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Sol-Gel Methods For The Preparation of Catalysts
Sol-Gel Methods For The Preparation of Catalysts
Sol-Gel Methods For The Preparation of Catalysts
Outline
1. Objectives 2. Introduction 3. Preparation
3.1 Fundamentals of Sol-gel process 3.2 Drying of wet gels 3.3 Stabilization and post-treatment
4. Applications
4.1 Bulk catalytic materials 4.2 Multimetallic composite catalytic materials
OBJECTIVES
Show the fundamentals of the sol-gel methods Know the characteristics of the different preparation methods Review some applications of sol-gel processing
INTRODUCTION1*
1970s Synthesizing of metal-containing gels: disolving an adequate precursor of the metal in an alcoholic solution containing precursors of the support Supercritical removal of solvent to mantain porosity of the wet gel (collapse of of the structure)
1. * Regalbuto, J. (2007). Catalyst Preparation: Science and Engineering Reference along all the presentation. Other sources are cited as well in the upcoming slides
Sol-gel methodsfor the preparation of catalysts 4
Ni/Al2O3, Ni/Al2O3-SiO2, Cu/Al2O3 Aerogels (supercritical drying) Pd/Al2O3, Ru/SiO2, Pt/SiO2 , Pd/SiO2, Pt/Al2O3
1980s and 1990s Functionalized ligands anchored to silica (nanometer-size distributed metal phase)
Aerogel-like morphology
Mono/bimetallic catalysts (cogelled catalysts)
High activities and selectivities Excellent mass transfer Reasonable stability Easy regenerability
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2000s
Metal-containing carbon xerogels and aerogels Drying and pyrolisis oforganic gels obtained from the polycondensation of resorcinol and formaldehyde in aqueous media
PREPARATION
Fundamentals of sol-gel process
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Sol-gel process: a gel is formed from the particles of a sol. Attractive forces cause Particle sticking Network forming
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General sequence2:
3. Simpson, R., Lee, R., Tillotson, T., Hrubesh, L., Swansinger, R., & Fox, G. (2003).
Sol-gel methodsfor the preparation of catalysts
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Inorganic Gels
All metaloides can be synthesized by sol-gel methods: Al2O3, SiO2, TiO2, ZrO2 Most popular materials: metal alkoxides
M: Si Zr, Al, Ti x: Al (3), Ti, Si (4)
R: -CH3, -C2H5
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Example: TEOS
+ 2
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The reaction proceeds linking increasing number of molecules Inorganic polymer lattice4
4. Brinker, J. (1990). Sol-Gel Science: The physics and chemistry of sol gel processing
Sol-gel methodsfor the preparation of catalysts 18
4. Brinker, J. (1990). Sol-Gel Science: The physics and chemistry of sol gel processing
Sol-gel methodsfor the preparation of catalysts 19
Phase separation: separation of two immisible and interconected liquid phases: spinodal phase separation: oligomer-rich (solvent rich) and polymer rich (gel skeleton)
Sol-gel methodsfor the preparation of catalysts
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For silicon alkoxides, reactions (nucleophylic atack on silicon atom) occur more readily when in acidic media (HCl, CH3COOH, HF) or basic media (NH3, KOH, amines) Different structures depending on reaction conditions Better than precipitation method for mixed oxides preparation: Al2O3-SiO2, SiO2-ZrO2, SiO2-TiO2 Higher composite acidity than individual metal oxides
Sol-gel methodsfor the preparation of catalysts 21
Organic gels: Less used than inorganic ones Useful to synthesize three dimensional carbon structures in a solvent. Precursors of carbon gels by pyrolysis. Used materials
Hydroxylated benzene compounds: cathecol, resorcinol, phenol Aldehydes: formaldehyde, furfural
Sol-gel methodsfor the preparation of catalysts
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Resorcinolformaldehyde polymers are the most known of their kind: water as a solvent and basic media provided by Na2CO3.
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Depending on pH interval, micromacroporous, micro-mesoporous, only microporous or totally non-porous materials can be obtained
Same gel formation mechanisms: in this case, spinodal separation is more acepted.
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APPLICATIONS
Bulk catalytic phase materials2
Sol-gel method used to prepare metal-oxide phases with controlled size, shape, packing mode, etc. Careful choice of molecular precursor and sol-gel chemical route: activation/condensation kinetics, drying and crystallization conditions Production of TiO2, ZrO2, Nb2O5, CrOx with surface area > 200 m/g
2. De Jong, K. (2009). Synthesis of Solid Catalysts
Sol-gel methodsfor the preparation of catalysts
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Multimetallic composite catalytic materials Traditional supported metal catalysts preparation: Support preparation Distribution of active phase precursor over support Drying, calcination or pyrolysis (activation)
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Two steps method Sometimes used for enhance materials respect to their characteristics in one-step preparation methods In some cases, active phase remains entrapped or occluded in the bulk support
Pd-Ag/SiO2 aerogel Ru/SiO2 xerogels Ni/C aerogels
Steps
Preparation of the xerogel or aerogel suppport Supporting of active metal Methods like impregnation or ion exchange are used for metal supporting
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Method:
(Resorcinol metal precursor aqueous solution) + aqueous formaldehyde. 1 h geling, 85 C for seven days in oven (Resorcinol formaldehyde aqueous solution) + Zn propoxide. 30 min geling, 85 C for seven days in oven Resulting gels dried at 110 C for 10 h in N2. Xerogels obtained Carbonised derivatives by pyrolysis of xerogels at 1000 C in N2.
5. Rojas-Cervantes et al. (2004). Basic metalcarbons catalysts prepared by solgel method
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Method
Ru and Sn precursors in 1,2 ethanodiol Si precursor added dropwise Water addition Geling at 343 K Aged gels dried at decreasing pressure Reduction with NaBH4 solution Drying for 2h at 473K (N2 atmosphere)
Hajek et al. (2002). Preparation and properties influence of bimetallic Ru-Sn sol-gel catalysts: influence of catalyst reduction
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Hydrogenation of 3-pheynyl-2-propenal
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REFERENCES
1. 2. 3. 4.
5. 6.
Regalbuto, J. (2007). Catalyst Preparation: Science and Engineering (p. 474). Boca Ratn, FL: CRC Press. De Jong, K. (2009). Synthesis of Solid Catalysts (p. 401). Weinheim: Wiley-VCH. Simpson, R., Lee, R., Tillotson, T., Hrubesh, L., Swansinger, R., & Fox, G. (2003). Sol-gel manufactured energetic materials. Brinker, J. (1990). Sol-Gel Science: The physics and chemistry of sol gel processing (p. 908). San Diego, CA: Academic Press.
Rojas-Cervantes, M. ., Alonso, L., Daz-Tern, J., Lpez-Peinado, a. ., MartnAranda, R. ., & Gmez-Serrano, V. (2004). Basic metalcarbons catalysts prepared by solgel method. Carbon, 42(8-9), 15751582. Hajek, J., Kumar, N., Karhu, H., Cerveny, L., Vayrynen, J., Salmi, T. I., & Yu, D. (2002). Preparation and properties influence of bimetallic Ru-Sn sol-gel catalysts: influence of catalyst reduction. Studies in Surface Science and Catalyisis, 143, 757765.
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