Single-source synthesis of ceramic oxide nanoparticles

Patent metadata

Field	Value
Publication number	US-10407347-B2
Application number	US-201815901776-A
Country	US
Kind code	B2
Filing date	Feb 21, 2018
Priority date	Oct 27, 2016
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

The tris(trimethylsilyl)silanol (H-SST) ligand can be reacted with a Group 4 or 5 metal alkoxides in a solvent to form an SST-modified metal alkoxide precursor. Exemplary Group 4 precursors include [Ti(SST)2(OR)2] (OR=OPri, OBut, ONep); [Ti(SST)3(OBun)]; [Zr(SST)2(OBut)2(py)]; [Zr(SST)3(OR)] (OR=OBut, ONep); [Hf(SST)2(OBut)2]; and [Hf(SST)2(ONep)2(py)n] (n=1, 2), where OPri=OCH(CH3)2, OBut=OC(CH3)3, OBun=O(CH2)3CH3, ONep=OCH2C(CH3)3, and py=pyridine. Exemplary Group 5 precursors include [V(SST)3(py)2]; [Nb(SST)3(OEt)2]; [Nb(O)(SST)3(py)]; 2[H][(Nb(μ-O)2(SST))6(μ6-O)]; [Nb8O10(OEt)18(SST)2.⅕Na2O]; [Ta(SST)(μ-OEt)(OEt)3]2; and [Ta(SST)3(OEt)2]; where OEt=OCH2CH3. When thermally processed, the precursors can form unusual core-shell nanoparticles. For example, HfO2/SiO2 core/shell nanoparticles have demonstrated resistance to damage in extreme irradiation and thermal environments.

First claim

We claim:

1. A method to synthesize a metal-siloxide precursor, comprising reacting tris(trimethylsilyl)silanol ligand (H-SST) with a Group 4 or 5 metal alkoxide in a solvent to form an SST-modified metal alkoxide precursor.

2. The method of claim 1 , wherein the Group 4 metal comprises Ti, Zr, or Hf.

3. The method of claim 1 , wherein the Group 5 metal comprises V, Nb, or Ta.

4. The method of claim 1 , wherein the alkoxide comprises OCH 2 CH 3 , OCHMe 2 , or OCMe 3 , or OCH 2 CMe 3 .

5. The method of claim 1 , wherein the solvent comprises toluene or pyridine.

6. The method of claim 2 , wherein the SST-modified metal siloxide precursor comprises [Ti(SST) 2 (OR) 2 ], wherein OR=OPr i , OBu t , or ONep; [Ti(SST) 3 (OBu n )]; [Zr(SST) 2 (OBu t ) 2 (py)]; [Zr(SST) 3 (OR)], wherein OR=OBu t or ONep; or [Hf(SST) 2 (OBu t ) 2 ]; [Hf(SST) 2 (ONep) 2 (py) n ], wherein n=1 or 2, and wherein OPr i =OCH(CH 3 ) 2 , OBu t =OC(CH 3 ) 3 , OBu n =O(CH 2 ) 3 CH 3 , ONep=OCH 2 C(CH 3 ) 3 , and py=pyridine.

7. The method of claim 3 , wherein the SST-modified metal siloxide precursor comprises [V(SST) 3 (py) 2 ]; [Nb(SST) 3 (OEt) 2 ]; [Nb(O)(SST) 3 (py)]; 2[H][(Nb(μ-O) 2 (SST)) 6 (μ 6 -O)]; [Nb 8 O 10 (OEt) 18 (SST) 2 ·⅕Na 2 O]; [Ta(SST)(μ-OEt)(OEt) 3 ] 2 ; or [Ta(SST) 3 (OEt) 2 ]; wherein OEt=OCH 2 CH 3 and py=pyridine.

8. A method of making a ceramic oxide nanoparticle comprising heating the SST-modified metal alkoxide precursor of claim 1 to above a decomposition temperature.

9. The method of claim 8 , wherein the decomposition temperature is greater than or equal to 450° C.

10. The method of claim 8 , wherein the ceramic oxide nanoparticle comprises a core-shell nanoparticle.

11. The method of claim 10 , wherein the core-shell nanoparticle comprises a silicate core and a metal oxide shell.

12. The method of claim 11 , wherein the metal oxide shell comprises ZrO 2 .

13. The method of claim 10 , wherein the core-shell nanoparticle comprises a metal oxide core and a silicate shell.

14. The method of claim 13 , wherein the metal oxide core comprises HfO 2 .

15. The method of claim 8 , wherein the ceramic oxide nanoparticle comprises TiO 2 , Ta 2 O 3 , Nb 2 O 3 , or V 2 O 3 .

Assignees

• Nat Tech & Eng Solutions Sandia Llc

Inventors

• Boyle Timothy J
• Chan Rana
• Sears Jeremiah Matthew
• Hernandez-Sanchez Bernadette A

Classifications

• C07F7/0836 Primary

  Compounds with one or more Si-OH or Si-O-metal linkage · CPC title

• C04B2235/3427

  Silicates other than clay, e.g. water glass · CPC title

• C04B35/62892

  with a coating layer consisting of particles · CPC title

• C04B35/62823

  Zirconium or hafnium oxide · CPC title

• C04B35/62807

  Silica or silicates · CPC title