Method for producing high surface area chromia materials for catalysis
View Patent ↗Nanostructured chromium(III)-oxide-based materials using sol-gel processing and a synthetic route for producing such materials are disclosed herein. Monolithic aerogels and xerogels having surface areas between 150 m 2 /g and 520 m 2 /g have been produced. The synthetic method employs the use of stable and inexpensive hydrated-chromium(III) inorganic salts and common solvents such as water, ethanol, methanol, 1-propanol, t-butanol, 2-ethoxy ethanol, and ethylene glycol, DMSO, and dimethyl formamide. The synthesis involves the dissolution of the metal salt in a solvent followed by an addition of a proton scavenger, such as an epoxide, which induces gel formation in a timely manner. Both critical point (supercritical extraction) and atmospheric (low temperature evaporation) drying may be employed to produce monolithic aerogels and xerogels, respectively.
1. A sol-gel processing method for producing nanostructured chromium(III)-oxide-based materials comprising:
forming a solution containing at least one hydrated-chromium(III) inorganic salt and at least one solvent, wherein said solution has a pH less than 7 and a gelation point;
adjusting the pH of the solution with a first proton scavenger comprising a hydroxide base to a point just prior to the gelation point; and
adding an organic epoxide to the solution to induce gel formation of the solution, wherein following said addition a nanostructured chromium(III)-oxide-based gel is formed.
2. The method of claim 1 , wherein the solution contains water.
3. The method of claim 1 , further comprising:
drying said nanostructured chromium(III)-oxide-based gel by atmospheric evaporation to form a nanostructured monolith chromium(III)-oxide-based monolithic xerogel.
4. The method of claim 1 , further comprising:
drying said nanostructured chromium(III)-oxide-based gel by super critical solvent extraction to form a nanostructured monolith chromium(III)-oxide-based to form a monolithic aerogel.
5. The method of claim 4 , wherein said monolithic aerogel has a surface area greater than about 420 m 2/ g.
6. The method of claim 1 , wherein forming the solution is carried out using ethanol as the solvent.
7. The method of claim 1 , wherein all steps are carried out under ambient conditions.
8. The method of claim 1 , wherein forming the solution is carried out using a hydrated-chromium(III) inorganic salt selected from the group consisting of chromium(III) nitrate nonahydrate, chromium(III) chloride hexahydrate, chromium (III) bromide hexahydrate, chromium (III) fluoride tetrahydrate, and chromium (III) sulfate hydrate.
9. The method of claim 1 , wherein forming the solution is carried out using a solvent selected from the group of water, ethanol, methanol, 1-propanol, isopropanol, tert-butanol, 2-butanol, 2-ethoxyethanol, dimethylformamide, ethylene glycol, and dimethylsulfoxide.
10. The method of claim 1 , wherein the organic epoxide is propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, epichlorohydrin, epibromohydrin, epichlorohydrin, butadiene monoxide, glycidol, trimethylene oxide, 3,3-dimethyoxetane, 2,3 epoxy(propyl) benzene, cyclohexene oxide, or cis-2,3-epoxybutane.
11. The method of claim 1 , wherein forming the solution is carried out using between about a 0.03–0.06M solution in 200 proof ethanol, wherein the total proton scavenger equals the amount of proton scavenger added plus the amount of organic epoxide added and the quantity of total proton scavenger added is determined by using a molar ratio of total proton scavenger to Cr(III) of 6 or greater.
12. A sol-gel processing method for producing nanostructured chromium(III)-oxide-based materials comprising:
forming a solution containing at least one anhydrous chromium(III) inorganic salt and at least one solvent;
adding at least 3 equivalents of water to said solution causing said solution to have a pH less than 7 and a gelation point;
adjusting the pH of the solution with a first proton scavenger comprising a hydroxide base to a point just prior to the gelation point; and
adding an organic epoxide to the solution to induce gel formation of the solution, wherein following said addition a nanostructured chromium(III)-oxide-based gel is formed.
13. The method of claim 12 , wherein said second base is an epoxide, further comprising:
drying said nanostructured chromium(III)-oxide-based gel by atmospheric evaporation to form a nanostructured monolith chromium(III)-oxide-based monolithic xerogel.
14. The method of claim 12 , wherein said second base is an epoxide, further comprising:
drying said nanostructured chromium(III)-oxide-based gel by super critical solvent extraction to form a nanostructured monolith chromium(III)-oxide-based to form a monolithic aerogel.
15. The method of claim 13 , wherein said monolithic aerogel has a surface area greater than about 420 m 2/ g.
16. The method of claim 12 , wherein forming the solution is carried out using ethanol as the solvent.
17. The method of claim 12 , wherein all steps are carried out under ambient conditions.
18. The method of claim 12 , wherein the organic epoxide is propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, epichlorohydrin, epibromohydrin, epichlorohydrin, butadiene monoxide, glycidol, trimethylene oxide, 3,3-dimethyoxetane, 2,3 epoxy(propyl) benzene, cyclohexene oxide, or cis-2,3-epoxybutane.
19. The method of claim 12 , wherein forming the solution is carried out using between about a 0.03–0.06M solution in 200 proof ethanol, wherein the total proton scavenger equals the amount of proton scavenger added plus the amount of organic epoxide added and the quantity of total proton scavenger added is determined by using a molar ratio of total proton scavenger to Cr(III) of 6 or greater.