The study of proton conductivity processes has gained intensive attention in the past decades due to their potential applications in chemical sensors, electrochemical devices, and energy generation. The scientific community has focused its efforts on the development of high‐performing polymeric membranes as proton exchange membranes (PEMs) for fuel cell (FC) applications. In particular, high conductivity at different humidity and temperature and enhanced chemical and mechanical stability under operative conditions are considered the main goals to be reached. The design of mixed‐matrix membranes (MMMs) based on conductive polymers and inorganic fillers is an approach commonly used for achieving materials with improved conductive and mechanical properties. In the last five years, the use of metal‐organic frameworks (MOFs) as fillers for conductive MMMs has rapidly grown for their intrinsic stability and structural versatility. The recent progress around the proton conductivity of MOF based composite membranes on PEMs for FC applications is critically reviewed.

A novel mixed zirconium phosphate/phosphonate based on glyphosine, of formula Zr2(PO4)H5(L)2·H2O [L = (O3PCH2)2NCH2COO], was synthesized in mild conditions. The compound has a layered structure that was solved ab initio from laboratory PXRD data. It crystallizes in the monoclinic C2/c space group with the following cell parameters: a = 29.925(3), b = 8.4225(5), c = 9.0985(4) Å, and β = 98.474(6)°. Phosphate groups are placed inside the sheets and connect the zirconium atoms in a tetradentate fashion, while uncoordinated carboxylate and P-OH phosphonate groups are exposed on the layer surface. Due to the presence of these acidic groups, the compound showed remarkable proton conductivity properties, which were studied in a wide range of temperature and relative humidity (RH). The conductivity is strongly dependent on RH and reaches 1 × 10(-3) S cm(-1) at 140 °C and 95% RH. At this RH, the activation energy of conduction is 0.15 eV in the temperature range 80-140 °C. The similarities of this structure with related structures already reported in the literature were also discussed.

Reaction of cerium ammonium nitrate and tetrafluoroterephthalic acid in water afforded two new metal-organic frameworks with UiO-66 [F4_UiO-66(Ce)] and MIL-140 [F4_MIL-140A(Ce)] topologies. The two compounds can be obtained in the same experimental conditions, just by varying the amount of acetic acid used as crystallization modulator in the synthesis. Both F4_UiO-66(Ce) and F4_MIL-140A(Ce) feature pores with size < 8 Å, which classifies them as ultramicroporous. Combination of X-ray photoelectron spectroscopy and magnetic susceptibility measurements revealed that both compounds contain a small amount of Ce(III), which is preferentially accumulated near the surface of the crystallites. The CO2 sorption properties of F4_UiO-66(Ce) and F4_MIL-140A(Ce) were investigated, finding that they perform better than their Zr-based analogues. F4_MIL-140A(Ce) displays an unusual S-shaped isotherm with steep uptake increase at pressure < 0.2 bar at 298 K. This makes F4_MIL-140A(Ce) exceptionally selective for CO2 over N2: the calculated selectivity, according to the ideal adsorbed solution theory for a 0.15:0.85 mixture at 1 bar and 293 K, is higher than 1900, amongst the highest ever reported for metal-organic frameworks. The calculated isosteric heat of CO2 adsorption is in the range of 38-40 kJ mol-1 , indicating a strong physisorptive character. CeO(TFBDC)•H2O [F4_MIL-140A(Ce)] 548 mg (1mmol) of cerium ammonium nitrate [(NH4)2Ce(NO3)6), CAN] and 238 mg (1 mmol) of tetrafluoroterephthalic acid (H2TFBDC) were dissolved in 50 ml of deionized (DI) water in a round bottom flask. The solution was heated to 110 °C under stirring and refluxed for 24 h. The obtained yellow solid was collected and washed three times with DI water and once with acetone. The solid was then dried in oven at 80 °C for 24 h. Yield: 73% (calculated on the basis of Ce). Elemental analysis: C = 22.7% exp. (23.4% calc.), H = 0.76% exp. (0.49% calc.) CeO0.67(OH)0.67(TFBDC)•3H2O [F4_UiO-66(Ce)] 548 mg (1 mmol) of CAN, 238 mg (1 mmol) of H2TFBDC and 6 mL (100 mmol) of acetic acid were dissolved in 45 ml of DI water in a round bottom flask. The solution was heated to 110 °C under stirring and refluxed for 24 h. The obtained yellow solid was collected and washed three times with DI water and once with acetone. The solid was then dried in oven at 80 °C for 24 h. Yield: 66% (calculated on the basis of Ce). Elemental analysis: C = 23.5% exp. (22.6% calc.), H = 2.19% exp. (1.57% calc.) Analytical procedures Powder X-Ray Diffraction (PXRD). PXRD patterns were collected in reflection geometry with a 40 s step-1 counting time and with a step size of 0.016° 2θ on a PANalytical X'PERT PRO diffractometer, PW3050 goniometer, equipped with an X'Celerator detector by using the Cu Kα radiation. The long fine focus (LFF) ceramic tube operated at 40 kV and 40 mA. The pattern

In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery.

The first crystalline microporous zirconium phosphonate metal-organic framework (UPG-1) was synthesized using the novel tritopic ligand 2,4,6-tris(4-(phosphonomethyl)phenyl)-1,3,5-triazine. Its crystal structure was solved ab initio from laboratory powder X-ray diffraction data. UPG-1 displays remarkable thermal stability and hydrolysis resistance and has a good absorption affinity towards n-butane and CO2.

Metal-organic frameworks (MOFs) have gained widespread attention due to their modular construction that allows the tuning of their properties. Within this vast class of compounds, metal carboxylates containing tri- and...

Mixed membrane matrices (MMMs) made up with Nafion and nanocrystals of zirconium metal-organic framework (MOF) UiO-66 or the analogous sulfonated SOH-UiO-66 were prepared by varying the filler loading and the size of the crystals. The combined effects of size and loading, together with the presence of sulfonic groups covalently linked to the MOFs, were studied with regard to the conductivity and mechanical properties of the obtained composite matrices. A large screening of membranes was preliminarily made and, on the most promising samples, an accurate conductivity study at different relative humidities and temperatures was also carried out. The results showed that membranes containing large crystals (200 nm average size) in low amounts (around 2%) displayed the best results in terms of proton conductivity values, reaching values by 30% higher than those of pure Nafion, while leaving the mechanical properties substantially unchanged. On the contrary, MMMs containing MOFs of small size (20 nm average size) did not show any conductivity improvements if compared to pure Nafion membranes. The effect of MOF sulfonation was negligible at low filler loading whereas it became important at loading values around 10%. Finally, membranes with a high filler loading (up to 60 wt %) of sulfonated UiO-66 showed a slight reduction of conductivity in comparison with membranes loaded at 20% of nonsulfonated ones.

The flexible zirconium tetraphosphonate coordination polymer with formula Zr(O(3)PCH(2))(2)N-C(6)H(10)-N(O(3)CH(2)P)(2)X(2-x)H(2+x)·nH(2)O (X = H, Li, Na, K, 0 < x < 1, 4 < n < 7.5) (1) possesses an open framework structure with 1D cavities decorated with polar and acids P═O and P-OH groups. 1 has been fully protonated by adding HCl and then subjected to several acid-base ion-exchange reactions with alkaline metals hydroxides. 1 is a very robust coordination polymer because it can be regenerated in H- form using strong acid solutions and ri-exchanged several times without hydrolysis and loss of crystallinity. The flexibility of 1 has been also studied by means of TDXD (temperature dependent X-ray diffraction) evidencing remarkable phase transformations that lead to a different disposition of the water molecules. These transformations also influence the accessibility of the cations on the P-OH groups placed inside the channels and thus the ion-exchange properties. The dependence of the proton conductivity properties on these phase transitions has been also investigated and discussed.