Porous metal oxide and metal oxide-organic nanocomposites, methods of making and uses thereof

Patent metadata

Field	Value
Publication number	US-9593027-B2
Application number	US-201313783266-A
Country	US
Kind code	B2
Filing date	Mar 2, 2013
Priority date	Mar 2, 2012
Publication date	Mar 14, 2017
Grant date	Mar 14, 2017

Abstract

The disclosure provides relates to compositions and methods for water treatment. It also addresses a method for synthesizing TiO 2 (and other metal oxides) with or without dopants. This method enables control over size, phase, morphology and porosity and specific surface area of these materials. The disclosure also provides metal oxide composites that can be used in photocatalysts, photovoltaics, energy storage materials (e.g., Li-ion anodes), and solar hydrogen applications.

First claim

What is claimed is:

1. A method for fabricating a metal-organic composite having a defined size and geometry, comprising:
reacting a precursor for a compound with an organic dispersing agent in a solvent so as to obtain a metal-organic composite comprising a nanostructure that includes the compound cross-linked by the dispersing agent, wherein the compound is selected from the group consisting of metal oxides, metal sulfides, metal selenides, metal tellurides, metal nitrides, metal phosphides, and metal arsenides, and wherein the reaction is carried out at a pH from 6 to 11, at a temperature from 25° C. to 250° C. and at a pressure from 14 to 150 psi; and
extruding and/or machining the metal-organic composite to have a defined size and geometry;
drying the metal-organic composite by using a critical point dryer or by heating the composite in a drying oven; and
heating the metal-organic composite at a temperature greater than 300° C. to partially or fully pyrolyze the dispersing agent.

2. A method for fabricating a substrate coated with a metal-organic composite, comprising:
mixing a precursor for a compound with a dispersing agent in a solvent so as to obtain a metal-organic composite comprising a nanostructure that includes the compound cross-linked by the dispersing agent, the compound being selected from a group consisting of metal oxides, metal sulfides, metal selenides, metal tellurides, metal nitrides, metal phosphides, and metal arsenides, and
wherein the reaction is carried out at a pH from 6 to 11 and at a temperature from 25° C. to 250° C.;
coating a substrate with the metal-organic composite, and
heating the metal-organic composite at a temperature greater than 300° C. to partially or fully pyrolyze the dispersing agent.

3. The method of claim 1 or 2 , wherein the precursor is selected from the group consisting of aluminum bis-ethylacetoacetate monoacetylacetonate, aluminum diacetylacetonate ethyl acetoacetate, aluminum monoacetylacetonate bis-propyl acetoacetate, aluminum monoacetylacetonate bisbutyl acetoacetate, aluminum monoacetylacetonate bishexyl acetoacetate, aluminum monoethyl acetoacetate bispropyl acetoacetonate, aluminum monoethyl acetoacetate bisbutyl acetoacetonate, aluminum monoethylacetoacetate bis-hexyl acetoacetonate, aluminum monoethylacetoacetate bisnonylacetoacetonate, aluminum dibutoxide monoacetoacetate, aluminum dipropoxide monoacetoacetate, aluminum butoxide monoethylacetoacetate, aluminum-s-butoxide bis(ethyl acetoacetate), aluminum di-s-butoxide ethylacetoacetate, aluminum-9-octadecenyl acetoacetate diisopropoxide, titanium allylacetoacetate triisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), titanium bis ammonium lactato dihydroxide (TiBALDH), titanium methacryloxyethylacetoacetate triisopropoxide, titanium oxide bis(pentanedionate), titanium chloride, titanium sulfate, zirconium allylacetoacetate triisopropoxide, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide (bis-2,4-pentanedionate), zirconium diisopropoxide bis(tetramethylheptanedionate), zirconium diisopropoxide bis(ethylacetoacetate), zirconium methacryl icoxyethylacetoacetate triisopropoxide, zirconium butoxide (acetylacetate) (bisethylacetoacetate), and iron acetyl acetonate.

4. The method of claim 1 or 2 , wherein the precursor is titanium bis ammonium lactato dihydroxide (TiBALDH).

5. The method of claim 1 or 2 , wherein the dispersing agent is selected from phosphoglycerides; dioleylphosphatidyl ethanolamine (DOPE); dioleyloxypropyltriethylammonium (DOTMA); cholesterol; cholesterol ester; diacylglycerol; diacylglycerolsuccinate; diphosphatidyl glycerol (DPPG); hexanedecanol; polyethylene glycol (PEG); polyoxyethylene-9-lauryl ether; palmitic acid; oleic acid; fatty acid amides; sorbitan trioleate (Span 85); polysorbate 80 (TWEEN-80); sodium cholate methyl cellulose; gelatin; surfactin; a poloxomer; a sorbitan fatty acid; phosphatidylserine; phosphatidylinositol; phosphatidylethanolamine (cephalin); cardiolipin; phosphatidic acid; dicetylphosphate; dipalmitoylphosphatudylglycerol; stearylamine; dodecylamine; hexadecylamine; acetyl palmitate; glycerol ricinoleate; hexadecyl sterate; isopropyl myristate; tyloxapol; poly(ethylene glycol) 5000-phosphatidylethanolamine; polyvinyl alcohol (PVA); phospholipids; poloxamers, Poly(vinylphosphonic acid)Poly(acrylic acid), Poly(vinylsulfonic acid), Poly(methacrylic acid), poly (phosphonic acid) or any combinations thereof.

6. The method of claim 5 , wherein the dispersing agent is polyvinyl alcohol.

7. The method of claim 1 or 2 , wherein the reaction is carried out at a pH from 7.8 to 9.

8. The method of claim 1 or 2 , wherein the precursor is titanium bis ammonium lactato dihydroxide (TiBALDH) and the dispersing agent is polyvinyl alcohol.

9. The method of claim 8 , wherein the ratio of TiBALDH to PVA is between about 1:50 and 1:100,000.

10. The method of claim 1 or 2 , wherein the reaction is carried out at about 150° C.

11. The method of claim 2 , wherein the substrate is a light transmitting material.

12. The method of claim 11 , wherein the substrate is a fiber optic wire or tube.

13. The method of claim 1 , wherein the nanostructure is one of multiple nanostructures included in the metal-organic composite and different nanostructures are cross linked by the dispersing agent.

14. The method of claim 1 , wherein the dispersant crosslinks with the compound while the compound is being formed through a hydrolysis-condensation reaction.

Assignees

• Univ California

Inventors

• Kisailus David
• Kinsinger Nichola

Classifications

• C02F1/32 Primary

  with ultraviolet light · CPC title

• C01B19/007

  Tellurides or selenides of metals (C01B19/002 takes precedence) · CPC title

• C01G23/047

  Titanium dioxide · CPC title

• C02F2305/08

  Nanoparticles or nanotubes · CPC title

• C01B21/06

  Binary compounds of nitrogen with metals, with silicon, or with boron, {or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron}(azides C01B21/08) · CPC title