Development of Earth-Abundant Mixed-Metal Sulfide Nanoparticles For Use In Solar Energy Conversion
AssigneeFranklin and Marshall College
InventorKatherine Plass
Life of this patent
Estimating the term…
Abstract
This invention relates to a process for the phase-controlled synthesis of ternary and quaternary mixed-metal sulfide nanoparticles by reacting soft metal ions with hard metal ions in a high-boiling organic solvent in the presence of a complexing and activating ligands to control the reactivity of the metal ions. Ternary and quaternary mixed metal sulfides nanoparticles of copper, sulfur, and iron, aluminum, tin, and silicon are preferred. This invention also relates to the phase controlled preparation of polymorphs of bornite nanoparticles and the phase controlled preparation of stabilized α- and γ-chalconite nanoparticles.
Claims23
A process for the phase-controlled synthesis of ternary and quaternary mixed-metal sulfide nanoparticles comprising the steps of
- (a) mixing in a high-boiling organic solvent and under an inert atmosphere a molar equivalent of a soft metal ion complex;
- 0.1 to 20 molar equivalents of a hard metal ion complex;
- and 0.1 to 10 molar equivalents of sulfur;
- (b) adding a complexing ligand selected from the group consisting of bidentate, tridentate, and tetradentate ligands;
- and
- (c) stirring and heating the mixture at about 80° C. to 300° C. under an inert atmosphere for 0.1 to 12 hours;
- wherein said soft metal ion incorporated in the mixed-metal sulfide nanoparticles is selected from the group consisting of Cu+, Ag+, Ni2+, Pb2+, Zn2+, Cd2+, and Hg2+, wherein said hard metal ion is selected from the group consisting of Sc3+, Ti3+, Ti4+, V3+, V5+, Cr3+, Cr2+, Mn2+, Mn3+, Fe3+, Co3+, Al3+, Ga3+, In3+, Si4+, Ge4+, Sn4+, and Pb4+, and whereby said ternary and quaternary mixed-metal sulfide nanoparticles are produced.
A process for the phase-controlled synthesis of ternary and quaternary mixed-metal copper sulfide nanoparticles comprising the steps of
- (a) mixing in a high-boiling organic solvent and under an inert atmosphere equimolar amounts of a copper (II) complex;
- a metal complex of a metal ion selected from the group consisting of Cr3+, Mn2+, Fe3+, Fe2+, Co2+, Al3+, Tl3+, Si4+, Ge4+, and Sn4+, and 2 molar equivalents of sulfur;
- (b) adding a complexing ligand selected from the group consisting of bidentate, tridentate, and tetradentate ligands;
- and
- (c) stirring and heating the mixture at about 80° C. to 300° C. under an inert atmosphere;
- wherein said high-boiling solvent is selected from the group consisting of trioctylphosphine oxide, oleylamine, 1-dodecanethiol, oleic acid, diphenyl ether, and mixtures thereof, and whereby said ternary and quaternary mixed-metal copper sulfide nanoparticles are produced.
Mixed-metal copper sulfide nanoparticles prepared by a process comprising the steps of
- (a) mixing in a high-boiling organic solvent and under an inert atmosphere equimolar amounts of a copper complex and a complex of at least one hard-metal ion,
- (b) heating the mixture to about 80° C. to 300° C., and
- (c) injecting a solution of an equivalent of sulfur and heating the mixture about 280° C. for at least one hour,
- wherein said hard-metal ion is selected from the group consisting of Fe3+, Al3+, Si4+, and Sn4+, and wherein said inert solvent is trioctylphosphine oxide, oleylamine, or dodecanethiol.
Bornite nanoparticles prepared by a phase-controlled process comprising the steps of
- (a) mixing under an inert atmosphere one molar equivalent of copper (II) acetylacetonate, 0.2 molar equivalents of iron (III) acetylacetonate, and 1.0 to 3.0 molar equivalents of sulfur in a dodecanethiol/oleic acid solvent mixture, and
- (b) heating the mixture in the range of about 130 to 260° C. for about one hour.
A process for the phase-controlled synthesis of stabilized chalcocite (Cu2S) nanoparticles comprising the steps of
- (a) mixing under an inert atmosphere 2 molar equivalents of a copper (II) acetylacetonate, 1 molar equivalent of sulfur, and 0.01 to 0.10 molar equivalents of iron (III) acetylacetonate in oleylamine, and
- (b) heating the mixture at about 200 to 260° C. for at least one hour,
- whereby said stabilized chalcocite nanoparticles are produced.
A process for the phase-controlled synthesis of stabilized tetragonal chalcocite (γ-Cu2S) nanoparticles comprising the steps of
- (a) mixing under an inert atmosphere 2 molar equivalents of a copper (II) acetylacetonate, 1 molar equivalent of sulfur, and 0.01 to 0.10 molar equivalents of aluminum (III) acetylacetonate in 1-dodecanethiol/oleic acid solvent mixture, and
- (b) heating the mixture at about 200 to 260° C. for at least one hour,
- whereby said stabilized tetragonal chalcocite (γ-Cu2S) nanoparticles are produced.
A kit of reagents for facilitating the production of ternary and quaternary mixed-metal copper sulfide nanoparticles, said nanoparticles comprising copper ion, sulfur, and at least one hard metal ion selected from the group consisting of Sc3+, Ti3+, Ti4+, V3+, V5+, Cr3+, Cr2+, Mn2+, Mn3+, Fe3+, Co3+, Al3+, Ga3+, In3+, Si4+, Ge4+, Sn4+, and Pb4+, said kit comprising:
- (a) a container of reagent comprising an activating ligand for enhancing the reactivity of the hard metal ion, wherein said activating ligand is selected from the group consisting of I−, Br−, 1,2-ethanedithiol, 2,2′-thiodiethanethiol, t-butyl alcohol, thioacetic acid, thioacetamide, and HSR wherein R is alkyl,
- (b) a container of reagent comprising a complexing ligand for moderating the activity of the copper ion, wherein said complexing ligand is selected from the group consisting of
- (c) a container of a high-boiling organic solvent selected from the group consisting of trioctylphosphine oxide, oleylamine, 1-dodecanethiol, oleic acid, diphenyl ether, and mixtures thereof.
Dependencies are inferred from the claim text.