Composite nanoparticles containing rare earth metal and methods of preparation thereof

Patent metadata

Field	Value
Publication number	US-9938628-B2
Application number	US-201514715704-A
Country	US
Kind code	B2
Filing date	May 19, 2015
Priority date	May 19, 2015
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.

First claim

What is claimed is:

1. A process for preparation of composite nanoparticles in an electrochemical cell comprising a first sacrificial anode, a second sacrificial anode, a cathode, and a reaction solution, the process comprising:
(a) applying an electric current to the first sacrificial anode and to the cathode, wherein the first sacrificial anode is a metal anode or a rare earth element anode;
(b) applying an electric current to the second sacrificial anode and to the cathode, wherein the second sacrificial anode is a metal anode or a rare earth element anode;
provided that when the first sacrificial anode is the metal anode, the second sacrificial anode is the rare earth element anode; and
provided that when the first sacrificial anode is the rare earth element anode, the second sacrificial anode is the metal anode;
wherein the reaction solution comprises an organic solvent, an electrolyte, and a complexing ligand;
whereby composite nanoparticles are formed in the reaction solution, wherein the complexing ligand is a compound of formula (I):

wherein
R 1 is H, alkyl, arylalkyl, or aryl;
R 2 is H, alkyl, arylalkyl, or aryl;
R 3 is alkylene, -alkylene-arylene-, arylene, or alkylene substituted with alkyl or aryl;
R 4 is alkylene, -alkylene-arylene-, arylene, or alkylene substituted with alkyl or aryl;
R 5 is H, alykl, arylalkyl, or aryl;
Z is —O—, —S—, —N(H)—, or —N(R 6 )—, wherein R 6 is alkyl; and
n is 0 or 1.

2. The process of claim 1 , further comprising collecting the composite nanoparticles from the reaction solution.

3. The process of claim 2 , further comprising performing heat treatment of the composite nanoparticles.

4. The process of claim 1 , wherein step (b) is performed subsequently to step (a).

5. The process of claim 1 , wherein step (a) and step (b) are performed concurrently.

6. The process of claim 1 , wherein the metal anode is a transition metal anode or a post-transition metal anode.

7. The process of claim 1 , wherein the metal anode is selected from the group consisting of iron, cobalt, nickel, manganese, platinum, aluminum, copper, zirconium, and chromium anodes.

8. The process of claim 1 , wherein the rare earth element anode is selected from the group consisting of samarium, praseodymium, neodymium, gadolinium, yttrium, dysprosium, and terbium anodes.

9. The process of claim 1 , wherein the first sacrificial anode is a metal anode and the second sacrificial anode is a rare earth element anode.

10. The process of claim 1 , wherein the first sacrificial anode is a cobalt anode and the second sacrificial anode is a samarium anode.

11. The process of claim 1 , wherein the first sacrificial anode is a rare earth element anode and the second sacrificial anode is a metal anode.

12. The process of claim 1 , wherein the first sacrificial anode is a samarium anode and the second sacrificial anode is a cobalt anode.

13. The process of claim 1 , wherein the organic solvent is selected from the group consisting of tetrahydrofuran, acetone, acetonitrile, dimethylformamide, and dimethyl sulfoxide.

14. The process of claim 1 , herein the electrolyte is a quaternary ammonium salt or a quaternary phosphonium salt.

15. The process of claim 1 , wherein the electrolyte is a compound of formula (II):

wherein
R 7 is alkyl, arylalkyl, or aryl;
R 8 is alkyl, arylalkyl, or aryl;
R 9 is alkyl, arylalkyl, or aryl;
R 10 is alkyl, arylalkyl, or aryl;
Q 30 is N + or P + ; and
X − is chloride ion, bromide ion, iodide ion, hexafluorophosphate, carboxylate ion, or sulfonate ion.

16. The process of claim 1 , wherein the electrolyte is selected from the group consisting of tetraoctylammonium bromide, triethylbenzylammonium chloride, and tetrahexylammonium chloride.

17. The process of claim 1 , wherein, the electric current in step (a) has a voltage from about 0.28 V to about 50 V.

18. The process of claim 1 , wherein, the electric current in step (b) has a voltage from about 0.28 V to about 50 V.

19. The process of claim 1 , wherein the electric current in step (a) has a current from about 0.25 mA to about 30 mA.

20. The process of claim 1 , wherein the electric current in step (b) has a current from about 0.25 mA to about 30 mA.

21. The process of claim 1 , wherein the electrolyte has a concentration of from about 0.01 M to about 10 M.

22. The process of claim 1 , wherein the complexing ligand has a concentration of from about 0.05 M to about 50 M.

23. The process of claim 1 , wherein the rare earth to metal element stoichiometric ratio in the composite nanoparticles is selected from the group consisting of 1:1, 1:3, 1:5, 1:7, 1:13, 2:7, 2:17, and 5:19.

24. The process of claim 1 , wherein the composite nanoparticles have a mean diameter size from about 2 nm to about 500 nm.

25. The process of claim 1 , wherein the composite nanoparticles have an aspect ratio from 1 to 1000.

26. A process for preparation of composite nanoparticles in an electrochemical cell comprising a first sacrificial anode, a second sacrificial anode, a cathode, and a reaction solution, the process comprising:
(a) applying an electric current to the first sacrificial anode and to the cathode, wherein the first sacrificial anode is a metal anode or a rare earth element anode;
(b) applying an electric current to the second sacrificial anode and to the cathode, wherein the second sacrificial anode is a metal anode or a rare earth element anode;
provided that when the first sacrificial anode is the metal anode, the second sacrificial anode is the rare earth element anode; and
provided that when the first sacrificial anode is the rare earth element anode, the second sacrificial anode is the metal anode;
wherein the reaction solution comprises an organic solvent, an electrolyte, and a complexing ligand;
whereby composite nanoparticles are formed in the reaction solution, wherein the complexing ligand is selected from the group consisting of 2-[2-(dimethylamino)ethoxy]ethanol, 2-[2-(diethylamino)ethoxy]ethanol, 2-{[2-(dimethylamino)ethyly]dimethylamino}ethanol, and 4-(dimethylamino)-1-butanol.

27. The process of claim 26 , further comprising collecting the composite nanoparticles from the reaction solution.

28. The process of claim 27 , further comprising performing heat treatment of the composite nanoparticles.

29. The process of claim 26 , wherein step (b) is performed subsequently to step (a).

30. The process of claim 26 , wherein step (a) and step (b) are performed concurrently.

31. The process of claim 26 , wherein the metal anode is a transition metal anode, or a post-transition metal anode.

32. The process of claim 26 , wherein the metal anode is selected from the group consisting of iron, cobalt, nickel, manganese, platinum, aluminum, copper, zirconium, and chromium anodes.

33. The process of claim 26 , wherein the rare earth element anode is selected from the group consisting of samarium, praseodymium, neodymium, gadolinium, yttrium, dysprosium, and terbium anodes.

34. The process of claim 26 , wherein the

Assignees

• Gen Electric

Inventors

• Kandapallil Binil Itty Ipe
• Krishnan Lakshmi
• Johnson Francis

Classifications

• C25D15/00

  Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires · CPC title

• C25C7/06

  Operating or servicing · CPC title

• C25D3/56

  of alloys · CPC title

• C25B3/12

  Chemistry & Metallurgy · mapped topic

• C25C5/02

  from solutions · CPC title