Sol-gel methods for the preparation of catalysts

8th April 2013 Daniel Casas Orozco

Preparation of Catalysts Environmental Catalysis Group Engineering Faculty Universidad de Antioquia

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

Sol-gel methodsfor the preparation of catalysts

OBJECTIVES
Show the fundamentals of the sol-gel methods Know the characteristics of the different preparation methods Review some applications of sol-gel processing

Sol-gel methodsfor the preparation of catalysts

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
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Solvent Water Methanol Ethanol 1-propanol n-butanol

Tc (K) 647 513 514 537 563

Pc (MPa) 22,1 8,1 6,1 5,2 4,4

Sol-gel methodsfor the preparation of catalysts

Ni/Al2O3, Ni/Al2O3-SiO2, Cu/Al2O3 Aerogels (supercritical drying) Pd/Al2O3, Ru/SiO2, Pt/SiO2 , Pd/SiO2, Pt/Al2O3

Xerogels (evaporative drying)

Sol-gel methodsfor the preparation of catalysts

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

Sol-gel methodsfor the preparation of catalysts

PREPARATION
Fundamentals of sol-gel process

Sol: colloidal suspension of solid particles in a liquid

Colloid: suspension with very small dispersed phase (1nm 1 m)

Sol-gel methodsfor the preparation of catalysts

In a colloid, gravitational forces are negligible

Short-range effects: Van der Waals and electrostatic forces

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 Gel: continuous solid and liquid phases of colloidal dimensions

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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:

2. De Jong, K. (2009). Synthesis of Solid Catalysts

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3. Simpson, R., Lee, R., Tillotson, T., Hrubesh, L., Swansinger, R., & Fox, G. (2003).
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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

Tetraethyl orthosilicate 2 5 4 Metal alcoxides experiment hydrolysis:

+ 2

Further aggregation can happen: + 2

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Partially or completely hydrolyzed molecules can condensate together: 1 + 1 1 1 + 2 1 + 1 1 1 +

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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
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4. Brinker, J. (1990). Sol-Gel Science: The physics and chemistry of sol gel processing
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 Gel formation mechanisms

Aggregation: formation of particles by polycondensation followed by their aggregation

Phase separation: separation of two immisible and interconected liquid phases: spinodal phase separation: oligomer-rich (solvent rich) and polymer rich (gel skeleton)
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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
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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
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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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2. De Jong, K. (2009). Synthesis of Solid Catalysts

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2. De Jong, K. (2009). Synthesis of Solid Catalysts

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Drying of wet gels

Evaporative drying (xerogels): shrinkage of structure. For a 1 nm structure, water filled gel, capillary forces rise up to 1.5 x 108 Pa. Reduces pore volume and surface area 2 =
Use a solvent with lower surface tension .

Applied with silica gels

Resorcinol formaldehdyde gels (acetone water)

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Drying of wet gels

Supercritical drying (aerogels): avoids structure-damaging capillary forces. Autoclave the material, nitrogen atmosphere, hermetically closing and heating slightly above Tc. Give rise to extremely porous materials. Due to costs, supercritical drying in CO2 has been developed Solvent exchange by liquid CO2 For aqueous resorcinol-formaldehyde Prior exchange of water with acetone

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Drying of wet gels

Freeze drying (cryogels): pore liquids is frozen that subsequently sublimes. Applied for both inorganic and organic gels

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Stabilization and post-treatment

Calcination of inorganic gels
Elimination of pore residuals (alcohol,ligands Convert organic precursors of the active metal into metal oxides Burn off alkoxysilane-functionalized complexes in cogelled materials T = 400 500 C, flowing air or O2. Care must be taken to avoid sintering

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Stabilization and post-treatment Pyrolysis of organic gels

Convert resorcinol-formaldehyde xerogels and aerogels into carbon xerogels or aerogels T = 800 1000 C, inert atmosphere (N2) Steps:
Water release Formation of carbon entities Rearrangement of entities into graphitic semigraphitic structures Metals can act as catalysts for those rearrangement reactions

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Stabilization and post-treatment Reduction

Used when the metallic state is required for the catalyst to be active H2 at T = 350 400 C For bimetallic composites, allows the alloy formation Not always through H2 atmosphere: in aerogel environment, alcohol reducing properties do the work

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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
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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)

Unified in sol-gel method

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One step method

Metal can be introduced during formation of the support Often, more dispersion than impregnationprepared materials Stronger anchoring of metal species in the porosity of the support Higher temperature stability Attractive approach to multi-metal material on single or mixed oxides supports
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One step method Dissolution of metal salts in precursory sol-gel solution

Dissolution of active metal precursor in homogeneous solution of support precursor. Metal precursor does not participate directly in sol-gel chemistry Examples: Pd/SiO2 xerogels, Pd/Al2O3 aerogels, Co/Al2O3 xerogels, Co-Mo/SiO2 xerogels
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 Cogelation of metal chelates with support precursors

Used since 1980s Nanometer-sized uniform metal particles in silica The active metal is anchored through a complex to the support Reactants:
Metal precursor: acetates as Pd(OAc)2, Cu(Oac)2, Ag(Oac) Alkoxysilane-functionalized metal complex:

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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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 Rojas-Cervantes et al. (2004)5

Support: polymerization of resorcinol with formaldehyde and calcination of xerogels by nitrogen at 1000 C. Metal precursor
Na and K carbonates, Mg nitrate Zr propoxide copolymerization

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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Condensation of benzaldehyde with ethyl cyanoacetate (Knoevanagel reaction)

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 Hajek et al. (2002)6

Active phase: Ru-Sn Support: SiO2
Tetraethoxysylane RuCl3.xH2O SnCl2

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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