Nitride stabilized core/shell nanoparticles
Nitride stabilized metal nanoparticles and methods for their manufacture are disclosed. In one embodiment the metal nanoparticles have a continuous and nonporous noble metal shell with a nitride-stabilized non-noble metal core. The nitride-stabilized core provides a stabilizing effect under high oxidizing conditions suppressing the noble metal dissolution during potential cycling.
1. A method of forming nitride stabilized nanoparticles comprising,
a non-noble metal solid solution core with a size of less than 100 nm along at least one of three orthogonal axes, and
a continuous and nonporous noble metal shell surrounding the non-noble metal solid solution core;
wherein the non-noble metal solid solution core comprises a nitride of a non-noble metal selected from the group consisting of nickel (Ni) nitride, cobalt (Co) nitride, iron (Fe) nitride, copper (Cu) nitride and mixtures thereof;
formed by:
preparing a mixture comprising an organic solvent, a salt of a first metal, and a salt of a second metal;
evaporating the organic solvent from the mixture to leave a dry powder; and
annealing the dry powder under a nitrogen source to produce a nitride of the first metal.
2. The method of claim 1 wherein the nitrogen source comprises a nitrogen gas (N 2 ), an ammonium gas (NH 3 ) or a combination thereof.
3. The method of claim 1 , wherein the annealing comprises exposing the dry powder to a temperature from between about 400 and about 700° C. under NH 3 for 1 to 10 hours.
4. The method of claim 1 , wherein the mixture further comprises a carbon powder.
5. The method of claim 1 , further comprising sonicating the mixture before evaporating the organic solvent from the mixture.
6. The method of claim 1 , wherein first metal comprises at least one non-noble transition metal.
7. The method of claim 6 , wherein at least one non-noble transition metal comprises at least one of nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), tungsten (W) or a combination thereof.
8. The method of claim 1 , wherein the second metal comprises at least one noble metal.
9. The method of claim 8 , wherein the at least one noble metal comprises at least one of palladium (Pd), iridium (Ir), rhenium (Re), ruthenium (Ru), rhodium (Rh), osmium (Os), gold (Au), and platinum (Pt), or a combination thereof.
10. The method of claim 1 , wherein the first metal is nickel (Ni), and the second metal is platinum (Pt).
11. The method of claim 1 , wherein the first metal is nickel (Ni), and the second metal is palladium (Pd).
12. The method of claim 1 , wherein the first metal is nickel (Ni), and the second metal is palladium (Ir).
13. The method of claim 1 , wherein the salt of the first metal is Ni(acac) 2 , and the salt of the second metal is Pt(acac) 2 .
14. The method of claim 1 , wherein the salt of the first metal is Ni(acac) 2 , and the salt of the second metal is Pd(acac) 2 .
15. The method of claim 1 , wherein the salt of the first metal is Ni(acac) 2 , and the salt of the second metal is Ir(acac) 3 .
16. The method of claim 1 , wherein the mixture further comprises a salt of a third metal.
17. The method of claim 16 , wherein the third metal is different from the first metal and the second metal, and comprises at least one of nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), tungsten (W) palladium (Pd), iridium (Ir), rhenium (Re), ruthenium (Ru), rhodium (Rh), osmium (Os), gold (Au), or platinum (Pt).
18. The method of claim 16 , wherein the first metal is nickel (Ni), the second metal is palladium (Pd), and the third metal is gold (Au).
19. The method of claim 16 , wherein the salt of the first metal is Ni(acac) 2 , the salt of the second metal is Pd(acac) 2 , and the salt of the third metal is Au(CH 3 ) 2 (acac).
20. The method of claim 1 , wherein the organic solvent is at least one of acetone, chloroform, benzene, cyclohexane, dichloromethane, ethanol, diethyl ether, ethyl acetate, hexane, methanol, toluene, xylene, mixtures of two or more thereof, or derivatives of one or more thereof.