Composite nanoparticles containing rare earth metal and methods of preparation thereof
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.
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 first sacrificial anode is a metal anode and the second sacrificial anode is a rare earth element anode.
35. The process of claim 26 , wherein the first sacrificial anode is a cobalt anode and the second sacrificial anode is a samarium anode.
36. The process of claim 26 , wherein the first sacrificial anode is a rare earth element anode and the second sacrificial anode is a metal anode.
37. The process of claim 26 , wherein the first sacrificial anode is a samarium anode and the second sacrificial anode is a cobalt anode.
38. The process of claim 26 , wherein the organic solvent is selected from the group consisting of tetrahydrofuran, acetone, acetonitrile, dimethylformamide, and dimethyl sulfoxide.
39. The process of claim 26 , wherein the electrolyte is a quaternary ammonium salt or a quaternary phosphonium salt.
40. The process of claim 26 , 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.
41. The process of claim 26 , wherein the electrolyte is selected from the group consisting of tetraoctylammonium bromide, triethylbenzylammonium chloride, and tetrahexylammonium chloride.
42. The process of claim 26 , wherein the electric current in step (a) has a voltage from about 0.28 V to about 50 V.
43. The process of claim 26 , wherein the electric current in step (b) has a voltage from about 0.28 V to about 50 V.
44. The process of claim 26 , wherein the electric current in step (a) has a current from about 0.25 mA to about 30 mA.
45. The process of claim 26 , wherein the electric current in step (b) has a current from about 0.25 mA to about 30 mA.
46. The process of claim 26 , wherein the electrolyte has a concentration of from about 0.01 M to about 10 M.
47. The process of claim 26 , wherein the complexing ligand has a concentration of from about 0.05 M to about 50 M.
48. The process of claim 26 , 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.
49. The process of claim 26 , wherein the composite nanoparticles have a mean diameter size from about 2 nm to about 500 nm.
50. The process of claim 26 , wherein the composite nanoparticles have an aspect ratio from 1 to 1000.