Multifunctional lanthanum tetraphosphonates: flexible, ultramicroporous and proton-conducting hybrid frameworks

A new flexible ultramicroporous solid, La(H(5)DTMP)·7H(2)O (1), has been crystallized at room temperature using the tetraphosphonic acid H(8)DTMP, hexamethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid). Its crystal structure, solved by synchrotron powder X-ray diffraction, is characterised by a 3D pillared open-framework containing 1D channels filled with water. Upon dehydration, a new related crystalline phase, La(H(5)DTMP) (2) is formed. Partial rehydration of 2 led to La(H(5)DTMP)·2H(2)O (3). These new phases contain highly corrugated layers showing different degrees of conformational flexibility of the long organic chain. The combination of the structural study and the gas adsorption characterization (N(2) and CO(2)) suggests an ultramicroporous flexible framework. NO isotherms are indicative of a strong irreversible adsorption of NO within the pores. Impedance data indicates that 1 is a proton-conductor with a conductivity of 8 × 10(-3) S cm(-1) at 297 K and 98% of relative humidity, and an activation energy of 0.25 eV.     

Superhigh intrinsic proton conductivity in densely carboxylic covalent organic framework

Herein, we developed for the first time two carboxylic acid based intrinsic proton conductors (COOH-COF-1 and COOH-COF-2) via pre-assembly approach. The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities, but also exhibit superhigh intrinsic proton conductive behaviors. Especially, the intrinsic proton conductivity of COOH-COF-2 is up to 2.6 × 10⁻³ S/cm at 353 K and 98% RH, which is the highest value among all the reported acid functionalized COFs. This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.     

High proton conduction in a chiral ferromagnetic metal-organic quartz-like framework

A complex-as-ligand strategy to get a multifunctional molecular material led to a metal-organic framework with the formula (NH(4))(4)[MnCr(2)(ox)(6)]·4H(2)O. Single-crystal X-ray diffraction revealed that the anionic bimetallic coordination network adopts a chiral three-dimensional quartz-like architecture. It hosts ammonium cations and water molecules in functionalized channels. In addition to ferromagnetic ordering below T(C) = 3.0 K related to the host network, the material exhibits a very high proton conductivity of 1.1 × 10(-3) S cm(-1) at room temperature due to the guest molecules.     

High proton conductivity of water channels in a highly ordered nanowire

A proton-conductive material based on a crystalline assembly of trimesic acid and melamine (TMA?M, see picture) is reported. Because of the ordered structure of the assembly, the water-saturated proton conductivity for the TMA?M assembly is 5.5?S?cm(-1) , which is the highest proton conductivity measured to date. This exceptionally high conductivity and low-cost fabrication of the material make applications feasible for fuel-cell devices.     

Coordination-chemistry control of proton conductivity in the iconic metal-organic framework material HKUST-1

HKUST-1, a metal-organic framework (MOF) material containing Cu(II)-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu(II) sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the "as synthesized" version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu(II) to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by ~75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent.     

Enhanced proton conductivity of Mo_(154)-based porous inorganic framework

The construction of inorganic porous frameworks from discrete polyoxometalate (POM) units is a major research challenge.Herein,a three-dimensional (3D) all-inorganic porous structure{Mo_(154)}_n that consists of classic Mo_(154)rings connected by Mo–O–Mo covalent bonds was synthesized.Interestingly,the proton conductivity of the 3D-{Mo_(154)}_n framework is 1.1×10~(-2)S cm~(-1)at 22℃ and 100%relative humidity (RH),which is one of the highest proton conductivities reported thus far for POM-based conductive materials.Compared to the discrete{Mo_(154)}cluster and 1D-{Mo_(154)}_n,the enhanced conductivity of 3D-{Mo_(154)}_n suggests that assembling POM-based all-inorganic porous frameworks is a promising method for designing proton-conductive materials.     

Thermal conductivity of a hybrid nanofluid

Journal of Thermal Analysis and Calorimetry - Hybrid nanofluid can be considered as a new generation of nanofluids. Despite the success of the researchers in the field of hybrid nanofluids, no...     

High throughput screening and measurements of proton conductivity of newly developed PEM materials based on proton transport visualization

An electrochemical method for proton transport visualization was developed and applied to the investigation of proton-conducting membrane materials. The method employs the change in the visual appearance of chemo-chromic tungsten oxide WO₃ in the presence of atomic hydrogen. An all-solid electrochemical cell arranged by substituting a fuel cell cathode with a thin film of WO₃-electrode was built and shown to generate both optical and electrical response to hydrogen gas exposure. The design of the cell was extended to a high throughput screening system that was utilized to characterize proton transport properties of samples, including a number of new compounds synthesized in-house by sol–gel wet chemistry. Non-destructive introduction of superacidic groups promoting proton hopping in the membrane materials was achieved by photodecomposition of a photoacid generator just after membrane casting. A model quantitatively describing current–voltage relation in the cell was developed and successfully applied to derive area-specific resistance of proton-conductive membranes from the experimental results. Area-specific resistances of membranes are derived from the slopes of optically reconstructed voltage–current curves. Sensitivity and dynamic range of the screening method are discussed.     

Selective CO2 adsorption in a flexible non-interpenetrated metal-organic framework

We have prepared a flexible metal-organic framework and demonstrated that when activated by supercritical CO(2) it has greater gas sorption capacities than that activated by the heat-evacuation method, and it selectively adsorbs CO(2) over N(2) at room temperature.     

Light enhanced proton conductivity in a terbium phosphonate photochromic chain complex

Crystalline complexes that exhibited light switchable proton conductivity are of great interest but still a challenge in material science. Herein, a terbium phosphonate chain complex was synthesized through assembly of electron-rich phosphonate units, electron-deficient polypyridine components and paramagnetic Tb~(3+) ions. Via light irradiation and heat treatment, the photogenerated radicals could simultaneously and reversibly tune the photochromic, luminescent and magnetic properties. Originating from the abundant hydrogen bonding networks formed between PO_3 groups and lattice water molecules, proton conductive behaviour was explored with high proton conductivity of(1.74±0.19)×10~(-3) S cm~(-1) at 80 °C and 100% relative humidity. Importantly, accompanied with the colorless sample changed to blue, the proton conductivity increased about 20% after room temperature light illumination, implying that light irradiation could act as an external stimulus to enhance the conductive properties of original material. This work innovatively realized the light responsive conductive property in the electron transfer photochromic materials, providing a novel strategy for the construction of smart materials.     

Evaluation of proton conductivity of sulfonated polyimide/dihydroxy naphthalene charge‐transfer complex hybrid membranes

Sulfonated polyimide (SPI)/dihydroxynaphthalene (DHN) charge‐transfer (CT) complex hybrid films were investigated as possible alternative for polymer electrolyte membranes in polymer electrolyte fuel cells. SPI/DHN CT complex hybrid films include CT complexes, which might work as electronic conductors, and sulfonic acid units, which could work as proton conductors. Therefore, the origin of the conductivity of SPI/DHN complex hybrid films was evaluated by four‐probe impedance measurements in the through‐plane direction of the films. The obtained conductivity of the CT complex hybrid films increased with the increase of ion exchange capacity of the CT films and the decrease of CT complex concentration in the films. These results indicated that proton transfer dominantly occurred in the CT complex hybrid films. Proton conductivity of the CT complex hybrid films consisting of 2,6‐ or 1,5‐DHN showed the similar values, although the molecular geometries of the CT complex were different. The activation energy values for proton conductivity in the CT films were approximately the same as that of Nafion 212. Water uptake (WU) results were also conducted and suggest that CT complex formation could control the degree of WU of the films and prevent dissolution of SPI. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2991–2997     

Electrochemical atomic force microscopy study of proton conductivity in a Nafion membrane

High membrane conductivity is one of the key parameters in polymer electrolyte fuel cell applications. We introduce an electrochemical atomic force microscopy method that provides simultaneously the surface topography of a Nafion 112 membrane and the conductivity of ion channels with an unprecedented resolution of ca. 10 nm. For given conditions, a large fraction of the channel ports is found to conduct exactly the same number of protons per unit time. This is taken as evidence for an optimum pore size and structure for proton conduction, or alternatively, for an efficient connectivity of the ion channel network, so that the same conductivity is measured at all exit pores. The time response following a potential step and the influence of the relative humidity on the transport properties is investigated. The method will be of relevance for tailoring the production technology to yield an optimised micromorphology, and it permits detailed tests of membrane models and provides data for theoretical modelling of proton conductivity.     

Fabrication and characterization of graphene/sulfonated polyether sulfone octyl sulfonamide hybrid film with improved proton conductivity performance

Journal of Solid State Electrochemistry - In this study, graphene (G) was blended with sulfonated polyether sulfone octyl sulfonamide (SPESOS) in different ratios (1, 1.5, and 2 wt.%) to enhance...     

Formation, structure, and stability of titanate nanotubes and their proton conductivity

High-yield H-form trititanate nanotubes have been synthesized, and their structures have been characterized by using X-ray diffraction and high-resolution transmission electron microscopy. According to combined TGA/XRD studies, the nanotubes are not stable at high temperature. Thermal analysis suggests that the stoichiometry of the material is H(2)Ti(3)O(7).0.8H(2)O(abs). Conductivity measurements indicate that mainly protonic transport occurs at temperatures below 150 degrees C and that with increasing temperature and progressive breakdown of nanotubes and formation of crystalline TiO(2) phases protonic conductivity is lost, leaving only residual defect electronic conduction. The proton conductivity is ca. 5.5 x 10(-6) S cm(-1) at 300 K. The structural protons and trapped water were confirmed by solid-state NMR.     

Flexible side arms of ditopic linker as effective tools to boost proton conductivity of Ni8-pyrazolate metal-organic framework

Two primitive metal-organic frameworks （MOFs）,Ni L1 and Ni L2,based on Ni₈O₆-cluster and ditopic pyrazolate linkers,L1 （with rigid alkyne arms） and L2 （with flexible alkyne chains）,were prepared.The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms,Im@Ni L1 and Im@Ni L2,were measured and compared.Upon introduction of imidazole molecules,the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72×10...     

Wide control of proton conductivity in porous coordination polymers

The proton conductivities of the porous coordination polymers M(OH)(bdc-R) [H(2)bdc = 1,4-benzenedicarboxylic acid; M = Al, Fe; R = H, NH(2), OH, (COOH)(2)] were investigated under humid conditions. Good correlations among pK(a), proton conductivity, and activation energy were observed. Fe(OH)(bdc-(COOH)(2)), having carboxy group and the lowest pK(a), showed the highest proton conductivity and the lowest activation energy in this system. This is the first example in which proton conductivity has been widely controlled by substitution of ligand functional groups in an isostructural series.     

Conductivity,proton percolation,and gelation during the network growth in a flexible chain diepoxide and diamine mixture

The conductivity of a stoichiometric mixture of diglycidyl ether of 1,4‐butanediol and 1,6‐hexamethylene diamine has been studied during its polymerization at several temperatures where the ultimate product is a crosslinked gel. The decrease in the dc conductivity, σ₀, with the polymerization time, t, fits an equation for bond percolation, σ₀ ∼ [(t_gel‐t)/t_gel]^p, and yields a gelation time, t_gel which agrees with the t_gel determined from the viscosity and shear modulus measurements. It is proposed that as one covalent bond forms on chemical reaction, an indeterminable number of intermolecular H‐bonds in the structure vanish, and protonic conduction is disrupted. Thus, as the original H‐bond network gives way to a covalently bonded network, the mechanical rigidity increases, and protonic conductivity decreases. The gel point is reached when the increase in the number of covalent bonds brings the liquid's state up to its rigidity percolation threshold, and the decrease in the number of H‐bonds brings it down to its electrical percolation threshold. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 122–126, 2000     

A flexible porphyrin-annulene hybrid: a nonporphyrin conformation for meso-tetraaryldivacataporphyrin

An annulene–porphyrin hybrid, the diaaza‐deficient porphyrin 5,10,15,20‐tetraaryl‐21,23‐divacataporphyrin, has been synthesized by an extrusion of tellurium atom(s) from 5,10,15,20‐tetraaryl‐21,23‐ditelluraporphyrin under treatment with HCl. In addition, a monoaza‐deficient 5,10,15,20‐tetraaryl‐21‐tellura‐23‐vacataporphyrin was formed in the same reaction. The two new members of the vacataporphyrin family were characterized by X‐ray crystallography, as well as UV/Vis and NMR spectroscopy. These aromatic molecules preserve the fundamental structural and spectroscopic features of the parent tetraarylporphyrin. The X‐ray crystal structures of 21,23‐divacataporphyrin and 21‐tellura‐23‐vacataporphyrin show typical porphyrin patterns. The molecules are not strictly planar and show distortion of the annulene moieties. The N22???N24 distances (5.23 and 5.09 Å) are considerably longer than in regular porphyrins. For 21,23‐divacataporphyrin, variable‐temperature ¹H NMR spectroscopy data allowed the identification of divacataporphyrin stereoisomers differentiated by the geometry of the butadiene bridges. The forms remain in thermodynamic equilibrium.