An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions.

Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(II) with meso-tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10-3 S cm-1 at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.

Nafion/Surface Modified Ceria Hybrid Membranes for Fuel Cell Application.

Low chemical durability of proton exchange membranes is one the main factors limiting their lifetime in fuel cells. Ceria nanoparticles are the most common free radical scavengers. In this work, hybrid membranes based on Nafion-117 membrane and sulfonic or phosphoric acid functionalized ceria synthesized from various precursors were prepared by the in situ method for the first time. Ceria introduction led to a slight decrease in conductivity of hybrid membranes in contact with water. At the same time, conductivity of membranes containing sulfonic acid modified ceria exceeded that of the pristine Nafion-117 membrane at 30% relative humidity (RH). Hydrogen permeability decreased for composite membranes with ceria synthesized from cerium (III) nitrate, which correlates with their water uptake. In hydrogen-air fuel cells, membrane electrode assembly fabricated with the hybrid membrane containing ceria synthesized from cerium (IV) sulfate exhibited a peak power density of 433 mW/cm2 at a current density of 1080 mA/cm2, while operating at 60 °C and 70% RH. It was 1.5 times higher than for the pristine Nafion-117 membrane (287 mW/cm2 at a current density of 714 mA/cm2).

Ionic Mobility in Ion-Exchange Membranes.

Membrane technologies are widely demanded in a number of modern industries. Ion-exchange membranes are one of the most widespread and demanded types of membranes. Their main task is the selective transfer of certain ions and prevention of transfer of other ions or molecules, and the most important characteristics are ionic conductivity and selectivity of transfer processes. Both parameters are determined by ionic and molecular mobility in membranes. To study this mobility, the main techniques used are nuclear magnetic resonance and impedance spectroscopy. In this comprehensive review, mechanisms of transfer processes in various ion-exchange membranes, including homogeneous, heterogeneous, and hybrid ones, are discussed. Correlations of structures of ion-exchange membranes and their hydration with ion transport mechanisms are also reviewed. The features of proton transfer, which plays a decisive role in the membrane used in fuel cells and electrolyzers, are highlighted. These devices largely determine development of hydrogen energy in the modern world. The features of ion transfer in heterogeneous and hybrid membranes with inorganic nanoparticles are also discussed.

Proton conductivity as a function of the metal center in porphyrinylphosphonate-based MOFs.

The rational design of metal-organic frameworks (MOFs) is highly important for the development of new proton conductors. Porphyrinylphosphonate-based MOFs, providing the directed tuning of physical and chemical properties of materials through the modification of a macrocycle, are potentially high-conducting systems. In this work the synthesis and characterization of novel anionic Zn-containing MOF based on palladium(ii) meso-tetrakis(3-(phosphonatophenyl))porphyrinate, IPCE-2Pd, are reported. Moreover, the proton-conductive properties and structures of two anionic Zn-containing MOFs based on previously described nickel(ii) and novel palladium(ii) porphyrinylphosphonates, IPCE-2M (M = Ni(ii) or Pd(ii)), are compared in details. The high proton conductivity of 1.0 × 10-2 S cm-1 at 75 °C and 95% relative humidity (RH) is revealed for IPCE-2Ni, while IPCE-2Pd exhibits higher hydrolytic and thermal stability of the material (up to 420 °C) simultaneously maintaining a comparable value of conductivity (8.11 × 10-3 S cm-1 at 95 °C and 95% RH). The nature of the porphyrin metal center is responsible for the features of crystal structure of materials, obtained under identical reaction conditions. The structures of IPCE-2Pd and its dehydrated derivative IPCE-2Pd-HT are determined from the synchrotron powder diffraction data. The presence of phosphonic groups in compared materials IPCE-2M affords a high concentration of proton carriers that together with the sorption of water molecules leads to a high proton conductivity.

Porphyrinylphosphonate-Based Metal-Organic Framework: Tuning Proton Conductivity by Ligand Design.

A novel metal-organic framework [Zn3 (Ni-H2 TPPP)(Ni-H4 TPPP)(Ni-H5 TPPP)⋅7(CH3 )2 NH2 ⋅DMF⋅7 H2 O] (where Ni-Hx TPPP (x=2,4,5) are partially deprotonated [5,10,15,20-tetrakis(3-(phosphonatophenyl)-porphyrinato(2-))]nickel(II) species), IPCE-2Ni, with outstanding proton conductivity (1.0×10-2  S cm-1 at 75 °C and 95 % relative humidity) has been obtained. The high concentration of free phosphonate groups and compensating dimethylammonium cations bound by hydrogen bonds in the unique crystal structure of IPCE-2Ni is a key factor responsible for the observed high proton conductivity, which is one order of magnitude higher than for the corresponding MOF based on 5,10,15,20-tetrakis(4-(phosphonatophenyl)porphyrinato(2-))]nickel(II) IPCE-1Ni and comparable with that of leaders among MOFs.

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate.

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF (IPCE-1Ni), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10-3  S cm-1 at 75 °C and 80 % relative humidity).