests provide a means to stabilize reactive chemical intermediates, transfer biologically active cargo to a diseased cell, and construct molecular‐scale devices. By the virtue of inorganic host–guest self‐assembly, nucleation processes in the cavity of a {P₈W₄₈}‐archetype phosphotungstate has afforded a nanoscale 16‐Al^III‐32‐oxo cluster and its Ga^III analogue that contain the largest number of Al^III/Ga^III ions yet found in polyoxometalate (POM) chemistry. Interestingly, the rich Lewis acid Al^III centers within the Lewis base POM support shows an exceptional proton conductivity of 4.5×10^?2 S cm^?1 (85 °C, 70 % RH; RH: relative humidity), which is by far the highest conductivity reported among POM‐based single‐crystal proton conductors.     

Sulfonated polybenzimidazoles: Proton conduction and acid–base crosslinking

A series of soluble, benzimidazole‐based polymers containing sulfonic acid groups (SuPBI) has been synthesized. SuPBI membranes resist extensive swelling in water but are poor proton conductors. When blended with high ion exchange capacity (IEC) sulfonated poly(ether ether ketone) (SPEEK), a polymer that has high proton conductivity but poor mechanical integrity, ionic crosslinks form reducing the extent of swelling. The effect of sulfonation of PBI on crosslinking in these blends was gauged through comparison with nonsulfonated analogs. Sulfonic acid groups present in SuPBI compensate for acid groups involved in crosslinking, thereby increasing IEC and proton conductivity of the membrane. When water uptake and proton conductivity were compared to the IEC of blends containing either sulfonated or nonsulfonated PBI, no noticeable distinction between PBI types could be made. Comparisons were also made between these blends and pure SPEEK membranes of similar IEC. Blend membranes exhibit slightly lower maximum proton conductivity than pure SPEEK membranes (60 vs. 75 mS cm^?1) but had significantly enhanced dimensional stability upon immersion in water, especially at elevated temperature (80 °C). Elevated temperature measurements in humid environments show increased proton conductivity of the SuPBI membranes when compared with SPEEK‐only membranes of similar IEC (c.f. 55 for the blend vs. 42 mS cm^?1 for SPEEK at 80 °C, 90% relative humidity). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3640–3650, 2010     

BaCe0.8Ho0.2O3-a陶瓷的性质与应用

Ceramic BaCe0.8Ho0.2O3-α with orthorhombic perovskite structure was prepared by conventional solid state reaction, and its conductivity and ionic transport number were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 600-1000 ℃ in wet hydrogen and wet air, respectively. Using the ceramics as solid electrolyte and porous platinum as electrodes, the hydrogen-air fuel cell was constructed, and the cell performance at temperature from 600-1000 ℃ was examined. The results indicate that the specimen was a pure protonic conductor with the protonic transport number of 1 at temperature from 600-900 ℃ in wet hydrogen, a mixed conductor of proton and electron with the protonic transport number of 0.99 at 1000 ℃. The electronic conduction could be neglected in this case, thus the total conductivity in wet hydrogen was approximately regarded as protonic conductivity. In wet air, the specimen was a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers were 0.01-0.09, and the oxide-ionic transport numbers were 0.27-0.32. The oxide ionic conductivity was increased with the increase of temperature, but the protonic conductivity displayed a maximum at 900 ℃, due to the combined increase in mobility and depletion of the carriers. The fuel cell could work stably. At 1000 ℃, the maximum short-circuit current density and power output density were 346 mA/cm^2 and 80 mW/cm^2, respectively.     

Hydrogen‐Bonded Organic Frameworks (HOFs): A New Class of Porous Crystalline Proton‐Conducting Materials

Two porous hydrogen‐bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra‐high proton conduction values (σ) 0.75× 10^?2 S cm^?1 and 1.8×10^?2 S cm^?1 under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic‐based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen‐bonded porous organic frameworks as solid‐state proton conducting materials.     

Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity

Metal–organic polyhedra (MOPs) or frameworks (MOFs) based on Cr³⁺ are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties. It is now shown that the co‐existence of In³⁺ and Cr³⁺ induces a rapid crystal growth of large single crystals of heterometallic In‐Cr‐MOPs with the [M₈L₁₂] (M=In/Cr, L=dinegative 4,5‐imidazole‐dicarboxylate) cubane‐like structure. With a high concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H‐bonded network between cubes and surrounding H₂O molecules, the newly synthesized In‐Cr‐MOPs exhibit an exceptionally high proton conductivity (up to 5.8×10^?2 S cm^?1 at 22.5 °C and 98 % relative humidity, single crystal).