Patent Application
20080164141
The embodiments described herein relate to methods for making metal-containing nanoparticles or nanoalloy particles. In particular, metal nanoparticle components are provided that may be readily dispersed in oil and/or hydrocarbon materials for use in a wide variety of applications.
Metal-containing nanoparticles or nanoalloy particles may be used in a wide range of applications. For example, metal oxide nanoparticles may be used in: solid oxide fuel cells (in the cathode, anode, electrolyte and interconnect); catalytic materials (automobile exhausts, emission control, chemical synthesis, oil refinery, waste management); magnetic materials; superconducting ceramics; optoelectric materials; sensors (eg gas sensors, fuel control for engines); structural ceramics (eg artificial joints). Metal-containing nanoparticles such as metal oxide nanoparticles may also find use in cosmetics.
Conventional metal particles typically have grain sizes that fall within the micrometer range and often are supplied in the form of particles having particle sizes greater than the micrometer range. However, metal particles that are comprised of nanometer sized grains may have important advantages over conventional sized metal particles.
Until now, the ability to economically produce useful metal-containing nanoparticles or nanoalloy particles with uniform size and shape has proven to be a major challenge to materials science. Such challenges include producing fine-scale metal-containing nanoparticles, with: (a) the correct chemical composition; (b) a uniform size distribution; (c) the correct crystal structure; and (d) at a low cost.
Nevertheless, metal-containing nanoparticles or nanoalloy particles, such as metal oxides having very small grain sizes (less than 20 nm) have only been attained for a limited number of metal oxides. Processes used to achieve fine grain size for a wide variety of metal-containing nanoparticles or nanoalloy particles are typically very expensive, have low yields and may be difficult to scale up.
Conventional methods used for synthesizing nanoparticle size materials include gas phase synthesis, ball milling, co-precipitation, sol gel, and micro emulsion methods. Descriptions of such processes are provided in U.S. Pat. No. 6,752,979. The foregoing methods are typically applicable to different groups of materials, such as metals, alloys, intermetallics, oxides and non-oxides. Despite the methods described above, there continues to be a need for a simple, highly effective process for making metal-containing nanoparticles on a large scale for use in a variety of applications.
With regard to the above, exemplary embodiments described herein provide methods for making metal-containing nanoparticles. The method includes combining a metal organic compound selected from metal acetates, metal acetyl acetonates, and metal xanthates with an amine to provide a solution of metal organic compound in the amine. The solution is then irradiated with a high frequency radiation source to provide metal nanoparticles having the formula (Aa)m(Bb)nXx, wherein each of A, B is selected from a metal, X is selected from the group consisting of oxygen, sulfur, selenium, phosphorus, halogen, and hydroxide, subscripts a, b, and x represent compositional stoichiometry, and each of m and n is greater than or equal to zero with the proviso that at least one of m and n is greater than zero.
In another exemplary embodiment, the disclosure provides a method for producing oil dispersible nanoparticles. The method includes combining cerium acetate with a hydrocarbyl component to provide a cerium acetate solution. The solution is then irradiated with a high frequency radiation source to provide substantially stabilized dispersion of cerium oxide nanoparticles.
As set forth briefly above, embodiments of the disclosure provide unique nano-sized particles having a substantially uniform size and shape and methods for making such nano-sized particles. Nano-sized particles, particularly metal-containing nanoparticles made according to the disclosed embodiments, may be suitable for making stable dispersions of the nanoparticles in oil or hydrocarbon solvents for use in cosmetics, lubricants, or for use as catalysts in hydrocarbon processes and fuels.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the embodiments disclosed and claimed. The phrase “having the formula” is intended to be non-limiting with respect to nanoparticles or nanoalloy particles described herein. The formula is given for the purposes of simplification and is intended to represent mono-, di-, tri-, tetra-, and polymetallic nanoparticles.
For the purposes of this disclosure, the terms “hydrocarbon soluble,” “oil soluble,” or “dispersable” are not intended to indicate that the compounds are soluble, dissolvable, miscible, or capable of being suspended in a hydrocarbon compound or oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in an oil or hydrocarbon solvent to an extent sufficient to exert their intended effect in the environment in which the oil or solvent is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
As used herein, “hydrocarbon” means any of a vast number of compounds containing carbon, hydrogen, and/or oxygen in various combinations. The term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
The metal-containing nanoparticles described herein are made by a process that provides a substantially uniform size and shape, and metal nanoparticles with the formula (Aa)m(Bb)nXx, wherein each of A and B is selected from a metal, X is selected from the group consisting of oxygen, sulfur, selenium, phosphorus, halogen, and hydroxide, subscripts a, b, and x represent compositional stoichiometry, and each of m and n is greater than or equal to zero with the proviso that at least one of m and n is greater than zero. As set forth above, the metal nanoparticles described herein are not limited to the foregoing one or two metal sulfides or oxides, but may include additional metals as alloying or doping agents in the formula.
In the foregoing formula, A and B of the metal-containing nanoparticles may be selected from Groups 1A, 2A, 3A, 4A, 5A, and 6A of the Periodic Table, transition metals, lanthanides, actinides, and mixtures thereof. Representative metals include, but are not limited to, titanium, zirconium, hafnium, thorium, germanium, tin, niobium, tantalum, molybdenum, tungsten, uranium, cerium, the rare earth metals, copper, beryllium, zinc, cadmium, mercury, aluminum, yttrium, gallium, indium, lanthanum, manganese, iron, cobalt, nickel, calcium, magnesium, strontium, and barium.
The metal-containing nanoparticles described herein may be uniformly spherical, plate-like, or rod-like and will typically have a substantially uniform particle size of less than 50 nanometers. For example, the nanoparticles may have a uniform size ranging from about 1 to about 30 nanometers. Other uniform particle sizes may range from about 2 to about 10 nanometers. Still other uniform particle sizes may range from about 3 to about 6 nanometers.
According to the exemplary embodiments described herein, the metal-containing nanoparticles may be made by a relatively simple process. The process is primarily a two step process that includes combining one or more metal organic compounds with a hydrocarbyl component to provide a solution of metal organic compound in the hydrocarbyl component. The solution of metal organic compound is then irradiated by a high frequency electromagnetic radiation source to provide stabilized metal-containing nanoparticles.
In the first step of the process, one or more metal-organic compounds are dissolved in a hydrocarbyl component that is compatible with oils and hydrocarbon solvents. A suitable hydrocarbyl component is an amine or a mixture of amine and organic acid. The amine may be a saturated or unsaturated hydrocarbyl amine having from about 3 to about 24 carbon atoms. Suitable hydrocarbyl amines include, but are not limited to amines of the formula RNH2 in which R is an unsaturated hydrocarbyl radical having from 3 to 24 carbon atoms. A suitable range for R is from 10 to 20 carbon atoms. R may be an aliphatic or a cycloaliphatic, saturated or unsaturated hydrocarbon radical. Typical unsaturated hydrocarbyl amines which can be employed include hexadecylamine, oleylamine, allylamine, furfurylamine, and the like.
When used, the organic acid may be selected from unsaturated fatty acids containing from about 10 to about 26 carbon atoms. Suitable organic acids include, but are not limited to, oleic acid, erucic acid, palmitoleic acid, myristoleic acid, linoleic acid, linolenic acid, elaeosteric acid, arachidonic acid and/or ricinoleic acid. Fatty acid mixtures and fractions obtained from natural fats and oils, for example peanut oil fatty acid, fish oil fatty acid, linseed oil fatty acid, palm oil fatty acid, rapeseed oil fatty acid, ricinoleic oil fatty acid, castor oil fatty acid, colza oil fatty acid, soya oil fatty acid, sunflower oil fatty acid, safflower oil fatty acid and tall oil fatty acid, may also be used.
The metal organic compound solution may contain a molar ratio of amine to organic acid ranging from about 1:1 to about 3:1 amine to acid. Likewise, the solution may contain a molar ratio of amine to metal organic compound ranging from about 5:1 to about 10:1.
In addition to amines and/or acids other liganding solvents or stabilizers may be used to provide the nanoparticles according to the disclosure. Examples of other suitable hydrocarbyl components include, but are not limited to, alkyl thiols of variable chain length, phosphine surfactants such as trioctylphosphine oxide, and polymers such as polyamides and polystyrene may be used to provide coated nanoparticles. Mixtures of coordinating (liganding) solvents such as oleylamine and oleic acid and non-coordinating solvents such as hexadecene and octadecene may be used to control and/or optimize the shape of the nanoparticles.
After forming the solution of metal organic compound in the hydrocarbyl component, the solution may be heated for a period of time at elevated temperature to remove any water or crystallization and/or to form a clear solution. Accordingly, the solution may be heated and held at a temperature ranging from about 50° to about 150° C. for a period of time ranging from about 1 minute to about 50 minutes depending on the scale of the reaction mixture. A large volume of metal organic compound solution may require a longer heating time, while a smaller volume may require a shorter heating time.
Upon heating the solution, a substantially clear solution of metal organic compound in the hydrocarbyl component is obtained. The clear solution is then irradiated for a period of time using a high frequency electromagnetic radiation source to provide stabilized metal-containing nanoparticles in the hydrocarbyl component. A suitable high frequency electromagnetic radiation source is a microwave radiation source providing electromagnetic radiation with wavelengths ranging from about 1 millimeter to about 1 meter corresponding to frequencies from about 300 GHz to about 300 MHz, respectively. A more suitable frequency range for the electromagnetic radiation ranges from about 0.4 GHz to about 40 GHz. A particularly suitable frequency range is from about 0.7 GHz to about 24 GHz. The irradiation step may be conducted for a period of time ranging from about 10 seconds to about 50 minutes depending on the volume of reactants present in the reaction mixture.
Without being bound by theoretical considerations, it is believed that irradiation of the solution rapidly decomposes the metal-organic compound to produce metal ions which are then coordinated with the hydrocarbyl component to form uniformly dispersed metal-containing nanoparticles that are stabilized or coated by the hydrocarbyl component. It is also believed that the use of microwave radiation leads to selective dielectric heating due to differences in the solvent and reactant dielectric constants that provides enhanced reaction rates. Thus formation of metal-containing nanoparticles by the foregoing process is extremely rapid enabling large scale production of nanoparticles in a short period of time. Since microwave radiation is used, thermal gradients in the reaction mixture are minimized thereby producing a generally uniform heating effect and reducing the complexity required for scale-up to commercial quantities of nanoparticle products.
Microwave heating is able to heat the target compounds without heating the entire reaction container or oil bath, thereby saving time and energy. Excitation with microwave radiation results in the molecules aligning their dipoles within the external electrical field. Strong agitation, provided by the reorientation of molecules, in phase with electrical field excitation, causes an intense internal heating.
After the irradiation step, the stabilized dispersion may be washed with an alcohol to remove any free acid or amine remaining in the stabilized dispersion of nanoparticles. Alcohols that may be used to wash the stabilized metal-containing nanoparticles may be selected from C1 to C4 alcohols. A particularly suitable alcohol is ethanol.
The size and shape of metal-containing nanoparticles produced by the foregoing process depends on the amount of hydrocarbyl component, and heating time used to provide dispersible metal-containing nanoparticles.
The particle size of the metal-containing nanoparticles may be determined by examining a sample of the particles using TEM (transmission electron microscopy), visually evaluating the grain size and calculating an average grain size therefrom. The particles may have varying particle size due to the very fine grains aggregating or cohering together. However, the particles produced by the foregoing process are typically crystalline nanoparticles having a uniform particle size that is substantially in the range of from 1 to 10 nanometers.
The following examples are given for the purpose of illustration only, and are not intended to limit the disclosed embodiments.
The following procedure was used to produce cerium oxide nanoparticles having a particle size of less than 5 nanometers. Cerium acetate (1 gram, 0.00315 mols) was mixed with 7.5 mL of oleylamine (0.2279 mols) and 4.33 mL of oleic acid (0.13 mols) in a suitable vessel. The mixture was heated to 110° C. and held at that temperature for 10 minutes to provide a clear solution of cerium acetate without crystalline water in the solution. Next, the cerium acetate solution was irradiated with microwave irradiation for 10 to 15 minutes to produce a stable dispersion of cerium oxide in the amine and acid. The stabilized dispersion was washed 2-3 times with ethanol to remove any free amine or acid remaining in the dispersion. Finally, the stabilized cerium oxide product was dried overnight under a vacuum to provide the particles have a size of less than 5 nanometers. X-ray diffraction confirmed that nanoparticles of crystalline cerium oxide were produced. UV absorption of the product showed a peak at 300 nanometers which from extrapolation of the absorption edge indicated a band gap of 3.6 eV confirming that the nanoparticles have a diameter of less than 5 nanometers.
The following procedure was used to produce an alloy of magnesium and manganese oxide nanoparticles. Oleylamine (4.25 mL, 0.129 mols) and 1.36 mL of oleic acid (0.04 mols) was mixed in a suitable vessel that was stirred and heated in a hot oil bath to 120° C. and held at that temperature for 10 minutes. A mixture of magnesium acetate (0.14 grams) and manganese acetyl acetonate (0.34 grams) powder was added under vigorous stirring to the amine and acid to provide a clear solution. The solution was then microwaved for 15 minutes. After microwaving the solution, synthesized nanoparticles of magnesium/manganese oxide were flocculated with ethanol, centrifuged, and redispersed in toluene.
The Mg0.3Mn0.7O nanoparticles made by the foregoing process had an x-ray diffraction pattern as shown in
The following procedure was used to produce an alloy of cobalt and iron oxide nanoparticles having a particle size of less than 5 nanometers. Oleylamine (3.75 mL, 0.114 mols) and 3.6 mL of oleic acid (0.11 mols) was mixed in a suitable vessel that was stirred and heated in a hot oil bath to 120° C. and held at that temperature for 15 minutes. A mixture of iron acetyl acetonate (0.45 grams) and cobalt acetyl acetonate (0.16 grams) powder was added under vigorous stirring to the amine and acid to provide a clear solution. The solution was then microwaved for 10 minutes. After the solution was cooled, 300 μL hydrogen tetrachloroaurate (30 wt. % solution in hydrochloric acid) were injected into the alloyed particle solution under vigorous stirring for 10 minutes. The synthesized nanoparticles of cobalt/iron oxide were flocculated with ethanol, centrifuged, and redispersed in toluene.
The CoFe2O4 nanoparticles made by the foregoing process had an x-ray diffraction pattern as shown in
The following procedure was used to produce an alloy of copper and zinc sulfide nanoparticles having a particle size of less than 5 nanometers. A mixture of copper xanthate (0.17 grams) and zinc xanthate (0.17 grams) was added to 3 grams of hexadecylamine (0.012 mols) that was preheated in a hot oil bath to 80-110° C. and held at that temperature for 15 minutes to form a clear solution. The solution was then microwaved for 2 minutes with 30 second cycles (10 seconds off and 20 seconds on). After microwaving the solution, synthesized nanoparticles of copper/zinc sulfide were flocculated with methanol, centrifuged, and redispersed in toluene or dichloromethane.
The CuS and ZnS nanoparticles made by the foregoing process had an x-ray diffraction pattern as shown in
At numerous places throughout this specification has been made to one or more U.S. patents. All such cited documents are expressly incorporated in full into this disclosure as if fully set forth herein.
The foregoing embodiments are susceptible to considerable variation in its practice. Accordingly, the embodiments are not intended to be limited to the specific exemplifications set forth hereinabove. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including the equivalents thereof available as a matter of law.
The patentees do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.
