Anion transport through ceramic electrodialysis membranes made with hydrated cerium dioxide

This is the peer reviewed version of the following article: Mora-Gómez, Julia, García Gabaldón, Montserrat, Martí Calatayud, Manuel César, Mestre, Sergio, Pérez-Herranz, Valentín. (2017). Anion transport through ceramic electrodialysis membranes made with hydrated cerium dioxide.Journal of the American Ceramic Society, 100, 9, 4180-4189. DOI: 10.1111/jace.14978, which has been published in final form at http://doi.org/10.1111/jace.14978. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving[EN] In this research, low-cost ceramic anion-exchange membranes have been developed from porous supports manufactured, using a chamotte as a pore former. An inorganic anion-exchanger (hydrated cerium dioxide) has been deposited into the support and fixed by thermal treatment. The effects of some process variables (such as the temperature of the thermal treatment or the pH of the electrolyte) on the properties of the anion-exchange membranes have been investigated. The electrochemical performance of the resulting membranes has been compared to that exhibited by ceramic anion-exchange membranes based on another anion exchanger (hydrated zirconium dioxide) deposited into alumina-kaolin supports. The temperature of the thermal treatment applied to fix the hydrated cerium dioxide (HCeD) does not affect the structure nor the electrochemical properties of the membranes. The porosity of the supports obtained, using a chamotte as the pore former was lower than that of the alumina-kaolin ones, which led to a lower deposition of hydrated cerium dioxide than that obtained for hydrated zirconium dioxide (HZrD) in alumina-kaolin supports. The higher porosity registered for the HZrD-based membrane also implies higher membrane conductivities. The selective transport of anions through the membranes was enhanced by increasing the number of infiltrating steps, as confirmed from current to voltage curves. However, this behavior was only apparent at acidic or neutral pH, thus confirming the amphoteric character of the anion-exchanger. Comparing the parameter (equivalents of ion exchanger per gram of deposited oxide), it is concluded that the porosity of the ceramic supports, consequence of their distinct microstructure, is the main parameter responsible for the difference in the ion-exchange capacity obtained for HZrD and HCeD membranes. Consequently, the CeO2 particles used in this work are also good candidates to impart ion-exchange properties to microporous ceramic supports.Ministerio de Economia y Competitividad (Spain), Grant/Award Number: CTQ2012-3750-C02-01/PPQ, CTQ2012-3750-C02-02/PPQMora-Gómez, J.; García Gabaldón, M.; Martí Calatayud, MC.; Mestre, S.; Pérez-Herranz, V. (2017). Anion transport through ceramic electrodialysis membranes made with hydrated cerium dioxide. Journal of the American Ceramic Society. 100(9):4180-4189. https://doi.org/10.1111/jace.14978S418041891009Martí-Calatayud, M. C., Buzzi, D. C., García-Gabaldón, M., Ortega, E., Bernardes, A. M., Tenório, J. A. S., & Pérez-Herranz, V. (2014). Sulfuric acid recovery from acid mine drainage by means of electrodialysis. Desalination, 343, 120-127. doi:10.1016/j.desal.2013.11.031Ortiz, J. M., Sotoca, J. A., Expósito, E., Gallud, F., García-García, V., Montiel, V., & Aldaz, A. (2005). Brackish water desalination by electrodialysis: batch recirculation operation modeling. Journal of Membrane Science, 252(1-2), 65-75. doi:10.1016/j.memsci.2004.11.021Huang, K.-L., Holsen, T. M., & Selman, J. . (2003). Impurity diffusion through Nafion and ceramic separators used for electrolytic purification of spent chromium plating solutions. Journal of Membrane Science, 221(1-2), 135-146. doi:10.1016/s0376-7388(03)00254-0Sharifian, H. (1986). Electrochemical Oxidation of Phenol. Journal of The Electrochemical Society, 133(5), 921. doi:10.1149/1.2108763Linkov, V. ., & Belyakov, V. . (2001). Novel ceramic membranes for electrodialysis. Separation and Purification Technology, 25(1-3), 57-63. doi:10.1016/s1383-5866(01)00090-9Okada, T. (1999). Theory for water management in membranes for polymer electrolyte fuel cells. Journal of Electroanalytical Chemistry, 465(1), 1-17. doi:10.1016/s0022-0728(99)00065-0Okada, T. (1999). Theory for water management in membranes for polymer electrolyte fuel cells. Journal of Electroanalytical Chemistry, 465(1), 18-29. doi:10.1016/s0022-0728(98)00415-xGuddati, S. L., Holsen, T. M., Li, C.-C., Selman, J. R., & Mandich, N. V. (1999). Journal of Applied Electrochemistry, 29(9), 1129-1132. doi:10.1023/a:1003544822054Gallaher, G. R., & Liu, P. K. T. (1994). Characterization of ceramic membranes I. Thermal and hydrothermal stabilities of commercial 40 Å membranes. Journal of Membrane Science, 92(1), 29-44. doi:10.1016/0376-7388(94)80011-1Dzyazko, Y. S., Mahmoud, A., Lapicque, F., & Belyakov, V. N. (2006). Cr(VI) transport through ceramic ion-exchange membranes for treatment of industrial wastewaters. Journal of Applied Electrochemistry, 37(2), 209-217. doi:10.1007/s10800-006-9243-7Sui, Y., Fu, X., Zeng, R., & Ma, X. (2004). Preparation, characterization and application of a new type of ion exchanger and solid acid zirconium sulfonated oligo-polystyrenylphosphonate-phosphate supported on ZrO2. Journal of Molecular Catalysis A: Chemical, 217(1-2), 133-138. doi:10.1016/j.molcata.2004.03.003Rodrigues, L. A., Maschio, L. J., da Silva, R. E., & da Silva, M. L. C. P. (2010). Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide. Journal of Hazardous Materials, 173(1-3), 630-636. doi:10.1016/j.jhazmat.2009.08.131Dzyazko, Y. S., Rudenko, A. S., Yukhin, Y. M., Palchik, A. V., & Belyakov, V. N. (2014). Modification of ceramic membranes with inorganic sorbents. Application to electrodialytic recovery of Cr(VI) anions from multicomponent solution. Desalination, 342, 52-60. doi:10.1016/j.desal.2013.12.019Dzyazko, Y. S., Vasilyuk, S. L., Rozhdestvenskaya, L. M., Belyakov, V. N., Stefanyak, N. V., Kabay, N., … Yüksel, Ü. (2008). ELECTRO-DEIONIZATION OF Cr (VI)-CONTAINING SOLUTION. PART II: CHROMIUM TRANSPORT THROUGH INORGANIC ION-EXCHANGER AND COMPOSITE CERAMIC MEMBRANE. Chemical Engineering Communications, 196(1-2), 22-38. doi:10.1080/00986440802303715Martí-Calatayud, M. C., García-Gabaldón, M., Pérez-Herranz, V., Sales, S., & Mestre, S. (2015). Ceramic anion-exchange membranes based on microporous supports infiltrated with hydrated zirconium dioxide. RSC Advances, 5(57), 46348-46358. doi:10.1039/c5ra04169dMartí-Calatayud, M. C., García-Gabaldón, M., Pérez-Herranz, V., Sales, S., & Mestre, S. (2013). Synthesis and electrochemical behavior of ceramic cation-exchange membranes based on zirconium phosphate. Ceramics International, 39(4), 4045-4054. doi:10.1016/j.ceramint.2012.10.255Singh, S., Patel, P., Shahi, V. K., & Chudasama, U. (2011). Pb2+ selective and highly cross-linked zirconium phosphonate membrane by sol–gel in aqueous media for electrochemical applications. Desalination, 276(1-3), 175-183. doi:10.1016/j.desal.2011.03.048Tripathi, B. P., & Shahi, V. K. (2007). SPEEK–zirconium hydrogen phosphate composite membranes with low methanol permeability prepared by electro-migration and in situ precipitation. Journal of Colloid and Interface Science, 316(2), 612-621. doi:10.1016/j.jcis.2007.08.038Dzyaz’ko, Y. S., Linkov, V. M., & Belyakov, V. N. (2009). Transport of sulfate anions through inorganic membranes modified by ion-exchange material. Russian Journal of Electrochemistry, 45(12), 1333-1339. doi:10.1134/s1023193509120039Kogure, M., Ohya, H., Paterson, R., Hosaka, M., Kim, J.-J., & McFadzean, S. (1997). Properties of new inorganic membranes prepared by metal alkoxide methods Part II: New inorganic-organic anion-exchange membranes prepared by the modified metal alkoxide methods with silane coupling agents. Journal of Membrane Science, 126(1), 161-169. doi:10.1016/s0376-7388(96)00289-xOhya, H., Masaoka, K., Aihara, M., & Negishi, Y. (1998). Properties of new inorganic membranes prepared by metal alkoxide methods. Part III: New inorganic lithium permselective ion exchange membrane. Journal of Membrane Science, 146(1), 9-13. doi:10.1016/s0376-7388(98)00084-2Wu, C., Xu, T., & Yang, W. (2003). A new inorganic–organic negatively charged membrane: membrane preparation and characterizations. Journal of Membrane Science, 224(1-2), 117-125. doi:10.1016/j.memsci.2003.07.004Martí-Calatayud, M. C., García-Gabaldón, M., Pérez-Herranz, V., & Ortega, E. (2011). Determination of transport properties of Ni(II) through a Nafion cation-exchange membrane in chromic acid solutions. Journal of Membrane Science, 379(1-2), 449-458. doi:10.1016/j.memsci.2011.06.014Długołęcki, P., Anet, B., Metz, S. J., Nijmeijer, K., & Wessling, M. (2010). Transport limitations in ion exchange membranes at low salt concentrations. Journal of Membrane Science, 346(1), 163-171. doi:10.1016/j.memsci.2009.09.033Balster, J., Yildirim, M. H., Stamatialis, D. F., Ibanez, R., Lammertink, R. G. H., Jordan, V., & Wessling, M. (2007). Morphology and Microtopology of Cation-Exchange Polymers and the Origin of the Overlimiting Current. The Journal of Physical Chemistry B, 111(9), 2152-2165. doi:10.1021/jp068474tTaky, M., Pourcelly, G., Lebon, F., & Gavach, C. (1992). Polarization phenomena at the interfaces between an electrolyte solution and an ion exchange membrane. Journal of Electroanalytical Chemistry, 336(1-2), 171-194. doi:10.1016/0022-0728(92)80270-eClearfield, A. (1988). Role of ion exchange in solid-state chemistry. Chemical Reviews, 88(1), 125-148. doi:10.1021/cr00083a007Barragán, V. M., & Bauzá, C. R. (2002). Current–Voltage Curves for a Cation-Exchange Membrane in Methanol–Water Electrolyte Solutions. Journal of Colloid and Interface Science, 247(1), 138-148. doi:10.1006/jcis.2001.8065Tanaka, Y. (2003). Concentration polarization in ion-exchange membrane electrodialysis—the events arising in a flowing solution in a desalting cell. Journal of Membrane Science, 216(1-2), 149-164. doi:10.1016/s0376-7388(03)00067-xShapiro, V., Freger, V., Linder, C., & Oren, Y. (2008). Transport Properties of Highly Ordered Heterogeneous Ion-Exchange Membranes. The Journal of Physical Chemistry B, 112(31), 9389-9399. doi:10.1021/jp711169qChoi, J.-H., Lee, H.-J., & Moon, S.-H. (2001). Effects of Electrolytes on the Transport Phenomena in a Cation-Exchange Membrane. Journal of Colloid and Interface Science, 238(1), 188-195. doi:10.1006/jcis.2001.7510Kumar, M., Tripathi, B. P., & Shahi, V. K. (2009). Ionic transport phenomenon across sol–gel derived organic–inorganic composite mono-valent cation selective membranes. Journal of Membrane Science, 340(1-2), 52-61. doi:10.1016/j.memsci.2009.05.01

Composite inorganic matrix modified with ion-exchanger nanoparticles

The aim of the work was to elucidate a nature of charge-selective properties of macroporous composite inorganic membranes modified with nanoparticles of the ionexchanger, namely hydrated zirconium dioxide. The membrane was found to be selective towards anions in acidic media: membrane potential was registered in the solutions containing 10-100 mol m-3 HCl. Overlapping of intraporous diffusion constituents of electric double layer cannot be provided under these conditions. The membranes have been investigated using methods of standard contact porometry, potentiometry, scanning electron microscopy. The method of transmission electron microscopy was used to research individual ion-exchanger as well as ceramic powder, which had been obtained by crumbling up of the non-modified ceramic matrix. Differential curves of volume and surface distribution have been factorized using Lorentz functions, each maximum has been related to either structure element both of the matrix and the ion-exchanger. Calculations according to homogeneous and heterogeneous geometrical models were carried out to make this relation. Structure of the ceramic matrix has been shown to be formed with particles of micron size. Particles of the ion-exchanger (6 nm) form aggregates. It was found that the empties between the aggregates of ion-exchanger nanoparticles are responsible for charge selectivity because the aggregates cork pores of the matrix. Maximal radius of pores caused by the aggregates has been estimated as 25 nm. This is in agreement with porometric data. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/2058

Labile collagen matrix: transformation of hierarchical structure at nano- and micro-levels influenced by chemical treatment

Porous structure both of natural skin and collagen matrix obtained by chemical treatment of the skin with alkaline and acidic solutions, tannage with a Cr3+-containing solution, vegetable retannage and modification with bentonite was researched using scanning and transmission electron microscopy as well as standard contact porometry. Each stripe of porogrammes has been related to elements of multilevel structure. The pores were recognized using octane as a working liquid, the results obtained by this manner were used to determine loosening-compaction and ordering-disordering at each level of the structure, which includes nanosized macromolecules, microfibrils, fibrils and primary fibres of micron size. The measurements performed in aqueous media allowed us to determine hydrophilic pores and estimate their functions, secondary fibres have been also found by this manner. As for initial skin, porometric measurements diagnosed also non-collagen hydrophobic and hydrophilic inclusions, which form their own structure between microfibrils, fibrils, primary and secondary fibres of the matrix. The structure due to these inclusions is similar to that for collagen macromolecules. Microfibrils and fibrils have been found to form both ordered and disordered structures. Contribution of porosity of each organization level into the total porosity has been estimated, changes of collagen structure caused by chemical treatment and modification of inorganic ion-exchanger have been analyzed. Recommendation dealt to obtaining of materials for sorption and membrane separation have been given. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/2052

Hybrid organic-inorganic nanocomposites for ion-exchange processes

Two types of composite ion-exchangers, which are based on strongly acidic gellike cation-exchange resin and zirconium hydrophosphate, have been obtained. The first group contains both inorganic nanoparticles and their aggregates, the second one contains only aggregates. Analysis of differential porogrammes obtained with a method of standard contact porometry allowed us to estimate porous structure both of polymer matrix and inorganic constituent. Each stripe of the porogrammes has been related to structure element of polymer and ZrPh. Geometrical globular model has been applied to estimate a size of nanoparticles. A size of the nanoparticle size was shown to depend on their location: it reaches 16 nm, if the globules are placed in clusters of the polymer matrix, and 36 nm for aggregated nanoparticles in macropores. The results have been confirmed by data of scanning and transmission electron microscopy. Modification of ion-exchange resins causes transformation of porous structure of labile polymer matrix. The transformation occurs both at nano- and micro-levels. Recommendations regarding to structure of composite ion-exchangers for different applications are given. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/2057

Whey electrodialysis using organic-inorganic membranes

Organic-inorganic membranes based on heterogeneous ion exchange polymer supports, which were modified with hydrated zirconium dioxide (anion exchange membrane) and zirconium hydrophosphate (cation exchange separator), were used for whey desalination as well as for concentrate and permeate of whey nanofiltration. Comparing with pristine polymer membranes, the composite materials are characterized by stability against fouling inside pores. The membranes were applied to desalination of whey and products of its baromembrane treatment. Exponential decay of electrical conductivity over time has been found for the solutions being purified. The membrane resistance grew simultaneously

Selective to lithium ions nanocomposite sorbents based on TiO2 containing manganese spinel

A method for obtaining nanocomposite sorbents, which are selective towards Li+ ions, has been proposed. The samples were based on adsorptive-active anatase, the selective component being lithium-manganese spinel LiMn2O4. This component was synthesized preliminarily, its nanoparticles were added to the sol of insoluble titanium hydroxocomplexes, and the nanocomposite was precipitated from this suspension and calcined at 5000C. A number of sorbents with different molar ratio of Ti:Mn were prepared via this procedure; they were investigated by means of chemical analysis, X-ray diffraction analysis, optical microscopy, transmission electron microscopy and scanning electron microscopy. The size of nanocrystallites was 20–30 nm. An increase in the spinel amount caused a decrease in the sorbent grain size; however, they the sorbent grains were mechanically durable due to TiO2 which was a binder. Adsorption of Li+ from the solution containing an excess of Na+ ions was studied. The optimal amount of LiMn2O4 (13%) was determined. The sample was obtained in the form of rather large grains (0.3 mm) and the selectivity coefficient Li+/Na+ was about 500. The sorbent was regenerated by a 1 M HNO3 solution without manganese leakage. After 10 cycles of sorption-desorption, the concentrate was obtained. This concentrate can be used for Li2CO3 precipitation

П'ята міжнародна наукова-практична конференція «Комп’ютерне моделювання в хімії і технологіях та системах сталого розвитку»

Для встановлення механізму осадження гідратованих оксидів в аніонообмінній полімерній матриці застосовано комп'ютерний фрактальний аналіз ТЕМ зображень, знайдено, що фрактальна розмірність становить 2.38-2.72, отже, лімітуючою стадією утворення агрегатів є дифузія наночастинок.Computer fractal analysis of TEM images was applied to TEM images to establish the mechanism of precipitation of hydrated oxides in anion exchange polymer matrix. Fractal dimension has been found to reach 2.38-2.72, thus, diffusion of nanoparticles is the rate-determining stage of aggregate formation.Для установления механизма осаждения гидратированных оксидов в анионообменной полимерной матрице применен компьютерный фрактальный анализ ТЭМ изображений, найдено, что фрактальная размерность составляет 2.38-2.72, таким образом, лимитирующей стадией образования агрегатов является диффузия наночастиц