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Metal phosphates represent an important group of materials with established industrial applications that are still attracting special scientific interest, owing to their outstanding physical and chemical properties. In this review, we account on the different synthetic routes and applications of zirconium and titanium phosphates, with a special focus on their application in the medicinal field. While zirconium phosphate has been extensively studied and explored with several reported industrial and medicinal applications, especially for drug delivery applications, titanium phosphates have not yet attracted the deserved attention regarding their established applications. However, titanium phosphates have been the focus of several structural studies with their different polymorphic forms, varied chemical structures, and morphologies. These variations introduce titanium phosphates as a strong candidate for technological and, particularly, biomedical applications.

Today, about 95 % of hydrogen gas supply is produced from steam methane reforming process, which uses substance from fossil fuel origin. This unsustainable source of hydrogen production also leads to greenhouse gases emission. Hence, this paper presents the promising future of exploiting an alternative to water electrolysis; the elevated temperature copper chloride electrolysis as a sustainable hydrogen production using polybenzimidazole based membrane. Temperature and current density are investigated in the range of 100 to 115 áµ’C and 0.1 to 0.5 A cm-2, respectively. Hybrid membrane PBI was synthesized with zirconium oxide (ZrO2) followed by phosphoric acid (PA) doping while pristine PBI and Nafion 117 used as a reference. The membrane properties are characterized using Metrohm Autolab PGSTAT302N, thermogravimetric analyzer, UV-Vis spectrometer, and Lloyd universal tensile tester. From the result, the hybrid PBI/ZrP membrane properties improved significantly compared to pristine PBI. The PBI/ZrP exhibited superior proton conductivity, thermally stable with high tensile strength. The efficiency of the electrolyzer for hydrogen production was ranging from 91 to 97 %. The mixing of the pristine PBI with ZrO2 and PA doping has produced hybrid PBI/ZrP membrane that can be a promising effective polymer electrolyte and budget-friendly compared to Nafion.

The effect of Phosphotungstic acid (PWA) on the proton conductivity and morphology of zirconium phosphate (ZrP), porous polytetrafluoethylene (PTFE), glycerol (GLY) composite membrane was investigated in this work. The composite membranes were synthesized using two approaches: 1) Phosphotungstic acid (PWA) added to phosphoric acid and, 2) PWA + silicic acid were added to phosphoric acid. ZrP was formed inside the pores of PTFE via the in situ precipitation. The membranes were evaluated for their morphology and proton conductivity. The proton conductivity of PWA-ZrP/PTFE/GLY membrane was 0.003 S cm-1. When PWA was combined with silicic acid, the proton conductivity increased from 0.003 to 0.059 S cm-1 (became about 60% of Nafion’s). This conductivity is higher than the proton conductivity of Nafion-silica-PWA membranes reported in the literature. The SEM results showed a porous structure for the modified membranes. The porous structure combined with this reasonable proton conductivity would make these membranes suitable as the electrolyte component in the catalyst layer for direct hydrocarbon fuel cell applications.

[EN] Cation-exchange membranes made exclusively from ceramic materials have been synthesized by means of the impregnation of microporous ceramic supports with zirconium phosphate. Changes in the pore size distribution and total pore volume of the supports were provoked by the addition of starch as pore former in the fabrication procedure. This allowed the production of supports with increased effective electrical conductivities and with larger pores available for the zirconium phosphate deposition. An improved functionality for the exchange of cations was given to the ceramic membranes by means of their impregnation with the active particles of zirconium phosphate. The ion-exchange properties of the membranes were increased with further impregnation cycles and the resulting current–voltage curves showed a similar shape to that typical of commercial polymeric ion-exchange membranes. The production of ionexchange membranes with increased chemical and radiation stability will broaden their applicability for the treatment of specific industrial waste waters, which are very aggressive for the current commercial ion-exchange membranes.

The optimum temperature for fixing zirconium phosphate, obtained by precipitation, on a low-cost ceramic support was determined in order to obtain an inorganic cation exchange membrane for electrodialysis. Zirconium phosphate ion exchange capacity maximised between 450 and 550°C, thus it was considered the optimum processing temperature. The origin of this maximum was investigated by means of X-ray diffraction and termogravimetry and evolved gas analysis. Zirconium phosphate formation by precipitation in the porous network of the support was verified by scanning electron microscopy and energy dispersive X-ray analysis and mercury intrusion porosimetry. The membrane obtained after thermal treatment at 450°C displayed selectivity to the cations present in the spent rinse water of the chromium plating process. This property allows the recovery of chromium by removing the cations through the cation exchange ceramic membrane.

In this article, the innovative cation-exchange membranes obtained from ceramic materials are presented. Different microporous ceramic supports were obtained from an initial mixture of alumina and kaolin, to which a varying content of starch was added in order to obtain supports with different pore size distributions. The deposition of zirconium phosphate into the porous supports generates membranes with cation-exchange properties. The fabrication of ion-exchange membranes which could resist aggressive electrolytes such as strong oxidizing spent chromium plating baths or radioactive solutions would allow the application of electrodialysis for the decontamination and regeneration of these industrial effluents. The performance of the manufactured membranes was studied in nickel sulfate solutions by means of chronopotentiometry. An increase of the membrane voltage drop during chronopotentiometric measurements was observed in some membranes, which seems to be a consequence of concentration polarization phenomena resulting from the ionic transfer occurred through the membranes. Current voltage curves were obtained for the different ceramic membranes, allowing the calculation of their ohmic resistance. The ohmic resistance of the membranes increased when the open porosity (OP) of the samples was incremented up to a value of 50%. For values of OP higher than 50%, the resistance of the membranes decreased significantly with porosity.

Cation-exchange membranes made exclusively from ceramic materials have been synthesized by means of the impregnation of microporous ceramic supports with zirconium phosphate. Changes in the pore size distribution and total pore volume of the supports were provoked by the addition of starch as pore former in the fabrication procedure. This allowed the production of supports with increased effective electrical conductivities and with larger pores available for the zirconium phosphate deposition. An improved functionality for the exchange of cations was given to the ceramic membranes by means of their impregnation with the active particles of zirconium phosphate. The ion-exchange properties of the membranes were increased with further impregnation cycles and the resulting current voltage curves showed a similar shape to that typical of commercial polymeric ion-exchange membranes. The production of ionexchange membranes with increased chemical and radiation stability will broaden their applicability for the treatment of specific industrial waste waters, which are very aggressive for the current commercial ion-exchange membranes.

Several types of novel proton exchange membranes which could be used for both direct methanol fuel cells (DMFCs) and hydrogen/air fuel cells were investigated in this work. One of the main challenges for DMFC membranes is high methanol crossover. Nafion, the current perfluorosulfonic acid copolymer benchmark membrane for both DMFCs and hydrogen/air fuel cells, shows very high methanol crossover. Directly copolymerized disulfonated poly(arylene ether sulfone)s copolymers doped with zirconium phosphates and phenyl phosphonates were synthesized and showed a significant reduction in methanol permeability. These copolymer/inorganic nanocomposite hybrid membranes show lower water uptake and conductivity than Nafion and neat poly(arylene ether sulfone)s copolymers, but in some cases have similar or even slightly improved DMFC performance due to the lower methanol permeability. These membranes also show advantages for high temperature applications because of the reinforcing effect of the filler, which helps to maintain the modulus of the membrane, allowing the membrane to maintain proton conductivity even above the hydrated glass transition temperature (Tg) of the copolymer. Sulfonated zirconium phenyl phosphonate additives were also synthesized, and membranes incorporating these materials and disulfonated poly(arylene ether sulfone)s showed promising proton conductivity over a wide range of relative humidities. Single-Tg polymer blend membranes were studied, which incorporated disulfonated poly(arylene ether sulfone) with varied amounts of polybenzimidazole. The polybenzimidazole served to decrease the water uptake and methanol permeability of the membranes, resulting in promising DMFC and hydrogen/air fuel cell performance.

The effect of the treatment of solid skeletal electrolytes, such as double zirconium phosphates Me0.5Zr2(PO4)3 (Me = Ni and Co), with high-frequency H2 and Ar plasma on the adsorption and desorption of CO2 was examined. It was found that the treatment of cobalt zirconium phosphate with high-frequency H2 plasma increases its specific surface area, while the pore size is reduced approximately tenfold (from 6.2 to 0.56 nm). Treatment with H2 and Ar plasma influences the adsorption characteristics of CO2 in various ways. The activated character of CO2 adsorption on the initial NiZr and CoZr phosphates remains after their treatment with high-frequency H2 plasma, while the strength of binding between adsorbate molecules and the surface increases. Treatment with Ar plasma leads to a reduction of CO2 adsorption with increasing temperature, and the isosteric heats do not depend on the nature of the conductive ion (Co2+ or Ni2+). © 2016, Pleiades Publishing, Ltd.