Abstract
Porous nanocomposites made out of nickel dispersed on silica or alumina matrices were prepared as prospective catalysts for the nitroxidation of hydrocarbons in the form of aerogel or xerogel by adopting either a supercritical or a conventional gel drying procedure. The structural and textural features of the materials were investigated by X-ray diffraction, transmission electron microscopy and N2 physisorption and combined to the acid/base and reducibility data as deduced by adsorption microcalorimetry and temperature programmed reduction (TPR) profiles. The alumina-based samples are made out of nanocrystalline nickel aluminate and are mesoporous, although the aerogel has larger pore volumes and surface area than the xerogel. On the other hand, in the silica-based samples nickel oxide nanocrystals are dispersed on amorphous silica, the size of the nanocrystals being around 5 nm in the microporous xerogel and 14 nm in the mainly mesoporous aerogel. TPR data point out that the alumina-based samples have similar reducibility, whereas significant differences were observed in the silica-supported composites, the NiO–SiO2 aerogel exhibiting improved reducibility at low temperature. The NO-catalyst interaction was monitored by temperature programmed NO reaction coupled to mass spectrometry and preliminary tests on the use of the NiO–SiO2 xerogel and aerogel nanocomposites for the catalytic nitroxidation of 1-methyl-naphthalene to 1-naphthonitrile were obtained in a fixed-bed continuous-flow reactor. The data indicate that the aerogel exhibits larger selectivity than the corresponding xerogel, pointing out the importance of tuning the sol–gel parameters in the design of porous composite materials for catalytic applications.
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References
Ward DA, Ko EI (1995) Ind Eng Chem Res 34:421–433
Feng S Yang W (2011) Effect of the preparation method on the catalytic performance of Ca3Co4O5 for methane oxidation J Sol-Gel Sci Technol. doi:10.1007/s10971-010-2396-1
Sinha AK, Seelan S, Okumura M, Akita T, Tsubota S, Haruta M (2005) J Phys Chem B 109:3956–3965
Brinker CJ, Scherer GW (1990) Sol-gel science. Academic Press, San Diego, CA
Innocenzi P, Malfatti L, Kidchob T, Falcaro P (2009) Chem Mater 21:2555–2564
Framery E, Mutin PH (2002) J Sol-Gel Sci Technol 24:191–195
Husing N, Schubert U (1998) Angew Chem Int Ed 37:22–45
Pajonk GM (1991) Catal Today 72:217–266
Pajonk GM (1999) Catal Today 52:3–13
Schneider M, Baiker A (1995) Catal Rev-Sci Eng 37:515–556
Vallribera A, Molins E (2008) Aerogel supported nanoparticles in catalysis. In: Astruc D (ed) Nanoparticles and catalysis. Wiley, Weinheim, Germany
Falqui A, Loche D, Casula MF, Corrias A, Gozzi D, Latini A (2011) J Nanosci Nanotechnol 11:2215–2225
Ferino I, Casula MF, Corrias A, Cutrufello MG, Monaci R, Paschina G (2000) Phys Chem Chem Phys 2:1847–1854
Dusi M, Muller CA, Mallat T, Baiker A (1999) Chem Comm 2:197–198
Pajonk GM, Manzalji T (1993) Catal Lett 21:361–369
Pajonk GM (1997) Catal Today 35:319–337
Corrias A, Casula MF, Falqui A, Paschina G (2004) Chem Mater 16:3130–3138
Casula MF, Corrias A, Paschina G (2000) J Mater Res 15:2187–2194
PDF-2 File. ICDD—International Centre for Diffraction Data, 1601 Park Lane, Swarthmore, PA
Brunauer S, Emmet PH, Teller E (1938) J Am Chem Soc 60:309–319
Lippens BC, De Boer JH (1965) J Catal 4:319–323
Lecloux A, Pirard JP (1979) J Colloid Interface Sci 70:265–281
Dubinin MM (1955) Q Rev Chem Soc 9:101–114
Rouquerol F, Rouquerol J, Sing KSW (1999) Adsorption by powders and porous solids: principles, methodology and applications. Academic Press, London, UK
Barrett EP, Joyner LG, Halenda PP (1951) J Am Chem Soc 73:373–380
Fang K, Ren J, Sun Y (2005) J Mol Catal A Chem 229:51–58
Kirumakki SR, Shpeizer BG, Vidya Sagar G, Chary KVR, Clearfield A (2006) J Catal 242:319–331
He S, Jing Q, Yu W, Mo L, Lou H, Zheng X (2009) Catal Today 148:130–133
Wang Y, Wu R, Zhao Y (2010) Catal Today 158:470–474
Ran R, Xiong G, Yang W (2002) J Mater Chem 12:1854–1859
Gayán P, Dueso C, Abad A, Adanez J, de Diego LF, García-Labiano F (2009) Fuel 88:1016–1023
Roy B, Loganathan K, Pham HN, Datye AK, Leclerc CA (2010) Int J Hydrogen Energ 35:11700–11708
Salhi N, Boulahouache A, Petit C, Kiennemann A, Rabia C (2010) Steam reforming of methane to syngas over NiAl2O4 spinel catalysts. Int J Hydrogen Energ. doi:10.1016/j.ijhydene.2010.11.071
Acknowledgments
The Italian Institute of Technology (IIT) under the SEED project “NANOCAT” and Regione Autonoma della Sardegna through POR Sardegna FSE 2007–2013, L.R.7/2007 are gratefully acknowledged for financial support.
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Cutrufello, M.G., Rombi, E., Ferino, I. et al. Ni-based xero- and aerogels as catalysts for nitroxidation processes. J Sol-Gel Sci Technol 60, 324–332 (2011). https://doi.org/10.1007/s10971-011-2460-5
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DOI: https://doi.org/10.1007/s10971-011-2460-5