Abstract
Cesium salts of molybdophosphoric acid with varying amounts of the cations Cs1H2PMo12O40 and Cs3PMo12O40 have been prepared as pure or supported on SBA-15. The adsorption of ethanol and its temperature programmed desorption–TPD using thermogravimetry were studied for SBA-15 supported and unsupported Cs salts. The evolved gases during the adsorption–desorption of ethanol on CsHPM/SBA-15 composites were identified by online mass spectrometry coupled with thermogravimetry. The main products observed in the evolved gases during the desorption of ethanol were C2H4, C3H6 and unreacted ethanol. The amount of acidic sites of the composites was estimated by ammonia adsorption–desorption. The dehydration of ethanol was used to test the catalytic properties of the CsHPM samples incorporated on the silica matrix. SBA15—supported catalysts, appeared to be more active than bulk catalysts in vapor phase dehydration and dehydrogenation of ethanol reactions. The effect of the support leads to higher values of dehydration rates of ethanol as well as higher values of ethylene and acetaldehyde formation rates.
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References
Pope MT (1983) Heteropoly and isopoly oxometalates. Springer, Berlin
Mizuno N, Misono M (1998) Heterogeneous catalysis. Chem Rev 98:199–217
Okuhara T, Mizuno N, Misono M (2001) Catalysis by heteropoly compounds—recent developments. Appl Catal A 222:63–77
Moffat JB (2001) Metal-oxygen clusters: the surface and catalytic properties of heteropoly oxometalates. Springer, New York
Lu X, Yin H, Shen L, Feng Y, Wang A, Shen Y, Hang H, Mao D (2014) Reaction kinetics of the esterification reaction between ethanol and acetic acid catalyzed by Keggin heteropolyacids. React Kinet Mech Catal 111:15–27
Kim H, Jung JC, Kim P, Yeom SH, Lee K-Y, Song IK (2006) Preparation of H3PMo12O40 catalyst immobilized on surface modified mesostructured cellular foam (SM-MCF) silica and its application to the ethanol conversion reaction. J Mol Catal A 259:150–155
Sheng X, Zhou Y, Zhang Y, Xue M, Duan Y (2012) Immobilization of 12-tungstophosphoric acid on LaSBA-15 and its catalytic activity for alkylation of o-xylene with styrene. Chem Eng J 179:295–301
Ahmed Awad I, Samra SE, El-Hakam SA, Khder AS, El-Shenawy HZ, Abo El-Yazeed WS (2013) Characterization of 12-molybdophosphoric acid supported on mesoporous silica MCM-41 and its catalytic performance in the synthesis of hydroquinone diacetate. Appl Surf Sci 282:217–225
Popa A, Sasca V, Halasz J (2009) Catalytic properties of molecular sieves MCM-41 type doped with heteropolyacids for ethanol oxidation. Appl Surf Sci 255(5 PART I):1830–1835
Shen L, Feng Y, Yin H, Wang A, Yu L, Jiang T, Shen Y, Wu Z (2011) Gas phase dehydration of glycerol catalyzed by rutile TiO2-supported heteropolyacids. J Ind Eng Chem 17:484–492
Pruethiarenun K, Isobe T, Matsushita S, Ye J, Nakajima A (2014) Comparative study of photoinduced wettability conversion between [PW12O40]3−/brookite and [SiW12O40]4−/brookite hybrid films. Mater Chem Phys 144:327–334
Ferreira P, Fonseca IM, Ramos AM, Vital J, Castanheiro JE (2011) Acetylation of glycerol over heteropolyacids supported on activated carbon. Catal Commun 12:573–576
Patel A, Singh S (2014) A green and sustainable approach for esterification of glycerol using 12-tungstophosphoric acid anchored to different supports: kinetics and effect of support. Fuel 118:358–364
Liu Z, Cao S, Wang S, Zeng W, Zhang T (2014) Silica-supported phosphotungstic acid as a novel heterogeneous catalyst for b-pinene polymerization. React Kinet Mech Catal 111:577–590
Popa A, Pleşu N, Sasca V, Kiš EE, Marinković-Nedučin R (2006) Physicochemical features of polyaniline supported heteropolyacids. J Optoelectron Adv Mater 8(5):1944–1950
Jing F, Katryniok B, Dumeignil F, Bordes-Richard E, Paul S (2014) Catalytic selective oxidation of isobutane to methacrylic acid on supported (NH4)3HPMo11VO40 catalysts. J Catal 309:121–135
Soled S, Miseo S, McVicker G, Gates WE, Gutierrez A, Paes J (1997) Preparation of bulk and supported heteropolyacid salts. Catal Today 36:441–480
Okuhara T, Watanabe H, Nishimura T, Inumaru K, Misono M (2000) Microstructure of cesium hydrogen salts of 12-tungstophosphoric acid relevant to novel acid catalysis. Chem Mater 12:2230–2238
Srivani A, Parameswaram G, Prasad PS, Lingaiah N (2014) Metal exchanged heteropolytungstate: an efficient catalyst for the synthesis of formylated amines. React Kinet Mech Catal 112:425–436
Sheng X, Kong J, Zhou Y, Zhang Y, Zhang Z, Zhou S (2014) Direct synthesis, characterization and catalytic application of SBA-15 mesoporous silica with heteropolyacid incorporated into their framework. Microporous Mesoporous Mater 187:7–13
Bokade VV, Yadav GD (2011) Heteropolyacid supported on montmorillonite catalyst for dehydration of dilute bio-ethanol. Appl Clay Sci 53:263–271
Misono M (2001) Unique acid catalysis of heteropoly compounds (heteropolyoxometalates) in the solid state. Chem Commun 13:1141–1152
Haber J, Matachowski L, Mucha D, Stoch J, Sarv P (2005) New evidence on the structure of potassium salts of 12-tungstophosphoric acid, KxH3-xPW12O40. Inorg Chem 44:6695–6703
Holclajtner-Antunovic I, Mioc UB, Todorovic M, Jovanovic Z, Davidovic M, Bajuk-Bogdanovic D, Lausevic Z (2010) Characterization of potassium salts of 12-tungstophosphoric acid. Mater Res Bull 45:1679–1684
Narasimharao K, Brown DR, Lee AF, Newman AD, Siril PF, Tavener SJ, Wilson K (2007) Structure–activity relations in Cs-doped heteropolyacid catalysts for biodiesel production. J Catal 248:226–234
Sasca VZ, Verdes O, Avram L, Popa A, Erdohelyi A, Oszko A (2013) The CsxH3-XPW12O40 catalysts microstructure model. Appl Catal A 451:50–57
Pozniczek J, Bielanski A (1996) Ethanol conversion and coke formation on TiO2 supported molybdovanadophosphoric acids. React Kinet Catal Lett 58(2):299–306
Varisli D, Dogu T, Dogu G (2010) Petrochemicals from ethanol over a W-Si-based nanocomposite bidisperse solid acid catalyst. Chem Eng Sci 65:153–159
Popa A, Sasca V, Verdes O, Barvinschi P, Holclajtner-Antunović I (2014) Acidic and neutral cesium salts of 12-molybdophosphoric acid supported on SBA-15 mesoporous silica. The influence of Cs concentration and surface coverage on textural and structural properties. Mater Res Bull 50:312–322
Popa A, Sasca V, Holclajtner-Antunovic I (2012) The influence of surface coverage on textural, structural and catalytic properties of cesium salts of 12-molybdophosphoric acid supported on SBA-15 mesoporous silica. Micropor. Mesopor. Mat. 156:127–137
Zhao D, Feng J, Huo Q, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279:548–552
Zhao D, Sun J, Li Q, Stucky GD (2000) Morphological control of highly ordered mesoporous silica SBA-15. Chem Mater 12:275–279
Verdeş O, Avram L, Popa A, Sasca V (2012) The adsorption/desorption of ethanol on Cs xH3-xPW12O40 by TG/DTG-DTA analysis. J Optoelectron Adv Mater 14(5–6):537–543
Sasca V, Avram L, Verdes O, Popa A (2010) The n-butyl amine TPD measurement of Brønsted acidity for solid catalysts by simultaneous TG/DTG-DTA. Appl Surf Sci 256(17):5533–5538
Sasca V, Stefanescu M, Popa A (1999) Studies on the non-isothermal decomposition of H3PMo12O40·xH2O and H4PVMo11O40·yH2O. J Therm Anal Cal 56:569–578
Popa A, Sasca V, Stefanescu M, Kis EE, Marinkovic-Neducin R (2006) The influence of the nature and textural properties of different supports on the thermal behavior of Keggin type heteropolyacids. J Serb Chem Soc 71(3):235–249
Han Y, Lu C, Xu D, Zhang Y, Hu Y, Huang H (2011) Molybdenum oxide modified HZSM-5 catalyst: surface acidity and catalytic performance for the dehydration of aqueous ethanol. Appl Catal A 396:8–13
Turek W, Lapkowski M, Debiec J, Krowiak A (2005) Studies of the activity of catalysts based on heteropolyacids. Appl Surf Sci 252:847–852
Acknowledgments
These investigations were partially financed by Romanian Academy Project no. 3.3. and by the Ministry of Education and Science of Republic of Serbia, Grants 172043.
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Popa, A., Sasca, V., Verdes, O. et al. Adsorption–desorption and catalytic properties of SBA-15 supported cesium salts of 12-molybdophosphoric acid for the dehydration of ethanol. Reac Kinet Mech Cat 115, 355–375 (2015). https://doi.org/10.1007/s11144-015-0832-5
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DOI: https://doi.org/10.1007/s11144-015-0832-5