One-step synthesis of monodisperse transition metal core-shell nanoparticles with solid solution shells
Methods of forming monodispersed core-shell nanoparticles are provided. A cobalt(II)-ligand component, a metal(II)-ligand component, an organic reducing agent, and a capping agent can be added to an organic solvent to form a reaction mixture. The reaction mixture is then heated to a dissolving temperature while under a gas (e.g., including methane) such that the reaction mixture becomes a reaction solution while stirring at the dissolving temperature. The reaction solution is then be heated to a reaction temperature (e.g., about 200° C. or more) while under the gas to form the core-shell nanoparticles, and the core-shell nanoparticles can be collected from the reaction solution.
1. A method of forming monodispersed core-shell nanoparticles, the method comprising:
adding a cobalt(II)-ligand component, a metal(II)-ligand component, an organic reducing agent, and a capping agent to an organic solvent to form a reaction mixture, wherein the metal(II)-ligand comprises a metal(II) selected from the group consisting of copper(II), iron(II), chromium(II), scandium(II), nickel (II), and mixtures thereof;
heating the reaction mixture to a dissolving temperature while under a gas, wherein the reaction mixture becomes a reaction solution while stirring at the dissolving temperature, and wherein the gas comprises methane;
heating the reaction solution to a reaction temperature while under the gas to form the core-shell nanoparticles, wherein the reaction temperature is about 200° C. or more; and
collecting the core-shell nanoparticles from the reaction solution.
2. The method as in claim 1 , further comprising:
after collecting the core-shell nanoparticles, dispersing the core-shell nanoparticles in a solvent.
3. The method as in claim 1 , wherein the metal(II)-ligand component comprises a copper(II)-ligand.
4. The method as in claim 3 , wherein the copper(II)-ligand comprises copper(II)-acetylacetonate.
5. The method as in claim 3 , wherein the core-shell nanoparticles have a core enriched with copper, and wherein the core-shell nanoparticles have a shell enriched with cobalt.
6. The method as in claim 3 , wherein the cobalt ligand component comprises cobalt(II)-acetylacetonate.
7. The method as in claim 1 , wherein the organic solvent has a boiling point that is higher than the reaction temperature.
8. The method as in claim 1 , wherein the organic solvent comprises dibenzyl ether.
9. The method as in claim 1 , wherein the dissolving temperature is about 50° C. to about 150° C.
10. The method as in claim 1 , wherein the gas is natural gas.
11. The method as in claim 1 , wherein the organic reducing agent comprises a long chain alcohol.
12. The method as in claim 11 , wherein the long chain alcohol comprises 1,2-dodecanediol.
13. The method as in claim 1 , wherein the capping agent comprises a polymer having a repeating, exposed carbonyl group.
14. The method as in claim 1 , wherein the capping agent comprises polyvinyl pyrrolidone).
15. The method as in claim 1 , wherein the collected core-shell nanoparticles have an average size of about 7 nm to about 50 nm.
16. The method as in claim 1 , wherein the collected core-shell nanoparticles have a size distribution such that at least about 75% of the collected core-shell nanoparticles have an average size that is within about 5 nm of the mean average size of all the collected core-shell nanoparticles.
17. The method as in claim 1 , wherein the cobalt(II)-ligand component and the metal(II)-ligand component are present in the reaction mixture such that an atomic ratio of cobalt(II) to metal(II) is about 19:1 to about 1:19.
18. The method as in claim 1 , wherein the cobalt(II)-ligand component and the metal(II)-ligand component are present in the reaction mixture such that an atomic ratio of cobalt(II) to metal(II) is about 19:1 to about 4:1.