Process for preparing cellular inorganic monolithic materials and uses of these materials

Patent metadata

Field	Value
Publication number	US-10125021-B2
Application number	US-201113816771-A
Country	US
Kind code	B2
Filing date	Oct 10, 2011
Priority date	Oct 11, 2010
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

A process is provided for preparing an inorganic material in the form of an alveolar monolith of a silica matrix where the monolith includes interconnected macropores. The process includes at least one step of mineralizing an oil-in-water emulsion formed from droplets of an oily phase dispersed in a continuous aqueous phase and in which colloidal solid particles are present at the interface formed between the continuous aqueous phase and the dispersed droplets of oily phase. Such materials obtained according to this process may be used, especially for separative chemistry and filtration, for performing chemical reactions catalyzed in heterogeneous phase, as thermal or phonic insulators, or as templates for manufacturing controlled-porosity carbon skeletons.

First claim

The invention claimed is:

1. Process for preparing an inorganic material in the form of an alveolar monolith of a silica matrix having interconnected and monodispersed macropores, said process being capable of producing monodispersed macropores with a mean dimension d A ranging from 1 μm to 400 μm and micropores with a mean dimension d I of from 0.7 to 2 nm, said process comprising:
at least one step of mineralization of an oil-in-water emulsion formed from droplets of an oily phase dispersed in a continuous aqueous phase and in which colloidal solid particles are present at an interface formed between the continuous aqueous phase and the dispersed droplets of said oily phase,
wherein a volume fraction of the oily phase is greater than 50%,
wherein the said mineralization step is performed without stirring and at a pH less than or equal to 3, in the presence of at least one hydrolized silicon oxide precursor in an amount greater than or equal to 3% by mass relative to the mass of the continuous aqueous phase, and
wherein said colloidal solid particles are silicon oxide nanoparticles, said colloidal solid particles being functionalized at their surface to make them hydrophobic,
wherein said colloidal solid particles are adsorbed at said interface and said colloidal solid particles stabilize said oil-in-water emulsion,
wherein a mass of the colloidal solid particles in the oil-in-water emulsion ranges from 0.05 mg of particles/mL of the oily phase to 16 g of particles/mL of the oily phase, and
wherein when a surfactant is present in addition to said colloidal solid particles, the amount of said surfactant being of a mass ratio of a mass of said surfactant/mass of said colloidal solid particles ranges from 1 mg of said surfactant per gram of said colloidal solid particles to 0.8 g of said surfactant per gram of said colloidal solid particles.

2. Process according to claim 1 , wherein the oily phase of the oil-in-water emulsion includes one or more compounds chosen from either one of linear or branched alkanes, containing from 7 to 22 carbon atoms.

3. Process according to claim 2 , wherein said either one of linear or branched alkanes are chosen from either one of dodecane and hexadecane.

4. Process according to claim 1 , wherein the volume fraction of the oily phase of the oil-in-water emulsion ranges from 60% to 90%.

5. Process according to claim 1 , wherein in said oil-in water emulsion, the amount of the colloidal solid particles ranges from 0.05 mg of particles/mL of the oily phase to 8 mg of particles/mL of the oily phase.

6. Process according to claim 1 , wherein the colloidal solid particles are functionalized with compounds attached to their surface via covalent bonds, the said compounds comprising hydrophobic groups.

7. Process according to claim 1 , wherein said at least one silicon oxide precursors are selected from the group consisting of tetramethoxy-ortho-silane, tetraethoxy-ortho-silane, dimethyldiethoxysilane and mixtures of dimethyldiethoxysilane with tetraethoxy-ortho-silane and tetramethoxy-ortho-silane.

8. Process according to claim 1 , wherein a concentration of said at least one hydrolized silicon precursor in said continuous aqueous phase of said oil-in water emulsion ranges from 25% to 35% by mass relative to a mass of the continuous aqueous phase.

9. Process according to claim 1 , wherein the continuous aqueous phase of said oil-in water emulsion also comprises one or more precursors of a metal oxide of formula MeO 2 in which Me is a metal is selected from the group consisting of Zr, Ti, Th, Nb, Ta, V, W, and Al in an amount ranging from 1% to 30% by mass relative to a mass of said at least one hydrolized silicon precursors.

10. Process according to claim 9 , wherein said one or more metal oxide precursors are chosen from alkoxides, chlorides, and nitrates of metals selected from the group consisting of Zr, Ti, Th, Nb, Ta, V, W, and Al.

11. Process according to claim 1 , wherein the mineralization step is performed at a pH of less than or equal to 1.

12. Process according to claim 1 , wherein said process also comprises a step of impregnating said alveolar monolith using a solution containing a functionalizing agent.

13. A process according to claim 1 , said process further comprising a step of employing an inorganic material obtained according to claim 1 for separative chemistry and filtration, for performing chemical reactions catalysed in heterogeneous phase, as material for thermal or phonic insulation, or as templates for manufacturing controlled-porosity carbon skeletons.

14. Process according to claim 13 , further comprising the step of employing said inorganic material as high-frequency-selective acoustic insulator.

15. Process according to claim 13 , further comprising a step of employing said inorganic material for the preparation of chromatography columns with a macropore size gradient, wherein a chromatography column includes several macroporous alveolar monoliths stacked on each other, said macroporous alveolar monoliths comprising different macropore sizes resulting from the mineralization of oil-in-water emulsions comprising droplets of different sizes and mineralized to create a chromatography column with a macropore size gradient.

16. Process according to claim 1 , wherein the dispersed droplets of oily phase in the oil-in-water emulsion have a mean diameter ranging between 1 μm and 1 mm.

17. Process for preparing an inorganic material in the form of an alveolar monolith of a silica matrix having interconnected and monodispersed macropores, said process being capable of producing monodispersed macropores with a mean dimension d A ranging from 1 μm to 400 μm and micropores with a mean dimension d I of from 0.7 to 2 nm, said process comprising:
at least one step of mineralization of an oil-in-water emulsion formed from droplets of an oily phase dispersed in a continuous aqueous phase and in which colloidal solid particles are present at an interface formed between the continuous aqueous phase and the dispersed droplets of said oily phase,
wherein a volume fraction of the oily phase is greater than 50%, and

wherein the said mineralization step is performed at a pH less than or equal to 3, in the presence of at least one silicon oxide precursor in an amount greater than or equal to 3% by mass relative to the mass of the continuous aqueous phase, and
wherein said colloidal solid particles are silicon oxide nanoparticles, said colloidal solid particles being functionalized at their surface to make them hydrophobic,
wherein said colloidal solid particles are adsorbed at said interface and said colloidal solid particles stabilize said oil-in-water emulsion,
wherein a mass of the colloidal solid particles in the oil-in-water emulsion ranges from 0.05 mg of particles/mL of the oily phase to 16 g of particles/mL of the oily phase, and
wherein the oil-in-water emulsion is prepared in a single step by mixing:
i) said continuous aqueous phase containing at least one silicon oxide precursor in an amount of greater than or equal to 3% by mass relative to the mass of the aqueous phase, at least one acid in a sufficient amount to bring the continuous aqueous phase to a pH of less than or equal to 3, and the colloidal solid particles in an amount of greater than or equal to 3% by mass relative to the mass of the aqueous phase, and mechanically stirring it with
ii) said oily phase in an amount such that the volume fraction of the oily phase in the resulting oil-in-water emulsion is greater than 50%; the said oil-in-water emulsion then being l

Assignees

• Schmitt Veronique
• Backov Renal
• Destribat Mathieu
• Centre Nat Rech Scient

Inventors

• Schmitt Veronique
• Backov Renal
• Destribat Mathieu

Classifications

• C04B2235/3258

  Tungsten oxides, tungstates, or oxide-forming salts thereof · CPC title

• C04B2235/483

  Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes · CPC title

• C04B2235/444

  Halide containing anions, e.g. bromide, iodate, chlorite · CPC title

• C04B2235/3239

  Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate · CPC title

• C04B35/14

  based on silica · CPC title