Al-, Cr-SÜTUNLU KİLLERİN VE Cr-YERLEŞTİRİLMİŞ Al- SÜTUNLU KİLLERİN GÖZENEK YAPILARININ DFT VE DR ANALİZLERİ İLE KARAKTERİZASYONU

Yıl 2012, Cilt: 27 Sayı: 3, 0 - , 19.02.2013

Funda Basoglu Fatma Tomul

Öz

Al-sütunlu kil (Al-SK), krom-alüminyum karışık sütunlu killer (CrAl033-SK, CrAl1-SK) ve Cr-sütunlu kil (Cr-SK) Türkiye’nin Hançılı bölgesinden alınan bentonit örneği kullanılarak sentezlenmiştir. Metal yerleştirilmişsütunlu kil örneklerinin sıvı azot sıcaklığında N2 adsorpsiyon/desorpsiyon izotermleri elde edilmiş ve izotermverileri kullanılarak gözenek yapıları Yoğunluk Fonksiyonel Teori (Density Functional Theory DFT) veDubinin-Radushkevich (DR) metodları ile belirlenmiştir. DFT modelinin metal yerleştirilmiş sütunlu kilörneklerinin deneysel verisiyle uyumlu olduğu gözlenmiştir. En yüksek DFT ve DR mikrogözenek hacimdeğerleri 573 K de kalsine edilmiş CrAl033-SK örneği için 0,080 cm3g-1 ve 0,138 cm3g-1 olarak elde edilmiştir. DRmetot ile elde edilen mikrogözenek hacim değerlerinin SF metodla belirlenmiş mikrogözenek hacim değerleri ileuyumlu olduğu görülmüştür.

Anahtar Kelimeler

Cr yerleştirilmiş Al-sütunlu kil, gözenek yapısı, DFT metot, DR metot.

Kaynakça

• Gil, A., Korili, S.A., Vicente, M.A., “Recent
• Advances in the Control and Characterization of
• the Porous Structure of Pillared Clay Catalysts”,
• Catal. Rev., 50-2: 153–221, 2008.
• Tomul, F., Balcı, S., “Characterization of Al, Crpillared
• clays and CO oxidation”, Appl. Clay Sci.,
• :13-20, 2009.
• Başoğlu, F.T., Balcı, S., “Micro-mesopore analysis
• of Cu2+ and Ag+ containing Al-pillared bentonite”,
• Appl. Clay Sci., 50: 73-80, 2010
• Han, Y-S., Yamanaka, S., Choy, J-H., “Acidic and
• hydrophobic microporous clays pillared with
• mixed metal oxide nano-sols”, J. Solid State
• Chem., 144: 45-52, 1999.
• Bahranowski, K., Kielski, A., Serwicka, E.M.,
• Wisła-Walsh, E., Wodnicka, K., “Influence of
• doping with copper on the texture of pillared
• montmorillonite catalysts”, Micropor. Mesopor.
• Mat., 41: 201-215, 2000.
• Chmielarz, l., Kustrowski, P., Zbroja, M.,
• Rafalska-Lasocha, A., Dudek, B., Dziembaj, R., “SCR of NO by NH3 on alumina or titania-pillared
• montmorillonite various modified with Cu or Co.
• Part 1. General Characterization and catalysts
• screening”, Appl. Catal B- Environ. 45: 103-116,
• -
• Shin, Y-S., Oh, S-G., Ha, B-H., “Pore structures
• and acidities of Al-pillared montmorillonite”,
• Korean J. Chem. Eng., 20:1, 77-82, 2003.
• Marinkovic-Neducin, R.P., Kiss, E.E., Cukic,
• T.Z., Obadovic, D.Z., “Thermal behavior of Al-,
• AlFe- and AlCu- pillared interlayered clays”, J.
• Therm. Anal. Calorim., 78: 307-321, 2004.
• Jagtap, N., Ramaswamy, V., “Oxidation of aniline
• over titania pillared montmorillonite clays”,
• Appl.Clay Sci., 33: 89-98, 2006.
• Chmielarz, L., Kustrowski, P., Michalik, M.,
• Dudek, B., Piwowarska, Z., Dziembaj, R.,
• “Vermiculites intercalated with Al2O3 pillars and
• modified with transition metals as catalysts of
• DeNOx process”, Catal. Today, 137: 242-246,
• -
• Kooli, F., Liu, Y., Alshahateet, S.F., Siril, P.,
• Brown, R., “Effect of pillared clays on the
• hydroisomerization of n-heptane”, Catal. Today,
• : 244-249, 2008.
• Moronta, A., Oberto, T., Carruyo, G., Solano, R.,
• Sanchez, J., Gonzalez, E., Huerta, L.,
• “Isomerization of 1-butene catalyzed by ionexchanged,
• pillared and ion-exchanged/pillared
• clays”, Appl. Catal. A-Gen., 334: 173-178, 2008.
• Lowell, S., Shields, J.E., Thomas, M.A.,
• Thommes, M., “Characterization of Porous
• Solids and Powders: Surface Area, Pore Size
• and Density”, Kluwer Academic Publishers,
• -
• Thommes, M., “Introduction to Zeolite Science
• and Practise”, 3rd ed., Elsevier, 2007.
• Vega, L.F., “Nanomaterials: Design and
• Simulation”, Elsevier, 2007.
• Olivier, J.P., “Improving the models used for
• calculating the size distribution of micropore
• volume of activated carbons from adsorption
• data”, Carbon, 36, 10, 1469-1472, 1998.
• Ryu, Z., Zheng, J., Wang, M., Zhang, B.,
• “Characterization of pore size distributions on
• carbonaceous adsorbents by DFT”, Carbon, 37:
• -1264, 1999.
• Do, D.D., Nguyen, C., Do, H.D.,
• “Characterization of micro-mesoporous carbon
• media”, Colloid Surface A., 187-188: 51-71,
• -
• Gauden, P., Terzyk, A.P., Rychlicki, G.,
• Kowalczyk, P., Cwiertnia, M.S., Garbacz, J.K.,
• “Estimating the pore size distribution of activated
• carbons from adsorption data of different
• adsorbates by various methods”, J. Colloid Interf.
• Sci., 273: 39-63, 2004.
• Jagiello, J., Thommes, M., “Comparison of DFT
• characterization methods based on N2, Ar, CO2,
• and H2 adsorption applied to carbons with various
• pore size distributions”, Carbon, 42, 1227-1232,
• -
• Lopez de Letona Sanchez, M., Macias-Garcia, A.,
• Diaz-Diez, M.A., Cuerda-Correa, E.M., Ganan-
• Gomez, J., Nadal-Gisbert, A., “Preparation of
• activated carbons previously treated with
• hydrogen peroxide: Study of their porous texture”,
• Appl. Surf. Sci., 252, 5984-5987, 2006.
• Güçbilmez, Y., “Synthesis and characterization of
• supported and non-supported iron-incorporated
• catalysts”, J. Fac. Eng. Arch. Gazi Univ., 24, 2,
• -377, 2009.
• Occelli, M.L., Bertrand, J.A., Gould, S.A.C.,
• Dominguez, J.M., “Physicochemical
• characterization of a Texas montmorillonite
• pillared with polyoxocations of aluminum Part I:
• the microporous structure”, Micropor. Mesopor.
• Mat., 34: 195-206, 2000.
• Gil, A., Gandia, L.M., “Microstructure and
• quantitative estimation of the micropore-size
• distribution of an alumina-pillared clay from
• nitrogen adsorption at 77 K and carbon dioxide
• adsorption at 273 K”, Chem. Eng. Sci., 58: 3059-
• , 2003.
• Lastoskie, C.M., Quirke, N., Gubbins, K.E.,
• “Studies in surface science and catalysis”,
• vol.104, Elsevier, 1997.
• Olivier, J.P., Occelli, M.L., “Surface area and
• microporosity of pillared rectorite catalysts from a
• hybrid density functional theory method”,
• Micropor. Mesopor. Mat., 57: 291-296, 2003.
• Ravikovitch, P.I., Neimark, A.V.,
• “Characterization of nanoporous materials from
• adsorption and desorption isotherms”, Colloid
• Surface A., 187-188: 11-21, 2001.
• Dombrowski, R.J., Lastoskie, C.M., Hyduke,
• D.R., “The Horvath-Kawazoe method revisited”,
• Colloid Surface A., 187-188: 23-39, 2001.
• Yang, R.T., Chen, J.P., Kikkinides, E.S., Cheng,
• L.S., “Pillared clays as superior catalysts for
• selective catalytic reduction of NO with NH3”,
• Ind. Eng. Chem. Res. 31: 1440-1445, 1992.
• Tomul, F., Balcı, S., “Synthesis and
• characterization of Al-pillared interlayered
• bentonites”, G.U. J. of Sci. 21(1): 21-31, 2008.
• Zhao, D., Yang, Y., Guo, X., “Synthesis and
• characterization of hydroxyl-CrAl pillared clays”,
• Zeolites, 15: 58-66, 1995.
• Rouquerol, F., Rouquerol, J., Sing, K.,
• “Adsorption by powders and porous solids”,
• Academic Press, London, 1999.
• Duong, D.D., “Adsorbtion Analysis: Equilibria
• and Kinetics”, Vol 2, Imperial College Press,
• -
• Olivier, J.P., Occelli, M.L., “Surface area and
• microporosity of pillared rectorite catalysts from a
• hybrid density functional theory method”,
• Micropor. Mesopor. Mat. 57: 291–296, 2003.
• Gil, A., Korili, S.A., Vicente, M.A., “Recent
• advances in the control and characterization of the
• porous structure of pillared clay catalysts”, Catal.
• Rew. 50: 153-221, 2008.
• Gil, A., Gandia, L.M., Vicente, M.A., “Synthesis
• and catalytic application of pillared clays”, Catal.
• Rev. Sci. Eng. 42, 145–212, 2000.