Nanoparticles and their manufacturing method

Abstract

A process for producing nanoparticles from solid-phase precursor non-nanoparticles. A solid-phase precursor non-nanoparticle selected from metal and metalloid oxides, metal and metalloid carbides, metal and metalloid nitrides, metal and metalloid borides, metal and metalloid silicides, and metal and metalloid phosphides, and mixtures thereof, is contacted with one or more onium ions in water in a vessel. Some processes can be one-pot processes. The vessel is stirred and held at a temperature for a time sufficient to form nanoparticles having the same crystal structure as the solid-phase precursor non-nanoparticles as determined by XRD and / or TEM. Nanoparticles produced by this process. Processes for using this nanoparticles.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Patent Application No. 63 / 214,660, "Nanoparticles and Process of Producing Same," filed June 24, 2021, the entirety of which is incorporated herein by reference for all purposes.

[0002] Government Rights This invention was made with Government support under Contract No. 1740795 awarded by the National Science Foundation. The Government has certain rights in this invention.

[0003] Technical Field FIELD OF THE DISCLOSURE This disclosure relates generally to the field of nanomaterials, and more specifically to nanoparticles and processes for making and using same.

[0004] background Specific synthetic processes are employed to produce various nanoparticles, coatings, dispersions, or composites. Two basic strategies are used to produce nanoparticles: "top-down" and "bottom-up".

[0005] In the "bottom-up" strategy, structures are built by chemical processes. Bottom-up methods are based on physicochemical principles of self-organization of molecules or atoms. Gas-phase processes (aerosol processes) usually require flame, plasma, laser or hot-wall furnaces, resulting in products such as fullerenes or carbon nanotubes. These processes require high temperatures (1200-2200 °C) and / or very low pressures (vacuum). Wet chemical synthesis of nanomaterials is usually performed at lower temperatures than gas-phase synthesis, but is still a complex process. In the precipitation of solids from metal ion-containing solutions, not only metal oxides but also non-oxides and metal nanoparticles can be produced. The process is based on the reaction of salts in a solvent. A precipitating agent is added to obtain the desired particle precipitation, and the precipitate is filtered and thermally post-treated. The temperature, the pH value of the solution, the order of adding the raw materials, and the mixing process can affect the reaction kinetics.

[0006] Nanoreactors such as microemulsions, bubbles, micelles and liposomes are known. They consist of polar groups and non-polar hydrocarbon chains. Microemulsions require at least one surfactant (a substance that reduces the surface tension of the liquid) and at the same time it is difficult to prevent the particles from agglomerating. Zeolites (microporous aluminum-silicon compounds) are produced from superheated aqueous solutions in an autoclave (an airtight pressure chamber). Partial evaporation of the solvent creates pressure (several bars) in the autoclave, which causes chemical reactions that differ from those under standard conditions, such as changes in solubility.

[0007] Sol-gel processes involve the production or deposition of materials through a complex series of steps that transform a liquid sol state into a solid gel state through a sol-gel transformation. The sol-gel transformation involves three-dimensional cross-linking of nanoparticles in a solvent, which gives the gel its bulk properties. A controlled heat treatment in air can transform the gel into a ceramic oxide material. First, the sol-gel process produces organometallic compounds from a solution containing alkoxides (alcohols and metal compounds, e.g. silicon, titanium, aluminum) when an organic substance is added. The pH value of the solution is adjusted with an acid or base, which acts as a catalyst to induce the transformation of the alkoxide.

[0008] The subsequent reactions are hydrolysis (breaking of chemical bonds by water), condensation and polymerization. The course of the hydrolysis and polycondensation reactions depends on many factors, including the composition of the initial solution, the type and amount of catalyst, the temperature, the geometry of the reactor and the mixer. In all cases, gel formation is followed by a drying step. One of the disadvantages of the sol-gel method is the synthesis and drying steps, which are difficult to control, complicating the scale-up of the process. Furthermore, organic contaminants may remain in the gel. As a result, the necessary washing steps, drying and thermal post-treatments make this manufacturing process more complicated than gas-phase synthesis.

[0009] One drawback of wet chemical synthesis of nanomaterials is that it is often not possible to produce the desired crystalline shape and the resulting powders have low thermal stability, requiring thermal post-treatment.An advantage is that the liquid phase allows the production of highly porous materials that are usually not possible in gas phase reactors due to the high temperatures.

[0010] It would be an advancement in nanoparticle production if processes could be developed that exhibited cost-related improvements in energy efficiency, starting materials, or both, particularly for producing nanoparticles from relatively low-cost, typically solid chemical compositions, and that avoided potentially unsafe temperature and pressure conditions. Summary of the Invention

[0011] In accordance with the present disclosure, nanoparticles, and processes for making same, are described that reduce or overcome many of the shortcomings of previously known processes.

[0012] A first aspect of the present disclosure is a process comprising (or consisting essentially of, or consisting of):

[0013] a) mixing a solid-phase precursor, optionally non-nanoparticulate, selected from metal oxides, metal oxides, metal carbides, metal oxide carbides, metal nitrides, metal oxide nitrides, metal borides, metal oxide borides, metal phosphides, metal oxide phosphides, metal silicides, metal oxide silicides, and mixtures thereof, with one or more onium ions (e.g., ammonium ions) from one or more onium salts, in water (in certain embodiments, deionized water), with ammonium ions; contacting the mixture in a vessel with sufficient stirring at a temperature and for a time sufficient to form nanoparticles, said temperature being in the range of about 0° C. to about 100° C. (or about 25° C. to about 95° C., or about 30° C. to about 90° C., or about 35° C. to about 80° C.) for a period of at least 10 minutes (or in the range of about 1 to about 200 hours, or about 10 to about 190 hours, or about 12 to about 192 hours, or about 24 to about 144 hours, or about 48 to about 96 hours);

[0014] b) optionally contacting the nanoparticles of part (a) with an organic solvent (e.g., an alcohol, an ether, or a mixture thereof) to remove excess water;

[0015] c) optionally contacting the nanoparticles of part (b) with an inorganic salt solution (e.g., 1M LiCl) to form further purified nanoparticles; and d) optionally filtering and drying the nanoparticles of part (c) to form dry nanoparticles.

[0016] Without being bound to a particular theory or embodiment, nanoparticles according to the present disclosure can include 1Da (i.e., one-dimensional anatase material). 1Da can also be referred to as quat-derived nanomaterials (QDN).

[0017] The 1Da can include oxide-based nanofilaments and / or sub-nanofilaments, and can optionally include amounts of carbon. (As described herein, the nanofilaments can include, for example, titanium.) The composition can exist as a mesoporous powder in which the powder particulates include oxide-based nanofilaments and / or sub-nanofilaments. The 1Da composition can exist in the form of flakes, e.g., 2D bodies formed (e.g., via self-assembly) from the 1Da filaments. The 1Da composition can also exist as 3D bodies, e.g., nanoparticles.

[0018] 1 Da can exhibit an XRD pattern that exhibits reduced (104) and (105) peaks at about 38° and about 55° two-theta (2θ) when compared to the XRD pattern of nano or bulk anatase. 1 Da nanofilaments and / or sub-nanofilaments can, in some embodiments, exhibit Raman spectra very similar to those of bulk anatase, but can differ from bulk anatase with respect to their XRD spectra, as described herein.

[0019] 1Da can be obtained by reacting a starting material (e.g., MAX phase material, carbide, nitride, boride, sulfide, metal, etc.) with an onium salt (ammonium salt, TMAOH, TBAOH, TPAOH, etc.) at, for example, ambient pressure and at a temperature between room temperature and 100° C. The mixture can optionally include an ammonium salt. 1Da can exist as a 2D material, as described above, but this is not a requirement, as 1Da can also exist as nanoparticles, nanoribbons, nanowhiskers, nanotubes, 1D materials (e.g., fibers), or other forms.

[0020] In certain processes, the metals of the oxides, nitrides, carbides, silicides, borides, and phosphides can be selected from one or more transition metals, elements from groups 3 to 12 of the periodic table, or mixtures and combinations thereof. In certain embodiments, the transition metals can be selected from one or more of V, Nb, Mn, and Ti, and mixtures and combinations thereof. In certain embodiments, the metals can be selected from one or more alkaline earth metals, and mixtures and combinations thereof, including, but not limited to, Mg. In certain embodiments, the metalloid can be Si, although other metalloids (B, As, Ge, Sb, P, and Te) are also contemplated within the present disclosure. In some cases, metalloids and nonmetals, such as Si3N4, are also used.

[0021] A second aspect of the present disclosure is a nanoparticle produced from the process of the first aspect of the present disclosure. The specific product of the process of the first aspect comprises the same chemical formula as the solid phase precursor. The final composition of the nanoparticle is the same as the composition of the non-nanoparticle of the solid phase precursor.

[0022] As used herein, "composition" refers to the types of constituent atoms of the solid-phase precursor non-nanoparticles and the resulting nanoparticles. However, this does not mean that the atomic ratio is constant when comparing the solid-phase precursor non-nanoparticles to the nanoparticles; in fact, there is evidence that it varies. Furthermore, in all embodiments, the crystal structure of the nanoparticles (as determined by X-ray diffraction or XRD and / or transmission electron microscopy or TEM) remains the same as that of the solid-phase precursor non-nanoparticles.

[0023] However, this does not mean that the XRD peaks of the solid precursor non-nanoparticles and the nanoparticles will necessarily have the same shape. For example, the XRD peaks of the nanoparticles may be broader than the corresponding XRD peaks of the solid precursor non-nanoparticles. The solid precursor non-nanoparticles simply shrink in size to the nanoparticle scale.

[0024] A "nanoparticle" can comprise, consist essentially of, or consist of nanoparticles of the same structure as determined by XRD. For example, a nanoparticle can contain a small portion (e.g., less than 50%) of non-nanomaterials, a nanoparticle can consist substantially of nanoparticles and trace amounts (up to 5%, or up to 2%, or up to 0.1%) of non-nanomaterials, such as water, organic solvents, or other solid non-nanomaterials that do not impair the properties of the nanoparticles, or mixtures and combinations thereof, and a nanoparticle can consist of nanoparticles (and only nanoparticles). In certain process embodiments, washing the nanoparticles with a weak acid such as HCl can remove other reaction products, such as metal carbide oxides (MCO), that may be produced at the same time as the nanoparticles. We have found that, for example, HCl dissolves MCO but not nanoparticles, and thus production of substantially pure nanoparticles is possible using the processes of the present disclosure.

[0025] A third aspect of the present disclosure is an apparatus for carrying out the steps of the first aspect of the present disclosure.

[0026] Processes using one or more nanoparticles of the present disclosure are also provided, including, but not limited to, property-enhancing fillers in polymeric materials, and biomedical applications, such as cancer treatment.

[0027] The nanoparticles, devices, systems, and processes for making and using the nanoparticles of the present disclosure will become more apparent upon review of the Brief Description of the Drawings, the Detailed Description of the Disclosure, and the Claims that follow. [Brief description of the drawings]

[0028] In the drawings, which are not necessarily drawn to scale, like numerals may represent like components in different views. Like numerals with different letter suffixes may represent different instances of like components. The drawings illustrate generally, by way of example, but not by way of limitation, various aspects discussed in the present specification. In the drawings: [Figure 1]FIG. 1 is a schematic process flow diagram of a process and system embodiment according to the present disclosure. [Diagram 2] FIG. 2 is a more detailed schematic process flow diagram of another process and system embodiment according to the present disclosure. [Diagram 3] FIG. 3 is an illustrative diagram of a process according to the present disclosure. [Figure 4] FIG. 4 is an illustrative diagram of a process according to the present disclosure. [Diagram 5] Figure 5A is a photograph of an exemplary, non-limiting laboratory experiment and exemplary, non-limiting nanoparticles produced in accordance with the present disclosure. Figure 5B is a photograph of an exemplary, non-limiting laboratory experiment and exemplary, non-limiting nanoparticles produced in accordance with the present disclosure. [Figure 6] Figure 6A is an exemplary, non-limiting laboratory experiment and a photograph of exemplary, non-limiting nanoparticles produced in accordance with the present disclosure. Figure 6N is an exemplary, non-limiting laboratory experiment and a photograph of exemplary, non-limiting nanoparticles produced in accordance with the present disclosure. [Figure 7] Figure 7A is a photograph of an exemplary, non-limiting laboratory experiment and exemplary, non-limiting nanoparticles produced in accordance with the present disclosure. Figure 7B is a photograph of an exemplary, non-limiting laboratory experiment and exemplary, non-limiting nanoparticles produced in accordance with the present disclosure. [Figure 8] FIG. 8 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 9] FIG. 9 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 10] FIG. 10 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 11] FIG. 11 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 12] FIG. 12 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 13] FIG. 13 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 14] FIG. 14 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 15] FIG. 15 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 16] FIG. 16 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 17] FIG. 17 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 18] FIG. 18 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. [Figure 19] FIG. 19 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The present disclosure may be understood more readily by reference to the following detailed description of the preferred embodiments and the examples included therein.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In case of conflict, the present specification, including definitions, shall prevail. Preferred methods and materials are described below, but methods and materials similar or equivalent to those described herein may be used in the practice or testing. All publications, patent applications, patents and other documents described herein are incorporated by reference in their entirety. The materials, methods and examples disclosed herein are illustrative only and are not intended to be limiting.

[0031] The singular forms "a," "an," and "the" include plural referents unless the context clearly indicates otherwise.

[0032] As used herein and in the claims, the term "comprising" can include the embodiments "consisting of" and "consisting essentially of." As used herein, the terms "comprise(s)," "include(s)," "having," "has," "can," "contain(s)," and variations thereof are intended to be open-ended transitional phrases, terms, or words that require the presence of the recited components / steps and permit the presence of other components / steps. However, such descriptions should be construed as also describing the composition or process as "consisting of" and "essentially consisting of" the recited components / steps, which permits only the presence of the recited components / steps along with impurities that may result therefrom, and excludes other components / steps.

[0033] As used herein, the terms "about" and "at or about" mean that the quantity or value in question may be approximately or nearly the same as the other value specified. As used herein, it is generally understood to be a variation of ±10% of the nominal value unless otherwise indicated or inferred. The term is intended to convey that similar values ​​promote the same results or effects as described in the claims. That is, it is understood that the amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be precise, but can be approximated and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. In general, the amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate", whether or not they are expressly stated as such. When "about" is used before a quantitative value, it is understood that the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0034] Unless otherwise indicated to the contrary, numerical values ​​should be understood to include numerical values ​​that are the same when reduced to the same significant figures, and numerical values ​​that differ from the stated value by less than experimental error using conventional measuring techniques of the type described herein to determine the numerical value.

[0035] All ranges disclosed herein are inclusive of and independent of the endpoints recited. The endpoints of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values, but are sufficiently imprecise to include values ​​that are close to those ranges and / or values.

[0036] As used herein, approximation may be applied to modify any quantitative expression that may vary without resulting in a change in the basic function to which it is related. Thus, a value modified by terms such as "about" or "substantially" may not be limited to the exact value specified in some cases. In at least some instances, an approximation may correspond to the precision of an instrument measuring the value. The modifier "about" should also be considered to disclose a range defined by the absolute values ​​of the two endpoints. For example, the phrase "about 2 to about 4" also discloses a range of "2 to 4". The term "about" may refer to plus or minus 10% of the indicated numerical value. For example, "about 10%" may indicate a range of 9% to 11%, and "about 1" may mean 0.9 to 1.1. Other meanings of "about" are clear from the context, such as rounding, so for example, "about 1" may also mean 0.5 to 1.4. Additionally, the term "comprising" should be understood to have the open-ended meaning of the term "including," but the term "comprising" also includes the closed meaning of the term "consisting." For example, a composition comprising components A and B can be a composition comprising A, B, and other components, but can also be a composition consisting of only A and B. All documents cited herein are incorporated by reference in their entirety for all purposes.

[0037] Moreover, the use of negative limitations is specifically contemplated; for example, certain compositions, devices, systems, and processes can include numerous physical elements and features, but can lack certain optional chemical species, hardware, and / or other features. For example, certain nanoparticle embodiments can lack ingredients that are incompatible with nanoparticles. Certain nanoparticle compositions can lack MCO. Certain device embodiments can include containers that lack gaskets or O-rings, or welded or threaded joints. In certain embodiments, solid precursor non-nanoparticle materials can lack other than metal oxides.

[0038] As discussed elsewhere herein, most bottom-up processes for producing nanoparticles are either gas or liquid phase, with gas phase processes generally requiring high temperatures and low pressures, and liquid phase processes requiring complex processing involving many steps, all of which significantly increase capital and operating costs and increase the likelihood of accidents, especially at high temperatures and low pressures.

[0039] The following aspects and embodiments are merely illustrative and do not limit the scope of the disclosure or the appended claims.

[0040] A first aspect of the present disclosure is a process comprising (or consisting essentially of, or consisting of):

[0041] a) mixing a solid-phase precursor non-nanoparticle selected from a metal oxide, a metalloid oxide, a metal carbide, a metal semi-carbide, a metal nitride, a metal semi-nitride, a metal boride, a metal semi-boride, a metal sulfide, a metal semi-sulfide, a metal phosphide, a metal semi-phosphide, a metal silicide, a metal semi-silicide, and mixtures and combinations thereof, with one or more onium ions derived from one or more onium salts (e.g., ammonium salts) in water in a container for a sufficient amount of time; contacting the mixture for at least 10 minutes with stirring at a temperature and for a time sufficient to form nanoparticles, said temperature being in the range of about 0° C. to about 100° C. (or about 25° C. to about 95° C., or about 30° C. to about 90° C., or about 35° C. to about 80° C.) and said time being in the range of at least 10 minutes (or about 1 to about 200 hours, or about 10 to about 190 hours, or about 12 to about 192 hours, or about 24 to about 144 hours, or about 48 to about 96 hours);

[0042] b) optionally contacting the nanoparticles of (a) with an organic solvent (e.g., an alcohol, an ether, or a mixture thereof) to remove excess water;

[0043] c) optionally contacting the nanoparticles of (b) with an inorganic salt precipitation solution (e.g., 1 M LiCl); and

[0044] d) optionally filtering and drying the nanoparticles of (c) to form dry nanoparticles.

[0045] In certain embodiments, the "metal" (sometimes referred to herein simply as "M") can be at least one metal selected from the group consisting of Group 2 (alkaline earth metals), Groups 3-12 (transition metals), and combinations and mixtures thereof. In certain embodiments, the metal is at least one metal selected from the group consisting of Ti, Mn, Ni, Fe, and Mg, and combinations and mixtures thereof. In certain embodiments, the metal is at least one metal selected from the group consisting of Ti and Mg, and combinations and mixtures thereof.

[0046] In certain embodiments, the metal can be at least one Group 4 metal, such as Ti, Zr, and Hf, and combinations and mixtures thereof. In certain process and composition embodiments, the metal can be at least one Group 5-12 metal, such as, but not limited to, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, and Au, and combinations and mixtures thereof. In certain process and composition embodiments, the metal can be at least one Group 8 metal. In certain process embodiments, M is at least one Group 8 metal. In certain process embodiments, M can be at least one Group 4 metal. In certain process embodiments, M is at least one Group 4 metal. In certain process embodiments, M can be at least one Group 2 alkaline earth metal. In certain process embodiments, M is at least one Group 2 alkaline earth metal.

[0047] In certain embodiments, the metalloid (sometimes referred to herein simply as ("MD")) can include one or more MD selected from the group consisting of B, Si, Ge, As, Sb, Te, P, and S, and combinations and mixtures thereof. In certain embodiments, the MD is one or more metalloids selected from the group consisting of Si and Ge, and combinations and mixtures thereof. In certain embodiments, the MD can include Si and one or more of B, Ge, As, Sb, Te, S, and P, and combinations and mixtures thereof. In certain embodiments, the MD is a mixture or combination of Si and one or more of B, Ge, As, Sb, Te, P, and S, and combinations and mixtures thereof. In certain embodiments, the MD can include Si and one or more of B and Ge, and combinations and mixtures thereof. In certain embodiments, the metal can be bonded to any one or more reactive nonmetals (C, O, N, F, P, S, Cl, Se, Br, and I). In certain embodiments, the metalloid can bond to any one or more reactive nonmetals (C, O, N, F, P, S, Cl, Se, Br, and I).

[0048] Another aspect of the present disclosure is nanoparticles prepared according to the processes of the present disclosure. Certain process embodiments can use at least a portion of precursor non-nanomaterials having an anatase structure. Certain process embodiments can result in at least a portion of nanoparticles having an anatase-like or rutile-like structure. Certain process embodiments can use at least a portion of solid phase precursor non-nanomaterials having an anatase-like or rutile-like structure, resulting in the formation of nanoparticles, at least a portion of the nanoparticles having an anatase-like or rutile-like structure.

[0049] Certain processes can be carried out at temperatures ranging from about 0° C. to about 100° C., or from about 25° C. to about 95° C., or from about 30° C. to about 90° C., or from about 35° C. to about 80° C., for a time period ranging from at least 10 minutes, or from about 1 to about 200 hours, or from about 10 to about 190 hours, or from about 12 to about 192 hours, or from about 24 to about 144 hours, or from about 48 to about 96 hours. In certain process embodiments, the nanoparticles are produced using a so-called "one-pot" process (synthesis carried out in a single reaction vessel or container); in other words, the nanoparticles are produced directly in one container by contacting a solid-phase precursor non-nanoparticle with one or more onium ions derived from one or more onium salts in water at the times, temperatures, and pressures indicated herein, without further modifications and / or steps taught by the prior art.

[0050] Certain processes can be carried out at pressures ranging from subatmospheric to superatmospheric pressure, or from vacuum or near vacuum to a few bars, or from atmospheric to 10 bars, or from about 1 bar to about 5 bars.

[0051] The nanoparticles of the present disclosure can be conductive, non-conductive, semiconducting, porous, mesoporous (as described in U.S. Pat. No. 9,562,005), or non-porous, where "porous" includes mesoporous and more than mesoporous porosity, "nonporous" means less than mesoporous, and "mesoporous" refers to a porous material having an average pore size in the range of about 2 to about 50 nanometers (nm).

[0052] Solid-phase precursor non-nanoparticles

[0053] The solid-phase precursor non-nanoparticles serve as a source of metals (M) or metalloids (MD) and one or more reactive non-metals, such as, but not limited to, O, C, B, S, P, Si, N atoms, and combinations thereof, to generate nanoparticles. Suitable solid-phase precursor non-nanoparticles can be two-dimensional, three-dimensional, four-dimensional or higher dimensional materials. Two-dimensional materials can be, but are not limited to, TiC, TiB2, TiN, Ti5S3, TiAl3, TiO2, MnB, MgO, Si3N4, CoO, iron oxides, such as, but not limited to, Fe2O3, Mn3O4, MnO2, FeB, ZrC, Si3N4, SiC, and combinations or mixtures thereof. Other suitable solid-phase precursor non-nanoparticles can be three-dimensional M-containing materials or three-dimensional MD-containing materials. Three-dimensional M-containing and / or MD-containing materials can be, for example, but are not limited to, Ti3AlC2, Ti3SiC2, Ti3GaC2, Ti2SbP, Mn5SiB2, Mn2AlB2, Fe5SiB2, Fe2AlB2, Zr3AlC5, V2AlC, Nb2AlC, and combinations and mixtures thereof.

[0054] Onium cations and their salts

[0055] Without being bound to a particular theory, the onium salt (or its cation and / or anion) functions to chemically react with at least a portion of the non-nanoparticles of the solid-phase precursor to induce the formation of nanoparticles. The name onium is also used for cations resulting from the replacement of hydrogen atoms in the ion with other groups such as organic radicals or halogens. For example, tetraphenylphosphonium, (C6H5)4P+. The substituents can be divalent or trivalent, resulting in ions such as iminium and nitrilium. The onium ion of the onium salt can have a charge of +1, +2 (double onium), +3 (triple onium), or even higher.

[0056] The onium cation can have monovalent or polyvalent substitution.Suitable examples of monovalent substituted onium cations include, but are not limited to, primary onium cations in the formula RH3N+ (such as NH3OH+), secondary onium cations in the formula R2NH2+ (such as (CH3)2NH2+), tertiary onium cations in the formula R3NH+ (such as (CH3)3NH+), and quaternary onium cations in the formula R4N+, where R can be an organic or inorganic moiety.Enium cations, substituted enium cations, and inium cations are also contemplated in the present disclosure, where the substitution is organic or inorganic.

[0057] In certain embodiments, the onium ion may be derived from one or more onium salts, such as ammonium salts. Suitable ammonium salts include, but are not limited to, tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH), ammonium hydroxide (NH4OH), tetrahexylammonium hydroxide (THAOH), their amine derivatives, and combinations and mixtures thereof.

[0058] In other embodiments, the onium salt can be based on a protonated pnictogen, a protonated chalcogen, or a protonated halogen. An example of a pnictogen onium cation is NH + (Ammonium), pH 4 + (phosphonium), AsH4 + (Arsonium), SbH4 + (stibonium), and BiH4 + (bismuthium). Examples of chalcogenonium cations include (HO + (Oxonium), H3S + (Sulfonium), H3Se + (selenonium), and H3Te + (telluronium). An example of a halogen onium cation is H2F + (Fluoronium), H2Cl +(Chloronium), H2Br + (Br), and H2I + (iodonium). An example of a pseudohalogen onium cation is H2N3 + (aminodiazonium) and HCNH + (HC≡CH + Isomers, or C≡CH2 + Suitable carbo-onium cations include carbonium ions, e.g., alkanium cations, C n H2 n+3 + (For example, CH5 + (Methanium), C2H7 + (Ethanium), C3H9 + (either propanium, propan-1-ylium isomers, or propan-2-ylium isomers, or both), C4H 11 + (Butanium, one or more isomers, or a combination of two or more isomers), C8H 19 + (octonium, one or more isomers, or a combination of two or more isomers), Si n H 2n+3 + (silanium), GeH5 + Germanium, SnH3 + Stannonium, PbH3 + Other suitable onium cations include BH4 + (boronium cation) and formula B x H y + Protonated borane, HeH + (Heronium), NeH + (Neonium), ArH + (Argonium), KrH + (Kryptonium), XeH + (xenonium), and H3 + (hydrogenonium, or trihydrogen cation).

[0059] In certain embodiments, the onium ion can be selected from diquat, aliquat, polyquat, and other forms. Examples of diquat include, but are not limited to, didodecyldimethyl-gamma-diquaternium salt, N-dodecylpropylenediamine gamma-diquaternium bromide, etc. Examples of aliquat include, but are not limited to, N-methyl-N,N,N-trioctylammonium chloride (known as aliquat 336), tetrabutylammonium bromide (known as aliquat 100), methyltri-n-butylammonium chloride (known as aliquat 175), etc. Examples of polyquats include, but are not limited to, ethanol, 2,2',2''-nitrilotris-, polymer of 1,4-dichloro-2-butene and N,N,N',N''-tetramethyl-2-butene-1,4-diamine (also known as polyquaternium-1), poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea] (also known as polyquaternium-2), and the like (polyquaternium-X, where X is a number between 1 and 47, inclusive, assigned in accordance with the rules of the Personal Care Products Council (PCPC), indicating the order of registration of cosmetic ingredients in the International Nomenclature System).

[0060] In certain process embodiments, the onium salt is a cation ion that is a mixture of one or more oxidizing agents, such as H2O2, halogens such as fluorine (F2), chlorine (Cl2), and bromine (Br2), and permanganate ions (MnO4 - ) and dichromate ion (Cr2O7 2- ), as well as mixtures and combinations thereof.

[0061] In embodiments using one or more oxidizing agents, the molar ratio of onium salt to oxidizing agent can range from about 5:1 to about 1:5, or from about 4:1 to about 1:4, or from about 3:1 to about 1:3, or from about 2:1 to about 1:2.

[0062] In certain embodiments, the onium cation is present in water and the anion is a hydroxyl anion OH - However, the anion of the onium salt is not limited to the hydroxyl anion, but can be any organic or inorganic moiety, for example, a halogen anion (Fl - , Cl - etc.), complex halogen anions (e.g., [FeBr4] - etc.), but are not limited to these.

[0063] Organic solvents

[0064] The organic solvent, if used, functions to wash or purify the nanoparticles and remove excess water. The organic solvent can, for example, but is not limited to, remove some or all of the unreacted solid phase precursors, unreacted ammonium cations and anions, undissolved ammonium salts, etc. Suitable organic solvents include, but are not limited to, liquid oxygenated hydrocarbons such as alcohols, glycol ethers, and ketones. Examples of suitable alcohols include, but are not limited to, compounds such as ethyl alcohol (or ethanol), propyl alcohol (or propanol), n-butyl alcohol, t-butyl alcohol, etc. Suitable glycol ethers include, but are not limited to, ethylene glycol ether and propylene glycol ether. Suitable hydrocarbon solvents include pentane, hexane, heptane, octane, benzene, and mixtures and combinations thereof. Examples of these include normal, branched, and cyclic. Halogenated hydrocarbon solvents such as chlorobenzene, iodobenzene, etc. may also be suitable. Polar aprotic solvents such as dimethylformamide (DMF) can also be used alone, in combination with other polar aprotic solvents, or in mixtures and combinations with any of the above.

[0065] Inorganic salt solutions

[0066] If used, the inorganic salt solution also functions to wash or purify the nanoparticles, remove excess moisture, and / or dissolve other reaction products (not the nanoparticles). Suitable inorganic salt solutions include, but are not limited to, solutions of alkali metal and halogen salts, such as LiCl, NaCl, LiBr, and mixtures of two or more thereof, in molar amounts ranging from 0.001 up to 10 M. Other weak acids, such as HCl and citric acid, can also be used in similar molar ranges.

[0067] Centrifugation and filtration equipment

[0068] Once formed in the vessel, in certain embodiments, the nanoparticles are centrifuged (and / or ultracentrifuged) one or more times until a clear supernatant is formed, and then filtered. Suitable centrifugation techniques are well known and require little explanation. Benchtop and floor-standing centrifuges are available from Fisher Scientific, Eppendorf, Beckman Coulter, and others. Commercial-scale centrifuges, such as disc stack centrifuges, are available from Alfa Laval, and others. Suitable filtration techniques include gravity filtration and vacuum filtration. Suitable commercial-scale filtration units may include rotary vacuum filters, refrigerant-based chilled filters, and the like.

[0069] container

[0070] Suitable vessels for use in the process of the present disclosure may be continuous, semi-continuous, batch, or semi-batch reactors. When the onium ion is derived from TMAOH, polyethylene vessels (polyethylene, or polyethylene-lined vessels) have been found to be effective, but glass or glass-lined metal vessels have not. Glass or glass-lined steel (or PTFE, PFA, tantalum) vessels can be used in certain embodiments (e.g., when onium salts other than TMAOH are used). The volume of the vessel can range from laboratory scale (50 mL) to commercial scale (10,000 L or more) and can include accessories such as, but not limited to, pressure and temperature measuring devices, stirring devices, motors for running the stirrer, one or more inlets and outlets for inert gas purging, heating and cooling equipment, timers, and one or more human / machine interfaces (HMIs). Certain vessels can include one or more process controllers, pressure relief valves, access ways for human or non-human testing, sampling ports, pH probes, and the like. A suitable container must be capable of withstanding temperatures up to 200°C and pressures up to 2 bar for a period of up to 250 hours or more.

[0071] Inert gas

[0072] Generally, it is not necessary to use an inert gas blanket on the vessel, but in certain embodiments, it may be desirable. Examples of suitable inert gases include, but are not limited to, nitrogen, argon, hydrogen, and mixtures thereof. The source of the inert gas may be one or more conduits, pipelines, storage facilities, or cylinders. The inert gas may be supplied from a pipeline, cylinder, storage facility, cryogenic separation unit, membrane permeation separator, or adsorption unit such as a vacuum swing adsorption unit.

[0073] Referring now to the drawings, FIG. 1 is a high-level schematic process flow diagram of one process and system embodiment 100 according to the present disclosure, including vessel 2, optional organic solvent washer 4, optional inorganic salt solution washer 6, water wash vessel 8, optional centrifuge or shaker 10, and optional filter 12. In certain embodiments, some (or all) of these vessels or stages can be combined. Solid phase precursor non-nanoparticle material 18 (e.g., solid TiO2, TiN, TiC, Si3N4, and MgO as described in the Examples herein) is delivered to vessel 2, as is onium salt solution 20. After increasing the temperature and holding for a period of time as described in the Examples, vessel 2 produces nanoparticle composition 22, which is delivered to optional organic solvent washer 4, as is organic solvent 24. From optional organic solvent washer 4, a nanoparticle composition including reduced water 26 is produced, which can be delivered to optional vessel 6 along with optional inorganic salt solution 28 (e.g., 1M aqueous solution of LiCl). Optional vessel 6 and optional inorganic salt can be used to further wash the nanoparticles. The nanoparticles 30 are then sent to a vessel 8 for topping off with water 32 and through a conduit 33 to a centrifuge or shaker 10 where waste liquid and solids are removed (at 34). The supernatant liquid 35 is observed by human or machine vision, or both (14), and if clear (Y), no further centrifugation or shaking is required, but if the supernatant liquid is not clear (N), centrifugation or shaking is repeated until the supernatant liquid is clear. The final water-filled suspension of nanoparticles is then sent to a filter 12 to form a "filter film" of nanoparticles 36 and a waste stream 38.

[0074] 2 is a more detailed schematic process flow diagram of another process and system embodiment 200 according to the present disclosure. The embodiment 200 differs from the embodiment 100 in that an agitator or stirrer 64, 66 is included in the vessel 2 and the optional organic solvent washer 4, respectively, as well as various pumps and control valves, and a chute 19 for transferring the solid phase precursor non-nanoparticle material to the vessel 2. A pump 68 transfers the aqueous onium solution 20 to the vessel 2, a pump 70 transfers the nanoparticles from the vessel 2 to the optional organic solvent washer 4, a pump 72 transfers the nanoparticles from the optional organic solvent washer 4 to the optional vessel 6, optionally contacted with the inorganic salt solution 28, and a pump 74 transfers the nanoparticles to the water-filled vessel 8, where additional water is added for centrifugation or shaking, and the material is transferred by pump 82 to the centrifuge or shaker 10. After the supernatant liquid becomes clear as observed by human or machine vision at 14, the nanoparticles are transferred to a filter 12. A series of control valves 76, 78, 80, 84, 86, 88, and 90 (some of which are optional) are controlled by one or more supervisory controllers 92 (such as a supervisory computer) that control flow from pumps 68, 70, 72, 74, and 82, respectively, and can operate via wired or wireless control signals to operate the control valves, pumps, agitators, and other devices. Those skilled in the chemical processing arts will appreciate that many variations of embodiment 200 are possible. Additionally, many sensors that may be included in a particular industrial embodiment are not shown, such as mass flow sensors or meters, temperature sensors, pressure sensors, pH sensors, weight sensors, etc. One or more of these sensors or meters may also be controllers, such as a temperature indicating controller, a pressure indicating controller, etc. These sensors are not shown in FIG. 2 for simplicity.

[0075] 3 and 4 are logic diagrams of two process embodiments 300, 400 according to the present disclosure. Process embodiment 300 includes contacting a solid phase precursor non-nanoparticle material with onium ions derived from ammonium salts in deionized water in a container at atmospheric pressure with sufficient agitation at a temperature and for a time sufficient to form a nanoparticle composition, where the temperature ranges from about 0° C. to about 100° C. and the time is 10 minutes or longer, Box 302. Process embodiment 300 further includes optionally contacting the nanoparticle composition with an organic solvent to form a reduced aqueous nanoparticle composition, Box 304, and then optionally contacting the reduced aqueous nanoparticle composition with an inorganic salt solution, Box 306. Process embodiment 300 continues with centrifugation, Box 308, and filtration of the nanoparticle composition, Box 310.

[0076] Process embodiment 400 includes contacting solid-phase precursor non-nanoparticle TiO2, TiN, or TiC with tetramethylammonium hydroxide (TMAOH) in deionized water in a vessel at atmospheric pressure with sufficient agitation at a temperature and for a time sufficient to form TiO2, TiN, or TiC nanoparticles, box 402, where the temperature ranges from about 35° C. to about 80° C. and the time ranges from about 12 hours to about 192 hours. Process embodiment 400 further includes optionally contacting the TiO2, TiN, or TiC nanoparticle composition with an optional organic solvent to form a reduced aqueous TiO2, TiN, or TiC nanoparticle composition, box 404, followed by optionally contacting the reduced aqueous TiO2, TiN, or TiC nanoparticle composition with a LiCl solution to form a TiO2, TiN, or TiC nanoparticle composition, box 406. Process embodiment 400 continues with centrifuging, box 408, and filtering the TiO2, TiN, or TiC nanoparticle composition, box 410.

[0077] Thus, the systems and processes described herein, and equivalents thereof, provide a safe and economical method for producing nanoparticles from non-nano source materials. The following examples may be further helpful in understanding certain aspects of the systems and processes of the present disclosure.

[0078] Working Example

[0079] Experimental details

[0080] Table 1 lists all precursors and chemicals used in this study. Table 2 summarizes the processing conditions used in all runs. "TMAOH" refers to tetramethylammonium hydroxide. "TBAOH" refers to tetrabutylammonium hydroxide.

[0081] After the reaction of the solid-phase precursor with the onium salt, a black (except when the precursor was TiO2) dark mud was obtained, which was collected, rinsed with ethanol, shaken, and then centrifuged for multiple cycles at 3500 rpm until a clear supernatant was obtained. Once the supernatant was clear, 40 mL of deionized DI water was added to the washed product and shaken for 5 min. After centrifugation at 3500 rpm for 0.5 h without sonication, a stable dark (in most cases) nanoparticle composition was obtained. Unreacted powder precipitated. The nanoparticle composition was then vacuum filtered to produce a filter film FF, some of which were characterized.

[0082] Most of the characterization was performed on LiCl washed films for reasons that will be explained further herein. A 5M LiCl solution was added to the black nanoparticle composition. This resulted in the suspension being deaggregated. The precipitate was shaken, centrifuged at 5000 rpm for three cycles, and washed with deionized water. The LiCl / DI water washes were repeated until the pH was about 7. The washed precipitate was then sonicated in a cold bath under Ar flow for 1 hour, shaken for 5 minutes, and centrifuged at 3500 rpm for 0.5 hour. The nanoparticle composition was filtered to produce FF (filter film). It is noted that deaggregation also occurred using dilute solutions of NaOH, KOH, or KF. The FF was then left overnight in a vacuum chamber to dehydrate before further characterization.

[0083] X-ray diffraction, XRD

[0084] XRD patterns of the wet and dry samples were acquired using a powder diffractometer (Rigaku SmartLab) set up in Bragg-Brentano geometry using Cu Kα radiation in the range of 2–65°2θ with a step size of 0.02° and a dwell time of 1 s / step.

[0085] X-ray photoelectron spectroscopy, XPS

[0086] XPS was performed using a spectrometer (VersaProbe 5000, Physical Electronics, Chanhassen, MN). Monochromatic Al-Kα X-rays with a spot size of 200 μm were used for analysis. High-resolution spectra were collected with a pass energy of 23.5 eV for all scans, with an energy step of 0.05 eV and a step time of 0.5 s. The number of repetitions per scan was set to 10. XPS spectra were calibrated by setting the CC peak at 285.0 eV. Peaks were fitted using an asymmetric Gaussian / Lorentzian line shape. Background was determined using the Shirley algorithm. All samples were mounted on the XPS stage with carbon tape.

[0087] Scanning Electron Microscope, SEM

[0088] Micrographs and elemental compositions were obtained using a SEM (Zeiss Supra 50VP, Carl Zeiss SMT AG, Oberkochen, Germany) equipped with an energy dispersive X-ray spectrometer (EDS, Oxford EDS, Oxfordshire, UK). [Table 1] [Table 2] TIFF2024525395000004.tif205152

[0089] 5A, 5B, 6A, 6B, 7A, and 7B are photographs of example laboratory experiments and nanoparticle compositions according to the present disclosure. FIG. 5A shows a suspension of nanoparticle TiO2, and FIG. 5B shows a filter film of nanoparticle TiO2 formed by reacting non-nanoparticle TiO2 with TMAOH at 35° C. for 144 hours, washing with ethanol, filling with deionized water, centrifuging, and filtering. FIG. 6A shows a suspension of nanoparticle TiC, and FIG. 6B shows a suspension of nanoparticle TiC, and FIG. 6C shows a filter film of nanoparticle TiC formed by reacting solid-phase non-nanoparticle TiC with TMAOH at 80° C. for 120 hours, washing with ethanol, LiCl, shaking, and filtering. FIG. 7A shows a suspension of FeB nanoparticles, and FIG. 7B shows a filter film of nanoparticle FeB formed by reacting solid-phase non-nanoparticle FeB with TMAOH at 50° C. for 48 hours, washing with ethanol, filling with deionized water, centrifuging, and filtering.

[0090] Figures 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 are powder XRD graphs of nanoparticle samples produced according to Examples 7, 8, 9, 10, 11, 12, 15, 16, 17, 19, and 20, respectively. The broadening of at least some of the peaks confirmed the presence of nanoparticles.

[0091] We have discovered a simple, inexpensive, relatively high-yielding, near-ambient, and scalable bottom-up approach to fabricate nanoparticles from solid-phase precursor non-nanoparticles. The fact that the starting solid-phase non-nanoparticle materials are relatively inexpensive commodities will further stimulate the scientific community's interest in this new class of nanoparticles.

[0092] Certain apparatus and process embodiments of the present disclosure may be controlled by one or more controllers. For example, the reaction temperature may be controlled by monitoring one or more parameters selected from the temperature, mass and / or volumetric flow rate of reactants, the temperature, mass and / or volumetric flow rate of reaction products, and combinations thereof. Certain apparatus and processes of the present disclosure may also measure and / or monitor the feed rates of feed materials such as precursor materials, onium, and water, and use these measurements for control purposes. The position of the flow dividers may be adjusted or controlled to enhance heat transfer within the heat transfer substructure.

[0093] As with the vessels of the present disclosure, the various conduits, such as the ingredient supply conduits, the inert gas conduits, the heat transfer fluid supply and return conduits, can be constructed from polymers (e.g., polyethylene) or polymer-lined metal or glass, or combinations thereof.

[0094] The selection of a particular vessel or other construction materials will be determined, among other parameters, by the reactant chemistry used, pressure, temperature, and the type of nanoparticles produced with a particular feedstock, the amount of nanoparticles produced, etc. One of ordinary skill in the art with knowledge of the particular application, pressures, temperatures, and materials available will be able to design the most cost-effective, safe, and operable vessels, feedstock and product conduits for each particular application without undue experimentation.

[0095] Aspects

[0096] The following aspects are illustrative and not limiting of the scope of the disclosure or the appended claims. It should be understood that the present technology may include any or all of the following aspects in any combination.

[0097] Embodiment 1. A process comprising contacting a solid phase precursor (which may optionally be non-nanoparticles) comprising any one or more of a metal oxide, a metalloid oxide, a metal carbide, a metal semi-carbide, a metal nitride, a metal semi-nitride, a metal boride, a metal semi-boride, a metal silicide, a metal semi-silicide, a metal sulfide, a metal semi-sulfide, a metal phosphide, a metal semi-phosphide, and mixtures thereof, with one or more onium ions from one or more onium salts, in water, in a container with sufficient agitation, at a temperature and for a time sufficient to form nanoparticles, wherein said temperature is from about 0° C. to about 100° C., and said time is from at least about 10 minutes, e.g., from about 10 minutes to about 144 hours, and all intermediate values ​​and subranges.

[0098] Embodiment 2. The process of embodiment 1, wherein said metal is selected from the group consisting of transition metals (elements from groups 3 to 12 of the periodic table) and mixtures and combinations thereof.

[0099] Embodiment 3. The process of embodiment 2, wherein the transition metal is selected from the group consisting of Fe, Mn, Co, and Ti, and mixtures and combinations thereof.

[0100] Embodiment 4. The process of embodiment 1, wherein the metal is selected from the group consisting of one or more alkaline earth metals, and mixtures and combinations thereof.

[0101] Embodiment 5. The process of embodiment 4, wherein the alkaline earth metal is Mg.

[0102] Embodiment 6. The process of embodiment 1, wherein the metalloid is selected from the group consisting of Si, B, As, Ge, Sb, P, and Te, and mixtures and combinations thereof.

[0103] Embodiment 7. A composition comprising nanoparticles produced by the process of claim 1, said nanoparticles having the same crystal structure as solid phase precursor non-nanoparticles as determined by XRD and / or TEM.

[0104] Example 8. The process of example 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a material comprising Ti with one or more onium ions derived from the one or more onium salts.

[0105] Example 9. The process of example 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a two-dimensional material with one or more onium ions derived from the one or more onium salts.

[0106] Example 10. The process of example 9, wherein contacting the two-dimensional material with one or more onium ions from the one or more onium salts comprises contacting one or more of TiC, TiB2, TiN, TiC, Si3N4, MgO, Ti5S3, TiAl3, TiO2, MnB, Mn3O4, Mn2O3, FeB, Fe2O3, ZrC, Si3N4, Co(OH)2, and SiC, or mixtures or combinations thereof, with one or more onium ions from the one or more onium salts.

[0107] Example 11. The process of example 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting an M-three-dimensional material with one or more onium ions derived from the one or more onium salts.

[0108] Example 12. The process of example 11, wherein contacting the M-three-dimensional material with one or more onium ions derived from the one or more onium salts comprises contacting one or more of Ti3AlC2, Ti3SiC2, Ti3GaC2, Ti2SbP, Mn5SiB2, Mn2AlB2, Fe5SiB2, Fe2AlB2, Zr3AlC5, V2AlC, and Nb2AlC, or mixtures or combinations thereof, with one or more onium ions derived from the one or more onium salts.

[0109] Example 13. The process of example 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a MD-two-dimensional or MD-three-dimensional material with one or more onium ions derived from the one or more onium salts.

[0110] Example 14. The process of example 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a quaternary M-containing material comprising one or more metal elements with one or more onium ions derived from the one or more onium salts.

[0111] Embodiment 15. The process of embodiment 1, wherein the step of contacting the solid phase precursor non-nanoparticles with one or more onium ions from the one or more onium salts converts the solid phase precursor non-nanoparticles into:

[0112] a) one or more of TMAOH, TEAOH, TPAOH, TBAOH, NH4OH, or THAOH, or any combination thereof;

[0113] b) one or more amine derivatives of TMAOH, TEAOH, TPAOH, TBAOH, NH4OH, or THAOH, or any combination thereof; or

[0114] c) any combination of a) and b) A process comprising the step of contacting.

[0115] Example 16. The process of example 15, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with ammonium ions derived from TMAOH.

[0116] Example 17. The process of example 15, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with ammonium ions derived from TBAOH.

[0117] Example 18. The process of example 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with a composition comprising ammonium ions derived from TMAOH.

[0118] Aspect 19. The process of aspect 1, wherein the temperature ranges from about 35°C to about 80°C.

[0119] Example 20. The process of example 1, wherein the metal is selected from the group consisting of metals of groups 4, 5, 6, 7, 8, 9, 10, 11, and 12, and mixtures and combinations thereof.

[0120] Example 21. The process of example 20, wherein the metal is selected from the group consisting of Group 4 metals, and mixtures and combinations thereof.

[0121] Example 22. The process of example 20, wherein the metal is selected from the group consisting of Group 5 metals, and mixtures and combinations thereof.

[0122] Example 23. The process of example 20, wherein the metal is selected from the group consisting of Group 6 metals, and mixtures and combinations thereof.

[0123] Example 24. The process of example 20, wherein the metal is selected from the group consisting of Group 7 metals, and mixtures and combinations thereof.

[0124] Example 25. The process of example 20, wherein the metal is selected from the group consisting of Group 8 metals, and mixtures and combinations thereof.

[0125] Example 26. The process of example 20, wherein the metal is selected from the group consisting of Group 9 metals, and mixtures and combinations thereof.

[0126] Example 27. The process of example 20, wherein the metal is selected from the group consisting of Group 10 metals, and mixtures and combinations thereof.

[0127] Example 28. The process of example 20, wherein the metal is selected from the group consisting of Group 11 metals, and mixtures and combinations thereof.

[0128] Example 29. The process of example 20, wherein the metal is selected from the group consisting of Group 12 metals, and mixtures and combinations thereof.

[0129] Example 30. The process of example 15, wherein the metalloid is selected from the group consisting of Si, B, As, Ge, Sb, P, and Te, and mixtures and combinations thereof.

[0130] Example 31. The process of example 1, wherein the process is a one-pot process, i.e., a process carried out in a single vessel.

[0131] Embodiment 32. A composition comprising nanoparticles prepared according to the process of any one of embodiments 20 to 31.

[0132] Embodiment 33. A composition comprising nanoparticles prepared according to the process of any one of embodiments 20 to 31, the nanoparticles comprising a substantially anatase or substantially rutile structure.

[0133] The disclosed technology can also include any one or more of the following elements.

[0134] Element 1: The process in which the metal is a transition metal, an element in groups 3 to 12 of the periodic table.

[0135] Element 2: The process wherein the transition metal is selected from Mn and Ti, Fe, Cr, Ni.

[0136] Element 3: The process wherein the metal is one or more alkaline earth metals.

[0137] Element 4: The process wherein the alkaline earth metal is Mg.

[0138] Element 5: The process wherein the metalloid is selected from Si, B, As, Ge, Sb, P, Te, and mixtures thereof.

[0139] Element 6: The process, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from one or more onium salts comprises contacting a material comprising Ti with one or more onium ions derived from one or more onium salts.

[0140] Element 7: The process, wherein contacting the solid-phase precursor non-nanoparticles with one or more onium ions derived from one or more onium salts comprises contacting a two-dimensional material with one or more onium ions derived from one or more onium salts.

[0141] Element 8: The process, wherein the step of contacting the two-dimensional material with one or more onium ions derived from one or more onium salts comprises contacting one or more of TiC, TiB2, TiN, TiC, Si3N4, MgO, Ti5S3, TiAl3, TiO2, MnB, Mn3O4, Mn2O3, FeB, Fe2O3, ZrC, Si3N4, Co(OH)2, and SiC, or mixtures or combinations thereof, with the one or more onium ions derived from the one or more onium salts.

[0142] Element 9: The process, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from one or more onium salts comprises contacting an M-three-dimensional material with one or more onium ions derived from one or more onium salts.

[0143] Element 10: M—The process wherein contacting the three-dimensional material with one or more onium ions derived from one or more onium salts comprises contacting one or more of Ti3AlC2, Ti3SiC2, Ti3GaC2, Ti2SbP, Mn5SiB2, Mn2AlB2, Fe5SiB2, Fe2AlB2, Zr3AlC5, V2AlC, and Nb2AlC, or mixtures or combinations thereof, with the one or more onium ions derived from the one or more onium salts.

[0144] Element 11: The process, wherein contacting a solid phase precursor non-nanoparticle with one or more onium ions derived from one or more onium salts comprises contacting a MD-2D or MD-3D material with one or more onium ions derived from one or more onium salts.

[0145] Element 12: The process, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from one or more onium salts comprises contacting a quaternary M-containing material that includes one or more metal elements with one or more onium ions derived from one or more onium salts.

[0146] Element 13: The process, wherein contacting a solid phase precursor non-nanoparticle material with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticle with: (a) one or more of TMAOH, TEAOH, TPAOH, TBAOH, NHOH, or THAOH, or any combination thereof; (b) one or more amine derivatives of TMAOH, TEAOH, TPAOH, TBAOH, NHOH, or THAOH, or any combination thereof; or, (c) any combination of (a) and (b).

[0147] Element 14: The process, wherein contacting a solid phase precursor non-nanoparticle material with one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle material with TMAOH.

[0148] Element 15: The process, wherein contacting a solid phase precursor non-nanoparticle material with one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle material with TBAOH.

[0149] Element 16: The process, wherein contacting a solid phase precursor non-nanoparticle material with one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle material with an onium salt composition comprising TMAOH.

[0150] Element 17: The process, wherein the temperature is in the range of about 35°C to about 80°C.

[0151] Element 18: The process wherein the metal is at least one Group 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal.

[0152] Element 19: The process wherein the metal is at least one Group 4 metal.

[0153] Element 20: The process wherein the metal is at least one Group 5 metal.

[0154] Element 21: The process wherein the metal is at least one Group 6 metal.

[0155] Element 22: The process wherein the metal is at least one Group 7 metal.

[0156] Element 23: The process wherein the metal is at least one Group 8 metal.

[0157] Element 24: The process wherein the metal is at least one Group 9 metal.

[0158] Element 25: The process wherein the metal is at least one Group 10 metal.

[0159] Element 26: The process wherein the metal is at least one Group 11 metal.

[0160] Element 27: The process wherein the metal is at least one Group 12 metal.

[0161] Item 28: A composition prepared according to the steps of any one of Items 1 to 27.

[0162] Item 29: The composition prepared according to the process of any one of items 1 to 27, having an anatase-like and / or rutile-like structure.

[0163] Element 30: The process, wherein the production of nanoparticles is a one-pot process.

[0164] Although only a few exemplary embodiments of the present disclosure have been described in detail above, those skilled in the art can easily understand that many modifications are possible in the exemplary embodiments without substantially departing from the novel teachings and advantages of the present disclosure, and these modifications are considered as further elements according to the preceding paragraph that can be combined with all other embodiments.

[0165] For example, the vessels and processes described herein can be in any particular embodiment batch, semi-batch, continuous, or combinations thereof (e.g., a first batch vessel in which a first batch of nanoparticles is produced, followed by a second vessel operated continuously to produce a second nanoparticle composition). One, two, or more different solid-phase non-nanoparticle precursors can be used in a first vessel (e.g., two-dimensional precursors in a first vessel and three-dimensional precursors in a second vessel). Two or more than two different vessels can be arranged in parallel or series. Accordingly, all such modifications are intended to be included within the scope of the present disclosure as defined in the following claims.

[0166] In the claims, means-plus-function clauses permitted by 35 U.S.C. § 112F are not intended unless "means for" is expressly recited along with the relevant function. The "means for" phrase is intended to indicate that the structures, materials, and / or acts described herein perform the recited function and is intended to encompass not only structural equivalents, but also equivalent structures.

Claims

1. 1. A process, comprising: contacting a solid phase precursor non-nanoparticle comprising any one or more of a metal oxide, a metalloid oxide, a metal carbide, a metal semi-carbide, a metal nitride, a metal semi-nitride, a metal boride, a metal semi-boride, a metal silicide, a metal semi-silicide, a metal sulfide, a metal semi-sulfide, a metal phosphide, a metal semi-phosphide, and mixtures thereof, with one or more onium ions from one or more onium salts in water in a container with sufficient agitation at a temperature and for a time sufficient to form nanoparticles, said temperature being in the range of about 0° C. to about 100° C. and said time being at least 10 minutes; process.

2. 2. The process of claim 1, wherein the metal is selected from the group consisting of transition metals (elements from groups 3 to 12 of the periodic table) and mixtures and combinations thereof.

3. 3. The process of claim 2, wherein the transition metal is selected from the group consisting of Fe, Mn, Co and Ti, and mixtures and combinations thereof.

4. 10. The process of claim 1, wherein the metal is selected from the group consisting of one or more alkaline earth metals, and mixtures and combinations thereof.

5. 5. The process of claim 4, wherein the alkaline earth metal is Mg.

6. 2. The process of claim 1 , wherein the metalloid is selected from the group consisting of Si, B, As, Ge, Sb, P, and Te, and mixtures and combinations thereof.

7. 13. A composition comprising nanoparticles produced by the process of claim 1 having the same crystal structure as solid phase precursor non-nanoparticles as determined by XRD and / or TEM.

8. 2. The process of claim 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a material comprising Ti with one or more onium ions derived from the one or more onium salts.

9. 2. The process of claim 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a two-dimensional material with one or more onium ions derived from the one or more onium salts.

10. 10. The process of claim 9, wherein the step of contacting the two-dimensional material with one or more onium ions from the one or more onium salts comprises contacting the two-dimensional material with one or more onium ions from the one or more onium salts, such as TiC, TiB ２ , TiN, TiC, Si ３ N ４ , MgO, Ti ５ S ３ , TiAl ３ , TiO ２ , MnB, Mn ３ O ４ , Mn ２ O ３ , FeB, Fe ２ O ３ , ZrC, Si ３ N ４ , Co(OH) ２ and SiC, or a mixture or combination thereof, with one or more onium ions from said one or more onium salts.

11. 2. The process of claim 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting an M-three-dimensional material with one or more onium ions derived from the one or more onium salts.

12. 12. The process of claim 11, wherein the step of contacting the M-3D material with one or more onium ions from the one or more onium salts comprises contacting the M-3D material with one or more onium ions from the one or more onium salts with Ti ３ AIC ２ , Ti ３ SiC ２ , Ti ３ GaC ２ , Ti ２ SbP, Mn ５ SiB ２ , Mn ２ AIB ２ , Fe ５ SiB ２ , Fe ２ AIB ２ , Zr ３ AIC ５ , V ２ AlC, and Nb ２ A process comprising the step of contacting one or more of AlC, AlC, AlC, AlC+ ...

13. 2. The process of claim 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a MD-two-dimensional or MD-three-dimensional material with one or more onium ions derived from the one or more onium salts.

14. 2. The process of claim 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting a quaternary M-containing material comprising one or more metal elements with one or more onium ions derived from the one or more onium salts.

15. 10. The process of claim 1, wherein the step of contacting the solid phase precursor non-nanoparticles with one or more onium ions from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with: a) TMAOH, TEAOH, TPAOH, TBAOH, NH ４ OH, or THAOH, or any combination thereof; b) TMAOH, TEAOH, TPAOH, TBAOH, NH ４ one or more amine derivatives of OH, or THAOH, or any combination thereof, or c) any combination of a) and b) A process comprising the step of contacting.

16. 16. The process of claim 15, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with ammonium ions derived from TMAOH.

17. 16. The process of claim 15, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with ammonium ions derived from TBAOH.

18. 2. The process of claim 1, wherein contacting the solid phase precursor non-nanoparticles with one or more onium ions derived from the one or more onium salts comprises contacting the solid phase precursor non-nanoparticles with a composition comprising ammonium ions derived from TMAOH.

19. 10. The process of claim 1, wherein the temperature ranges from about 35°C to about 80°C.

20. 2. The process of claim 1 , wherein the metal is selected from the group consisting of metals of Groups 4, 5, 6, 7, 8, 9, 10, 11, and 12, and mixtures and combinations thereof.

21. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 4 metals, and mixtures and combinations thereof.

22. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 5 metals, and mixtures and combinations thereof.

23. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 6 metals, and mixtures and combinations thereof.

24. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 7 metals, and mixtures and combinations thereof.

25. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 8 metals, and mixtures and combinations thereof.

26. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 9 metals, and mixtures and combinations thereof.

27. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 10 metals, and mixtures and combinations thereof.

28. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 11 metals, and mixtures and combinations thereof.

29. 21. The process of claim 20, wherein the metal is selected from the group consisting of Group 12 metals, and mixtures and combinations thereof.

30. 16. The process of claim 15, wherein the metalloid is selected from the group consisting of Si, B, As, Ge, Sb, P, and Te, and mixtures and combinations thereof.

31. 10. The process of claim 1, wherein the process is a one-pot process.

32. A composition comprising nanoparticles prepared according to the process of any one of claims 20 to 31.

33. A composition comprising nanoparticles prepared according to the process of any one of claims 20 to 31, the nanoparticles comprising a substantially anatase or substantially rutile structure.

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