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  • 1 Dipartimento di Scienze Chimiche, Università di Cagliari, Complesso Universitario Monserrato, s.s. 554, Bivio Sestu, 09042, Monserrato, CA, Italy
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Abstract

In this study, MgNiAl mixed oxides derived from layered double hydroxide precursors were prepared by pH-controlled co-precipitation. Three samples were prepared with a (Mg2+ + Ni2+)/Al3+ ratio of 2 and a Ni2+/Mg2+ with ratios of 0.22, 0.47, and 4.05. The structural, textural and redox features of the oxides were investigated by a variety of techniques, including X-ray diffraction, transmission electron microscopy, N2 physisorption, and temperature-programmed reduction. The acid and base properties were assessed by NH3 and CO2 adsorption microcalorimetry, respectively. The acid–base features were also investigated by testing the catalytic behaviors of the oxides for the conversion of 4-methylpentan-2-ol under both mild and stressed conditions. The reactant alcohol can undergo dehydration into 4-methylpent-1-ene, 4-methylpent-2-ene, and skeletal isomers of C6-alkenes, as well as dehydrogenation to 4-methylpentan-2-one and higher ketones, the product selectivity being governed by the concentration and strength of the acid and base sites. Comparison between the calorimetric and test reaction results is discussed.

  • 1. Cavani, F, Trifirò, F, Vaccari, A. Hydrotalcite-type anionic clays: preparation, properties and applications. Catal Today. 1991;11:173301. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 2. Van der Pol, A, Mojet, BL, Van der Ven, E, De Boer, E. Ordering of intercalated water and carbonate anions in hydrotalcite. An NMR study. J Phys Chem. 1994;98:40504054. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Queiroz, RM, Pires, LHO, de Souza, RCP, Zamian, JR, de Souza, AG, da Rocha Filho, GN, da Costa, CEF. Thermal characterization of hydrotalcite used in the transesterification of soybean oil. J Therm Anal Calorim. 2009;97:163166. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 4. Palmer, SJ, Spratt, HJ, Frost, RL. Thermal decomposition of hydrotalcites with variable cationic ratios. J Therm Anal Calorim. 2009;95:123129. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Vaccari, A. Clays and catalysis: a promising future. Appl Clay Sci. 1999;14:161198. .

  • 6. Valente, JS, Hernandez-Cortez, J, Cantu, MS, Ferrat, G, López-Salinas, E. Calcined layered double hydroxides Mg–Me–Al (Me: Cu, Fe, Ni, Zn) as bifunctional catalysts. Catal Today. 2010;150:340345. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. McKenzie, AL, Fishel, CT, Davis, RJ. Investigation of the surface structure and basic properties of calcined hydrotalcites. J Catal. 1992;138:547561. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Kuśtrowski, P, Chmielarz, L, Bożek, E, Sawalha, M, Roessner, F. Acidity and basicity of hydrotalcite derived mixed Mg–Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2. Mater Res Bull. 2004;39:263281. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Gravelle, PC. Heat-flow microcalorimetry and its application to heterogeneous catalysis. Adv Catal. 1972;2:191263. .

  • 10. Auroux A . Les techniques Physiques d’Étude des Catalyseurs. In: Imelik B, Védrine JC, editors. Les techniques physiques d’étude des catalyseurs. Ch. 24. Paris: Editions Technip; 1988. p. 823.

    • Search Google Scholar
    • Export Citation
  • 11. Cardona-Martinez, N, Dumesic, JA. Applications of adsorption microcalorimetry to the study of heterogeneous catalysis. Adv Catal. 1992;38:149244. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Andersen PJ , Kung HH. Catalysis, specialist periodical reports. In: Bond GC, Webb G, editors. Ch. 11. London: The Royal Society of Chemistry; 1994.

    • Search Google Scholar
    • Export Citation
  • 13. Solinas, V, Ferino, I. Microcalorimetric characterization of acid-basic catalysts. Catal Today. 1998;41:179189. .

  • 14. Winterbottom JM . Hydration and dehydration by heterogeneous catalysts. In: Kemball C, Dowden DA, editors. Catal R Soc Chem 1981;4:141–74.

    • Search Google Scholar
    • Export Citation
  • 15. Gervasini, A, Auroux, A. Acidity and basicity of metal oxide surfaces II. Determination by catalytic decomposition of isopropanol. J Catal. 1991;131:190198. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Berteau, P, Delmon, B, Dallons, JL, Van Gysel, A. Acid-base properties of silica-aluminas: use of 1-butanol dehydration as a test reaction. Appl Catal. 1991;70:307323. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Lauron-Pernot, H, Luck, F, Popa, JM. Methylbutynol: a new and simple diagnostic tool for acidic and basic sites of solids. Appl Catal. 1991;78:213225. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Auroux, A, Artizzu, P, Ferino, I, Solinas, V, Leofanti, G, Padovan, M, Messina, G, Mansani, R. Dehydration of 4-methylpentan-2-ol over zirconia catalysts. J Chem Soc Faraday Trans. 1995;91:32633267. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Auroux, A, Artizzu, P, Ferino, I, Monaci, R, Rombi, E, Solinas, V, Petrini, G. Dehydration of 4-methylpentan-2-ol over lanthanum and cerium oxides. J Chem Soc Faraday Trans. 1996;92:26192624. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Auroux, A, Artizzu, P, Ferino, I, Monaci, R, Rombi, E, Solinas, V. Conversion of 4-methylpentan-2-ol over alkali–metal ion-exchanged X and Y zeolites: a microcalorimetric and catalytic investigation. Micropor Mater. 1997;11:117126. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Cutrufello, MG, Ferino, I, Solinas, V, Primavera, A, Trovarelli, A, Auroux, A, Picciau, C. Acid-base properties and catalytic activity of nanophase ceria-zirconia catalysts for 4-methylpentan-2-ol dehydration. Phys Chem Chem Phys. 1999;1:33693375. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. Ferino, I, Casula, MF, Corrias, A, Cutrufello, MG, Monaci, R, Paschina, G. 4-Methylpentan-2-ol dehydration over zirconia catalysts prepared by sol-gel. Phys Chem Chem Phys. 2000;2:18471854. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Colón, G, Navío, JA, Monaci, R, Ferino, I. CeO2–La2O3 catalytic system. Part I. Preparation and characterisation of catalysts. Phys Chem Chem Phys. 2000;2:44534459. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Mulas, G, Monagheddu, M, Cocco, G, Cutrufello, MG, Ferino, I, Rombi, E. Conversion of 4-methylpentan-2-ol over powder catalysts prepared by ball milling. J Mater Synth Process. 2000;8:385391. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Cutrufello, MG, Ferino, I, Monaci, R, Rombi, E, Colón, G, Navío, JA. CeO2–La2O3 catalytic system. Part II. Acid–base properties and catalytic activity for 4-methylpentan-2-ol dehydration. Phys Chem Chem Phys. 2001;3:29282934. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Cutrufello, MG, Ferino, I, Monaci, R, Rombi, E, Solinas, V. Doped zirconia catalysts for the dehydration of 4-methylpentan-2-ol. Stud Surf Sci Catal. 2001;140:175184. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Solinas V , Rombi E, Ferino I, Cutrufello MG, Colón G, Navío JA. Preparation, characterisation and activity of CeO2–ZrO2 catalysts for alcohol dehydration. J Mol Catal A Chem. 2003; 204205:629–35.

    • Search Google Scholar
    • Export Citation
  • 28. Cutrufello, MG, Ferino, I, Rombi, E, Solinas, V, Colón, G, Navío, JA. Catalytic activity of Ceria-Lanthana system for 4-methylpentan-2-ol dehydration. React Kinet Catal Lett. 2003;79:9399. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 29. Cutrufello, MG, Ferino, I, Rombi, E, Solinas, V, Colón, G, Navío, JA. Acid-base properties of a Ceria-Lanthana catalytic system. J Therm Anal Calorim. 2003;72:223229. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30. Cutrufello, MG, Ferino, I, Monaci, R, Rombi, E, Solinas, S. Acid-base properties of zirconium, cerium and lanthanum oxides by calorimetric and catalytic investigation. Top Catal. 2002;19:225240. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 31. Casenave, S, Martinez, H, Guimon, C, Auroux, A, Hulea, V, Cordoneanu, A, Dumitriu, E. 2001 Acid-base properties of Mg–Ni–Al mixed oxides using LDH as precursors. Thermochim Acta. 379:8593. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 32. Casenave, S, Martinez, H, Guimon, C, Auroux, A, Hulea, V, Dumitriu, E. Acid and base properties of MgCuAl mixed oxides. J Therm Anal Calorim. 2003;72:191198. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 33. Xu, M, Gines, MJL, Hilmen, AM, Stephens, BL, Iglesia, E. Isobutanol and methanol synthesis on copper catalysts supported on modified magnesium oxide. J Catal. 1997;171:130147. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 34. Han, Y, Shen, J, Chen, Y. Microkinetic analysis of isopropanol dehydrogenation over Cu/SiO2 catalyst. Appl Catal A. 2001;205:7984. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 35. David O , Meloni D, Monaci R, Solinas V, Ungureanu A, Chirieac A, Dumitriu E. The catalytic dehydrogenation of trans-cinnamaldehyde over mixed oxides derived from quaternary hydrotalcite-like precursors. Iasi: Faculty of chemical Engineering ZFIC; 2008. pp. 21726.

    • Search Google Scholar
    • Export Citation
  • 36. Sing, KSW, Everett, DH, Haul, RAW, Moscow, L, Pierotti, RA, Rouquerol, J, Siemieniewska, T. Reporting physisorption data for gas/solid systems—with special reference to the determination of surface area and porosity. Pure Appl Chem. 1985;57:603619. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 37. Ruthven, DM. Principles of adsorption & adsorption processes. New York: Wiley; 1984.

  • 38. Reid RC , Pransuitz JM, Sherwood TK. The properties of gases and liquids. 3rd ed. vol 27. New York: Mc Graw-Hill; 1977. p. 40335.

  • 39. Sedlácek, J, Kraus, M. Quantum chemical calculations on the catalytic dehydration of 2-propanol. React Kinet Catal Lett. 1975;2:5763. .

  • 40. Nondek, L, Sedlácek, J. Mechanism of dehydrogenation of secondary alcohols on chromia. J Catal. 1975;40:3439. .

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation
1969
Volumes
per Year
4
Issues
per Year
24
Founder Akadémiai Kiadó
Founder's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher
Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)

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