Synthesis, Characterization and Gas Separation Properties of MOF-5 Mixed Matrix Membranes

Yıl 2017, Cilt:6 ICOCEE Özel Sayı, 415 - 423, 27.12.2017

Hülya Aykaç Özen , Bahtiyar Öztürk , Hamdi Öbekcan

https://doi.org/10.17100/nevbiltek.332792

Cited By: 1

Öz

With the rapid development of hydrogen economy and
membrane science, membrane-based gas separation technology shows great
potential for the hydrogen purification. Mixed matrix membranes (MMM) have been
developed in order to increase the gas separation performance of a membrane.
However, MMMs result in poor filler-polymer compabilities and filler
segregation. Metal organic frameworks (MOFs) as new fillers with high surface
area and pore volume overcome these drawbacks and enhance the H₂ gas
adsorption properties. In this
study, MOF- 5 was synthesized, characterized and incorporated into polyimide
(PI) to investigate the effect of filler on the single gas permeation. MOF-5/PI MMMs were fabricated at different loading
rates (5wt.%, 10wt.%, 15wt.% MOF-5). The characterization a membrane was
performed by scanning electron microscopy (SEM), infrared spectroscopy (IR),
X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The
prepared  membranes with varying filller
contents were used to investigate the H₂, CO₂ and CH₄
permeation properties and H₂/CO₂, CO₂/CH₄,
H₂/CH₄ selectivities. The results showed that the single
gas permeation experiments for all gases increased with MOF-5 loading at room
temperature and pressure of 200 kPa. At higher loadings, ideal selectivity of H₂/CO₂,
CO₂/CH₄, H₂/CH₄  were found less compared to the pure polymer.
Consequently, the incorparation of MOF-5 into the polimer  incresed the membrane gas permeation rates
but decreased the selectivity.

Anahtar Kelimeler

Metal organic framework, Polymer, Mixed matrix membrane, Permeability, Selectivity

MOF-5 Bağlı Karışık Matriksli Membranların Sentezi, Karakterizasyonu ve Gaz Ayırma Özellikleri

Öz

Membran biliminin ve hidrojen ekonomisinin hızlı
gelişimi ile hidrojen saflaştırmada membrane dayalı ayırma teknolojisi yüksek
bir potansiyel göstermektedir. Gaz ayırma membranlarının performansını
arttırmak için karışık matrisli membranlar (MMM) geliştirilmiştir. Fakat,
MMM’lar, zayıf dolgu-polimer etkileşimine ve dolgu malzemesinin topaklanmasına
neden olmaktadır. Yüksek yüzey alanı ve por hacmine sahip yeni bir dolgu
malzemesi olan metal organik kafes sistemi (MOF) bu olumsuzlukarın üstesinden
gelmekte ve H₂ gas adsoprsiyon özellikleini iyileştirmektedir. Bu
çalışmada, MOF-5 sentezlenerek, bu yapının karakteristik özellikleri
incelenmiştir. Gaz geçirgenliği üzerinde dolgu maddesinin etkisini incelemek
üzere, farklı yükleme oranlarında (0, %5, %10, %15) hazırlanan MOF-5
kristalleri poliimit membrane içine ilave edilmiştir. Karakterizasyonları,
taramalı electron mikroskobu (SEM), kızık ötesi spektrometresi (IR), x ışını
kırınım cihazı (XRD), termogravimetrik analiz (TGA) ile tayin edilmiştir.
Farklı oranlarda hazırlanan membranlar, H₂, CO₂ ve CH₄
gazlarının geçirgenlikleri ile H₂/CO₂, CO₂/CH₄
ve H₂/CH₄ seçiciliklerini belirlemek üzere kullanılmıştır.
Tüm gazlarda geçirgenlik 200 kPa ve oda sıcaklığında artış göstermiş fakat  yükleme oranı arttıkça H₂/CO₂,
CO₂/CH₄ ve H₂/CH₄ seçicilikleri saf
polimere gore azalmıştır. Sonuç olarak, polimere MOF-5’in ilavesi geçirgenlik
performansını arttırmasına rağmen, seçicilik azalma göstermiştir.

Anahtar Kelimeler

Metal organik kafes, Polimer, Karışık matrisli membran, Geçirgenlik, Seçicilik

Kaynakça

• [1] Arjmandi M., Pakizeh M.,. “Mixed matrix membranes incorporated with cubic MOF-5 for improved polyetherimide gas separation membranes: Theory and experiment” Journal of Industrial and Engineering Chemistry, 20, 3857–3868, 2014
• [2] Robeson L. M.,. “Correlation of separation factor versus permeability for polymeric membranes” Journal of Membrane Science 62, 165-185, 1991
• [3] Robeson L. M., “The upper bound revisited” Journal of Membrane Science, 320, 390–400, 2008
• [4] Zornoza B., Gorgojo P., Casado C., Téllez C., Coronas J., “Mixed matrix membranes for gas separation with special nanoporous fillers” Desalination andWater Treatment, 27, 42-47, 2011
• [5] Chung T. S., Jiang L. Y., Li Y., Kulprathipanja S., “Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation”Progress in Polymer Science, 32, 483–507, 2007
• [6] Jeazet H.B.T., Staudt C., Janiak C., “Metal–organic frameworks in mixed- matrix membranes for gas separation” An International Journal of Inorganic Chemistry, 41, 14003-14027, 2012
• [7] Zornoza B., Tellez C., Coronas J., Gascon J., Kapteijn F,. “ Metal organic framework based mixed matrix membranes: An increasingly important field of research with a large application potential” Microporous and Mesoporous Materials, 166, 67–78, 2013.
• [8] Li H., Eddaoudi M., O’Keeffe M., Yaghi O.M., “ Design and synthesis of an exceptionally stable and highly porous metal-organic framework” Nature,402, 276–279, 1999
• [9] Yang M., Liu Q., Sun W.Y., “Shape and size control and gas adsorption of Ni(II) doped MOF-5 nano/microcrystals” Microporous and Mesoporous Materials, 190, 26-31, 2014
• [10] Zhao Z., Ma X., Li Z., Lin Y.S., “Synthesis, characterization and gas transport properties of MOF-5 membranes” Journal of Membrane Science, 382, 82-90, 2011
• [11] Rowsell J.L.C., Milward A.R., Park K.S., Yaghi O.M., “Hydrogen sorption in functionalized metal organic frameworks” Journal of American Society,126, 5666–5667, 2004
• [12] Panella B., Hirscher M., “Hydrogen physisorption in metal–organic porous crystals” Advanced Material, 17, 538–541, 2005
• [13] Panella B., Hirscher M., Putter H., Muller U., “Hydrogen adsorption in metal organic frameworks: Cu-MOFs and Zn- MOFs compared” Advanced Functional Materials,16, 520–524, 2006
• [14] Ullah S., Bustam M.A., Shariff A.M., Elkhalifah A.E.I., Murshid G. And Riaz N., “Synthesis and CO2 adsrption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite” AIP Proceedings, 1621,34-39, 2011
• [15] Hermes S., Schröder F., Amirjalayer S., Schmid R., Fischer R.A., “Loading of porous metal-organic open frameworks with organometallic CVD precursors: inclusion compounds of the type [LnM]a@MOF-5” Journal of Materials Chemistry, 16, 2464–2472, 2006
• [16] Sabouni R. , Kazemian H. , Rohani S., “A novel combined manufacturing technique for rapid production of IRMOF-1 using ultrasound and microwave energies” Chemical Engineering Journal, 165, 966-973, 2010
• [17] Li J., Cheng S., Zhao Q., Long P., Dong J., “Synthrsis and hydrogen storage behavior of metal organic framework MOF-5” International Journal of HydrogenEnergy, 34, 1377-1382, 2009
• [18] Perez E.V, Balkus., K.J., Ferraris J.P., Musselman, I.H., “Mixed-matrix membranes containing MOF-5 for gas separations” Journal of Membrane Science, 328, 165-173, 2009
• [19] Hafizovic J., Bjorgen M., Olsbye U., Dietzel P.D.C., Bordiga S., Prestipino C., Lamberti C., Lillerud K.P., “The inconsistency in adsorption properties and powder XRD data of MOF-5 is rationalized by framework interpenetration and the presence of organic and inorganic species in the nanocavities” Journal of American Society, 129, 3612-3620, 2007
• [20] Basu S., Cano-Odena A., Vankelecom I. F.J., “MOF-containing mixed-matrix membranes for CO2/CH4 and CO2/N2 binary gas mixture separations, Separation and Purification Technology, 81, 31–40, 2011
• [21] Aroon,M.A., Ismail A.F, MatsuuraT., Montazer-Rahmati M., “Performance studies of mixed matrix membranes for gas separation: A review”. Separation and PurificationTechnology, 75, 229–242, 2010