Method of microbially producing metal gallate spinel nano-objects, and compositions produced thereby

Patent metadata

Field	Value
Publication number	US-9868899-B2
Application number	US-201314399679-A
Country	US
Kind code	B2
Filing date	Mar 14, 2013
Priority date	May 8, 2012
Publication date	Jan 16, 2018
Grant date	Jan 16, 2018

Abstract

A method of forming a metal gallate spinel structure that includes mixing a divalent metal-containing salt and a gallium-containing salt in solution with fermentative or thermophilic bacteria. In the process, the bacteria nucleate metal gallate spinel nano-objects from the divalent metal-containing salt and the gallium-containing salt without requiring reduction of a metal in the solution. The metal gallate spinel structures, as well as light-emitting structures in which they are incorporated, are also described.

First claim

What is claimed is:

1. A method of forming a metal gallate spinel structure, the method comprising:
providing a supply of fermentative or thermophilic bacteria;
reacting a divalent metal-containing salt and a gallium-containing salt with the supply of fermentative or thermophilic bacteria, wherein treatment of the divalent metal-containing salt and the gallium-containing salt with the fermentative or thermophilic bacteria nucleates a divalent metal gallate spinel structure.

2. The method of claim 1 , further comprising including at least one dopant in the presence of said divalent metal-containing salt, gallium-containing salt and fermentative or thermophilic bacteria to nucleate a divalent metal gallate spinel structure containing said at least one dopant.

3. The method of claim 1 , wherein the fermentative or thermophilic bacteria comprises Thermoanaerobacter bacteria.

4. The method of claim 1 , wherein the divalent metal-containing salt, the gallium-containing salt and the supply of fermentative or thermophilic bacteria are contained in an aqueous solution.

5. The method of claim 1 , wherein a zinc gallate spinel structure is formed by selecting the divalent metal-containing salt as a zinc-containing salt, wherein treatment of the zinc-containing salt and the gallium-containing salt with the fermentative or thermophilic bacteria nucleates a zinc gallate spinel structure.

6. The method of claim 5 , further comprising including at least one dopant in the presence of said zinc-containing salt, gallium-containing salt and fermentative or thermophilic bacteria to nucleate a zinc gallate spinel structure containing said at least one dopant.

7. The method of claim 5 , wherein the zinc-containing salt is selected from zinc chloride (ZnCl 2 ), zinc bromide (ZnBr 2 ), zinc nitrate hydrate (Zn(NO 3 ) 2 .xH 2 O), zinc sulfate hydrate (ZnSO 4 .xH 2 O), zinc phosphate (Zn 3 (PO 4 ) 2 ), zinc acetate hydrate ((CH 3 CO 2 ) 2 Zn).xH 2 O), zinc stearate ([CH 3 (CH 2 ) 16 COO] 2 Zn), zinc fluoride (ZnF 2 ), zinc iodide (ZnI 2 ), zinc methoxide (C 2 H 6 O 2 Zn), zinc acrylate ((H 2 C═CHCO 2 ) 2 Zn), and combinations thereof.

8. The method of claim 1 , wherein the gallium-containing salt is selected from gallium chloride (GaCl 3 ), gallium chloride (GaCl 2 ), gallium nitrate hydroxide (GaNO 3 .xH 2 O), gallium fluoride (GaF 3 ), gallium iodide (GaI 3 ), gallium bromide (GaBr 3 ), gallium sulfate hydrate (GaSO 4 .xH 2 O), and combinations thereof.

9. The method of claim 5 , wherein the zinc gallate spinel structure is ZnGa 2 O 4 .

10. The method of claim 1 , wherein the treatment of the divalent metal-containing salt and the gallium-containing salt with the fermentative or thermophilic bacteria to nucleate the divalent metal gallate spinel structure comprises adjusting a pH of a solution of the divalent metal-containing salt, the gallium-containing salt, and the fermentative or thermophilic bacteria within a range of 5.5 to 8.5.

11. The method of claim 1 , wherein the treatment of the divalent metal-containing salt and the gallium-containing salt with the fermentative or thermophilic bacteria to nucleate the divalent metal gallate spinel structure comprises adjusting an E h of a solution of the divalent metal-containing salt, the gallium-containing salt, and the thermophilic bacteria within a range of 100 mV to -350 mV.

12. The method of claim 5 , wherein the zinc gallate spinel structure is a blue phosphor.

13. The method of claim 2 , wherein the dopant is at least one selected from the group consisting of Mn, Cr, Eu, Co, Dy, and combinations thereof.

14. The method of claim 6 , wherein the doping of the zinc gallate spinel comprises Co 2+ dopant and the wavelength of light emission ranges from 400 nm to 495 nm.

15. The method of claim 6 , wherein the zinc gallate spinel is doped with Mn 2 + dopant and the wavelength of light emission ranges from 495 nm to 570 nm.

16. The method of claim 15 , wherein doping of the zinc gallate spinel structure with Mn 2+ comprises mixing a manganese salt selected from manganese chloride hydrate(MnCl 2 .xH 2 O), manganese nitrate hydrate (Mn(NO 3 ) 2 .xH 2 O), manganese sulfate hydrate (MnSO 4 .xH 2 O), manganese iodide (MnI 2 ), manganese bromide (MnBr 2 ), manganese fluoride (MnF 3 ), manganese acetate hydrate (Mn(CH 3 COO) 2 .xH 2 O), and manganese carbonate (MnCO 3 ) with said divalent metal-containing salt, gallium-containing salt, and supply of fermentative or thermophilic bacteria in said method of forming a metal gallate spinel structure in claim 1 , wherein said divalent metal-containing salt is a zinc-containing salt, to produce said zinc gallate spinel doped with Mn 2+ .

17. The method of claim 6 , wherein the zinc gallate spinel is doped with Cr 3+ or Eu 3+ and the wavelength of light emission ranges from 570 nm to 750 nm.

18. The method of claim 17 , wherein doping of the zinc gallate spinel structure with Cr 3+ comprises mixing a chromium salt selected from chromium chloride hydrate (CrCl 3 .xH 2 O), chromium nitrate hydrate (Cr(NO 3 ) 3 .xH 2 O), chromium acetate hydroxide ((CH 3 CO 2 ) 7 Cr 3 (OH) 2 ), chromium sulfate hydrate (Cr 2 (SO 4 ) 3 .xH 2 O), chromium fluoride hydrate (GaF 3 .xH 2 O), chromium iodide hydrate (CrI 3 .xH 2 O), chromium bromide hydrate (CrBr 3 .xH 2 O), and chromium phosphate hydrate (Cr(PO 4 ).xH 2 O), with said divalent metal-containing salt, gallium-containing salt, and supply of fermentative or thermophilic bacteria in said method of forming a metal gallate spinel structure in claim 1 , wherein said divalent metal-containing salt is a zinc-containing salt, to produce said zinc gallate spinel doped with Cr 3+ .

19. The method of claim 17 , wherein doping of the zinc gallate spinel structure with Eu 3+ comprises mixing a europium salt selected from europium chloride hydrate (EuCl 3 .xH 2 O), europium fluoride hydrate (EuF 3 .xH 2 O), europium nitrate hydrate (Eu(NO 3 ) 3 .xH 2 O), europium acetate hydroxide ((CH 3 CO 2 ) 7 Eu 3 (OH) 2 ), europium bromide hydrate (EuBr 3 .xH 2 O), and europium sulfate hydrate (Eu 2 (SO 4 ) 3 .xH 2 O with said divalent metal-containing salt, gallium-containing salt, and supply of fermentative or thermophilic bacteria in said method of forming a metal gallate spinel structure in claim 1 , wherein said divalent metal-containing salt is a zinc-containing salt, to produce said zinc gallate spinel doped with Eu 3+ .

20. The method of claim 6 , wherein the zinc gallate spinel is doped with Dy 3+ dopant and the wavelength of light emission is in a wavelength ranging from 450 nm to 510 nm, or a wavelength ranging from 560 nm to 610 nm, or a wavelength ranging from 660 nm to 720 nm, or a wavelength ranging from 755 nm to 800 nm.

21. The method of claim 20 , wherein doping the zinc gallate spinel structure with Dy 3+ comprises mixing a dysprosium salt selected from dysprosium chloride hydrate (DyCl 3 .xH 2 O), dysprosium fluoride hydrate (DyF 3 .xH 2 O), dysprosium nitrate hydrate (Dy(NO 3 ) 3 .xH 2 O), dysprosium acetate hydroxide ((CH 3 CO 2 ) 7 Dy 3 (OH) 2 ), dysprosium bromide hydrate (DyBr 3 .xH 2 O), and dysprosium sulfate hydrate (Dy 2 (SO 4 ) 3 .xH 2 O) with said divalent metal-containing salt, gallium-containing salt, and supply of fermentative or thermophilic bacteria in said method of forming a metal gallate spinel structure in claim 1 , wherein said divalent metal-containing salt is a zinc-containing salt, to produce said zinc gallate spinel doped with Dy 3+ .

22. The method of claim 2 , furt

Assignees

• Ut Battelle Llc

Inventors

• Duty Chad E
• Jellison Jr Gerald E
• Love Lonnie J
• Moon Ji Won
• Phelps Tommy J
• Ivanov Ilia N
• Kim Jongsu
• Park Jehong
• Lauf Robert

Classifications

• C01G15/006

  Compounds containing gallium, indium or thallium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C30B29/26

  with formula BMe2O4, wherein B is Mg, Ni, Co, Al, Zn, or Cd and Me is Fe, Ga, Sc, Cr, Co, or Al · CPC title

• C01G15/00

  Compounds of gallium, indium or thallium · CPC title

• C12P3/00

  Preparation of elements or inorganic compounds except carbon dioxide {(recovery of carbon dioxides as by-products C12F3/02)} · CPC title

• C01P2002/52

  containing elements as dopants · CPC title