Nanoporous detectors of monocyclic aromatic compounds and other pollutants

• US 9,562,882 B2
• Filed: 05/06/2014
• Issued: 02/07/2017
• Est. Priority Date: 07/11/2008
• Status: Active Grant

• Current Assignee: Centre National De La Recherche Scientifique, Commissariat A L'Energie Atomique et AUX Energies Alternatives
• Original Assignee: Centre National De La Recherche Scientifique, Commissariat A L'Energie Atomique et AUX Energies Alternatives
• Inventors: Crunaire, Sabine, Tran-Thi, Thu-Hoa
• Primary Examiner(s): Soderquist, Arlen
• Application Number:
  US14/270,459
• Publication Number:
  US 20140242713A1
• Time in Patent Office: 1,008 Days
• Field of Search: 436127-130, 436139-142, 436/164, 436/167, 436/172, 436177-178
• US Class Current: 1/1
• CPC Class Codes: B01J 20/10 comprising silica or silicate
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/28047 Gels
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: C03B 19/12 by liquid-phase reaction processes
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: G01N 33/0004 Gaseous mixtures, e.g. polluted air gaseous biological material G01N33/497; exhaust gas of internal combustion engines G01M15/102
• CPC Class Codes: Y02P 40/57 Improving the yield, e-g- reduction of reject rates
• CPC Class Codes: Y10T 436/20 Oxygen containing
• CPC Class Codes: Y10T 436/200833 Carbonyl, ether, aldehyde or ketone containing
• CPC Class Codes: Y10T 436/201666 Carboxylic acid
• CPC Class Codes: Y10T 436/202499 Formaldehyde or acetone
• CPC Class Codes: Y10T 436/21 Hydrocarbon
• CPC Class Codes: Y10T 436/212 Aromatic
• CPC Class Codes: Y10T 436/214 Acyclic [e.g., methane, octane, isoparaffin, etc.]
• CPC Class Codes: Y10T 436/216 Unsaturated [e.g., ethylene, diene, etc.]
• CPC Class Codes: Y10T 436/25375 Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
• CPC Class Codes: Y10T 436/255 including use of a solid sorbent, semipermeable membrane, or liquid extraction

Abstract

Porous sol-gel material essentially consisting of units of one or more first polyalkoxysilanes chosen from the following compounds: (chloromethyl)triethoxysilane; 1,3-dimethyltetramethoxydisiloxane; ethyltrimethoxysilane; triethoxy(ethyl)silane; triethoxymethylsilane; triethoxy(vinyl)silane; trimethoxymethylsilane; trimethoxy(vinyl)silane; tetraethoxysilane or tetramethoxysilane (TMOS) and of units of one or more second polyalkoxysilanes chosen from the following compounds: (N-(3-(trimethoxysilyl)propyl)ethylenediamine; 3-aminopropyltriethoxysilane (APTES) and 3-aminopropyltrimethoxysilane, in a first polyalkoxysilane/second polyalkoxysilane molar ratio of 1/0.01 to 1/1, optionally comprising a probe molecule, method of preparation and applications in the trapping of monocyclic aromatic hydrocarbons and other pollutants or in their detection.

Claims

1. A porous sol-gel material consisting essentially of:

units of one or more first polyalkoxysilane(s) selected from the following compounds;

(chloromethyl)triethoxysilane;

1,3-dimethyltetramethoxydisiloxane;

ethyltrimethoxysilane;

triethoxy(ethyl)silane;

triethoxymethylsilane;

triethoxy(vinyl)silane;

trimethoxymethylsilane;

trimethoxy(vinyl)silane;

tetraethoxysilane and tetramethoxysilane (TMOS); and

units of one or more second polyalkoxysilane(s) selected from the following compounds;

(N-(3-(trimethoxysilyl)propyl)ethylenediamine;

3-aminopropyltriethoxysilane (APTES) and 3-aminopropyltrimethoxysilane, in a first polyalkoxysilane(s)/second polyalkoxysilane(s) mole ratio of 1/0.01 to 1/1;

wherein the porous sol-gel matrix is solid, self-standing and transparent to UV radiation; and

an optional probe molecule; and

wherein the pores of said porous sol-gel material have a pH of from 7 to 8.2; and

wherein the sol-gel material is prepared according to a process comprising;

mixing the first polyalkoxysilane(s), at a temperature of −

45 to +15°

C., with a water-miscible organic solvent therefor, then

adding a second polyalkoxysilane(s),

adding water; and

continuing stirring to obtain a sol and then the defined sol-gel; and

drying said sol-gel at a controlled temperature and under an atmosphere of dry inert gas so as to evaporate off residual solvents.

2. A sol-gel material as claimed in claim 1, wherein the first polyalkoxysilane(s)/second polyalkoxysilane(s) mole ratio is from 1/0.01 to 1/0.30.

3. A sol-gel material as claimed in claim 1, wherein the first polyalkoxysilane(s) are chosen from the following compounds:

methyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane and tetramethoxysilane (TMOS).

4. A sol-gel material as claimed in claim 1, wherein:

the first polyalkoxysilane is limited to a single material from the defined list, or

the first polyalkoxysilane is limited to a single material from the defined list and the second polyalkoxysilane is limited to a single material from the defined list.

5. A sol-gel material as claimed in claim 1, wherein the second polyalkoxysilane is 3-aminopropyltriethoxysilane.

6. A sol-gel material as claimed in claim 1, which includes a probe molecule.

7. A sol-gel material as claimed in claim 6, wherein the probe molecule is chosen from hydralazine, 4-amino-3-penten-2-one, 2,4-dinitrophenylhydrazine, iodine oxides, triphenylmethane derivatives, azobenzene derivatives and alkyl halides.

8. A process for preparing a sol-gel material as defined in claim 1, wherein the first polyalkoxysilane(s) are mixed, at a temperature of −

45 to +15°

C., with a water-miscible organic solvent therefor, the second polyalkoxysilane is then added, water is added, supplemented, if desired, with a catalyst or a structuring agent, or both, and stirring is continued to obtain the sol and then the expected sol-gel, which, if desired, is placed in sol form in molds to obtain expected sol-gel blocks.

9. A process as claimed in claim 8, wherein the mixing of the first polyalkoxysilane(s) with a water-miscible organic solvent therefor is performed for a time of between 1 and 10 minutes.

10. A process as claimed in claim 8, wherein the olyalkoxysilanes/solvent/water mole ratio is from 1/4/1 to 1/100/30.

11. A process for preparing a sol-gel material incorporating a probe molecule as defined in claim 8, wherein a probe molecule is added either directly during the preparation of the sol of the sol-gel material, or by diffusion of this probe molecule into the material via gas-phase or liquid-phase diffusion.

12. A process for trapping monocyclic aromatic hydrocarbons using, as sensor, a sol-gel material as defined in claim 1, in which a stream that may contain monocyclic aromatic hydrocarbons is placed in contact with the sol-gel material, or such a stream is made to circulate thereon.

13. A process as claimed in claim 12, wherein the detection of the monocyclic aromatic hydrocarbons trapped on the sol-gel materials is also performed.

14. A process for trapping pollutants chosen from aldehydes, aromatic compounds, alkanes, carboxylic acids, ketones and chlorine using as sensor a sol-gel material as defined in claim 1, incorporating a probe molecule, in which a stream that may contain a pollutant from among those mentioned above is placed in contact with said sol-gel material incorporating a probe molecule, or such a stream is made to circulate thereon.

15. A system for trapping or detecting monocyclic aromatic hydrocarbons or a pollutant using as sensor a sol-gel material as defined in claim 1.

16. A sol-gel material according to claim 1 wherein, in the water addition step, the water is supplemented with a catalyst, a structuring agent, or both.

17. A porous sol-gel material consisting essentially of:

units of one or more first polyalkoxysilane(s) selected from the following compounds;

(chloromethyl)triethoxysilane;

1,3-dimethyltetramethoxydisiloxane;

ethyltrimethoxysilane;

triethoxy(ethyl)silane;

triethoxymethylsilane;

triethoxy(vinyl)silane;

trimethoxymethylsilane;

trimethoxy(vinyl)silane;

tetraethoxysilane or tetramethoxysilane (TMOS);

units of one or more second polyalkoxysilane(s) selected from the following compounds;

(N-(3-(trimethoxysilyl)propyl)ethylenediamine;

3-aminopropyltriethoxysilane (APTES) and 3-aminopropyltrimethoxysilane, in a first polyalkoxysilane(s)/second polyalkoxysilane(s) mole ratio of 1/0.01 to 1/1;

wherein the porous sol-gel matrix is solid, self-standing and transparent to UV radiation; and

an optional probe molecule; and

wherein the pores of said sol-gel material have a pH of from 7 to 8.2; and

wherein said porous sol-gel material is prepared according to the process comprising;

mixing the first polyalkoxysilane(s), at a temperature of −

45 to +15°

C., with a water-miscible organic solvent therefor, then

adding a second polyalkoxysilane(s),

adding water,

continuing stirring to obtain a sol,

placing the sol in a mold,

obtaining a solid, self-standing and transparent to UV radiation block of the defined sol-gel; and

drying said sol-gel at a controlled temperature and under an atmosphere of dry inert gas so as to evaporate off residual solvents.

18. A sol-gel material according to claim 17 wherein, in the water addition step, the water is supplemented with a catalyst, a structuring agent, or both.

19. A sol-gel material as claimed in claim 17, wherein the first polyalkoxysilane(s)/second polyalkoxysilane(s) mole ratio is from 1/0.01 to 1/0.30.

20. A sol-gel material as claimed in claim 17, wherein the first polyalkoxysilane(s) are chosen from the following compounds:

methyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane and tetramethoxysilane (TMOS).

21. A sol-gel material as claimed in claim 17, wherein:

the first polyalkoxysilane is limited to a single material from the defined list, or

the first polyalkoxysilane is limited to a single material from the defined list and the second polyalkoxysilane is limited to a single material from the defined list.

22. A sol-gel material as claimed in claim 17, wherein the second polyalkoxysilane is 3-aminopropyltriethoxysilane.

23. A sol-gel material as claimed in claim 17, which includes a probe molecule.

24. A sol-gel material as claimed in claim 23, wherein the probe molecule is chosen from hydralazine, 4-amino-3-penten-2-one, 2,4-dinitrophenylhydrazine, iodine oxides, triphenylmethane derivatives, azobenzene derivatives and alkyl halides.

25. A process for preparing a sol-gel material as defined in claim 17, wherein the first polyalkoxysilane(s) are mixed, at a temperature of −

45 to +15°

C., with a water-miscible organic solvent therefor, the second polyalkoxysilane is then added, water is added, supplemented, if desired, with a catalyst or a structuring agent, or both, and stirring is continued to obtain the sol and then the expected sol-gel, which, if desired, is placed in sol form in molds to obtain expected sol-gel blocks.

26. A process as claimed in claim 25, wherein the mixing of the first polyalkoxysilane(s) with a water-miscible organic solvent therefor is performed for a time of between 1 and 10 minutes.

27. A process as claimed in claim 25, wherein the olyalkoxysilanes/solvent/water mole ratio is from 1/4/1 to 1/100/30.

28. A process for preparing a sol-gel material incorporating a probe molecule as defined in claim 25, wherein a probe molecule is added either directly during the preparation of the sol of the sol-gel material, or by diffusion of this probe molecule into the material via gas-phase or liquid-phase diffusion.

29. A process for trapping monocyclic aromatic hydrocarbons using, as sensor, a sol-gel material as defined in claim 17, in which a stream that may contain monocyclic aromatic hydrocarbons is placed in contact with the sol-gel material, or such a stream is made to circulate thereon.

30. A process as claimed in claim 29, wherein the detection of the monocyclic aromatic hydrocarbons trapped on the sol-gel materials is also performed.

31. A process for trapping pollutants chosen from aldehydes, aromatic compounds, alkanes, carboxylic acids, ketones and chlorine using as sensor a sol-gel material as defined in claim 17, incorporating a probe molecule, in which a stream that may contain a pollutant from among those mentioned above is placed in contact with said sol-gel material incorporating a probe molecule, or such a stream is made to circulate thereon.

32. A system for trapping or detecting monocyclic aromatic hydrocarbons or a pollutant using as sensor a sol-gel material as defined in claim 17.