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  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

• the present disclosure relates generally to the field of nanomaterials, and more specifically to nanoparticles and processes of producing and using same.
• the process is based on reactions of salts in solvents.
• a precipitating agent is added to yield the desired particle precipitation, and the precipitate is filtered out and thermally post-treated.
• Temperature, pH value of the solution, the sequence in which the source materials are added, and mixing processes can influence reaction kinetics.
• Nanoreactors such as microemulsions, bubbles, micelles, and liposomes, are known. They are composed of a polar group and a non-polar hydrocarbon chain. Microemulsions require at least one tenside (substance that reduces the surface tension of liquids) while at the same time preventing particle agglomeration, which can be difficult. Zeolites (microporous aluminum-silicon compounds) are produced from aqueous superheated solutions in autoclaves (airtight pressure chambers). The partial vaporization of the solvent creates pressure in the autoclaves (several bars), triggering chemical reactions that differ from those under standard conditions, for example by altering the solubility.
• sol-gel processes material production or deposition takes place through a complicated series of steps from a liquid sol state, which is converted into a solid gel state via a sol-gel transformation.
• the sol-gel transformation involves a three- dimensional cross-linking of the nanoparticles in the solvent, whereby the gel takes on bulk properties.
• a controlled heat treatment in air can transform gels into a ceramic oxide material.
• adding organic substances in the sol-gel process produces an organometallic compound from a solution containing an alkoxide (metallic compound of an alcohol, for example with silicon, titanium, or aluminum).
• the pH value of the solution is adjusted with an acid or a base which, as a catalyst, also triggers the transformation of the alkoxide.
• the subsequent reactions are hydrolysis (splitting of a chemical bond by water) followed by condensation and polymerization.
• the course of hydrolysis and the poly condensation reaction depend on many factors: the composition of the initial solution, the type and amount of catalyst, temperature as well as the reactor- and mixing geometry.
• gel formation is followed by a drying step.
• One disadvantage of the sol-gel process lies in the difficult-to-control synthesis and drying steps, which complicate scaling up the process. Moreover, organic contaminants can remain in the gel. The resulting necessary cleaning steps, drying and thermal posttreatment makes this production process more complex than gas phase synthesis.
• nanoparticles, and processes of producing same are described which reduce or overcome many of the faults of previously known processes.
• a first aspect of the present disclosure are processes comprising (or consisting essentially of, or consisting of):
• an ammonium ion) derived from one or more onium salts in water (in certain embodiments deionized water) in a vessel with sufficient agitation and at a temperature and for a time period sufficient to form a nanoparticles, the temperature 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 of at least 10 minutes, (or ranging from about 1 to about 200 hrs., or from about 10 to about 190 hrs., or from about 12 to about 192 hrs., or from about 24 to about 144 hrs., or from about 48 to about 96 hrs.);
• a nanoparticle according to the present disclosure can comprise a IDa (i.e., a 1-dimensional anatase material).
• the IDa can also be termed a quat-derived nanomaterial (QDN).
• a IDa can comprise an oxide-based nanofilament and/or subnanofilament, and can optionally comprise an amount of carbon.
• a nanofilament can comprise, e.g., titanium.
• the composition can be present as a mesoporous powder in which the powder particulates comprise the oxide-based nanofilaments and/or subnanofilaments.
• the IDa composition can be present in the form of flakes, e.g., 2D bodies formed (e.g., via self-assembly) of IDa filaments.
• the IDa composition can also be present as 3D bodies, e.g., nanoparticles.
• a IDa can exhibit a XRD pattern that, when compared to a XRD pattern of nano- or bulk anatase, exhibit reduced (104) and (105) peaks at around 38° and about 55° two theta (2Q).
• IDa nanofilaments and/or subnanofilaments can, in some embodiments, exhibit a Raman spectrum that is quite similar to that of bulk anatase, but can differ from bulk anatase in terms of the XRD spectrum, as described herein.
• An IDa can be obtained by reacting starting materials (e.g., MAX-phase materials, carbides, nitrides, borides, sulfides, metals, and the like) with an onium salt (such as ammonium salts, TMAOH, TBAOH, TPAOH), e.g., at a temperature of from room temperature to 100 °C under ambient pressure.
• an onium salt such as ammonium salts, TMAOH, TBAOH, TPAOH
• the admixture can optionally include an ammonium salt.
• An IDa can, as mentioned, be present as a 2D material, but this is not a requirement, as the IDa can also be present as a nanoparticle, a nanoribbon, nanowhiskers, nanotubes, a ID material (e.g., fibers), or in other form.
• the metals of the oxides, nitrides, carbides, silicides, borides, and phosphides can be selected from one or more transition metals, the elements in Groups 3 - 12 of the Periodic Table, or mixtures and combinations thereof.
• the transition metals can be selected from one or more of V, Nb, Mn, and Ti, and mixtures and combinations thereof.
• the metals can be selected from one or more alkaline earth metals and mixtures and combinations thereof, for example, but not limited to, Mg.
• the metalloid can be Si, but other metalloids (B, As, Ge, Sb, P, and Te) are considered within the present disclosure. In some cases, a metalloid and a non-metal, e.g., S13N4.
• a second aspect of the present disclosure is nanoparticles produced from the processes of the first aspect of the present disclosure. Certain products of the processes of the first aspect comprise the same chemical formula as the solid phase precursor. The final composition of the nanoparticles is the same as the composition of the solid phase precursor non-nanoparticles.
• composition refers to the types of constituent atoms of the solid phase precursor non-nanoparticles and the product nanoparticles. This does not mean, however, that the ratio of atoms remains constant when comparing the solid phase precursor non-nanoparticles and the nanoparticles; in fact, we have evidence that it does change. Moreover, in all embodiments the crystalline structure of the nanoparticles (as determined by X-ray diffraction, or XRD and/or transmission electron microscopy, or TEM) remains the same as the crystalline structure of the solid phase precursor non nanoparticles.
• the XRD peaks of the solid phase precursor non-nanoparticles and the XRD peaks of the nanoparticles are necessarily identical in shape.
• the XRD peaks of the nanoparticles can be broader than the corresponding XRD peaks of the solid phase precursor non-nanoparticles.
• the solid phase precursor non-nanoparticles simply shrink in size to the nanoparticle scale.
• Nanoparticles can comprise, consist essentially of, or consist of nanoparticles of the same structure as determined by XRD.
• nanoparticles can comprise a minor portion (e.g., less than 50 percent) of a non-nanomaterial
• nanoparticles can consist essentially of nanoparticles and trace amounts (up to 5 percent, or up to 2 percent, or up to 0.1 percent) of non-nanomaterials, for example water, organic solvent, or other solid non-nanomaterials that do not detract from the properties of the nanoparticles, or mixtures and combinations thereof
• nanoparticles can consist of nanoparticles (and only nanoparticles).
• washing the nanoparticles with mild acids can remove other reaction products, such as metal-carbide-oxides (MCOs) which are sometimes produced at the same time as the nanoparticles.
• MCOs metal-carbide-oxides
• a third aspect of the present disclosure is an apparatus for carrying out the processes of the first aspect of the present disclosure.
• Processes of using one or more nanoparticles of the present disclosure are also presented, such as property enhancement fillers in polymeric materials, and biomedical applications, for example, but not limited to, cancer treatment.
• FIG. 1 is a schematic process flow diagram of one process and system embodiment in accordance with the present disclosure
• FIG. 2 is a more detailed schematic process flow diagram of another process and system embodiment in accordance with the present disclosure.
• FIG. 3 is an illustrative diagram of a process in accordance with the present disclosure.
• FIG. 4 is an illustrative diagram of a process in accordance with the present disclosure.
• FIG. 5A is a photograph of an illustrative, non-limiting laboratory experiment and illustrative, non-limiting nanoparticles produced according to the present disclosure.
• FIG. 5B is a photograph of an illustrative, non-limiting laboratory experiment and illustrative, non-limiting nanoparticles produced according to the present disclosure.
• FIG. 6A is a photograph of an illustrative, non-limiting laboratory experiment and illustrative, non-limiting nanoparticles produced according to the present disclosure.
• FIG. 6N is a photograph of an illustrative, non-limiting laboratory experiment and illustrative, non-limiting nanoparticles produced according to the present disclosure.
• FIG. 7A is a photograph of an illustrative, non-limiting laboratory experiment and illustrative, non-limiting nanoparticles produced according to the present disclosure.
• FIG. 7B is a photograph of an illustrative, non-limiting laboratory experiment and illustrative, non-limiting nanoparticles produced according to the present disclosure.
• FIG. 8 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 9 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 10 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 11 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 12 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 13 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 14 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 15 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 16 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 17 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 18 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure.
• FIG. 19 is a powder XRD graph of a nanoparticle sample produced according to the present disclosure. DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
• the term “comprising” can include the embodiments “consisting of' and “consisting essentially of.”
• the terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps.
• compositions or processes as “consisting of and “consisting essentially of' the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any impurities that might result therefrom, and excludes other ingredients/steps.
• the terms “about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
• an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
• approximating language can be applied to modify any quantitative representation that can vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not be limited to the precise value specified, in some cases. In at least some instances, the approximating language can correspond to the precision of an instrument for measuring the value.
• the modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” can refer to plus or minus 10% of the indicated number.
• compositions that comprises components A and B can be a composition that includes A, B, and other components, but can also be a composition made of A and B only. Any documents cited herein are incorporated by reference in their entireties for any and all purposes.
• compositions, apparatus, systems, and processes can comprise a number of physical components and features, but can be devoid of certain optional chemical species, hardware and/or other features.
• certain nanoparticle embodiments can be devoid of components that are not compatible with nanoparticles.
• Certain nanoparticle compositions can be devoid of MCOs.
• Certain apparatus embodiments can comprise vessels devoid of any gaskets or O-rings, or welds or threaded fittings.
• the solid precursor non-nanoparticle material can be devoid of anything but metal oxides.
• a first aspect of this disclosure are processes comprising (or consisting essentially of, or consisting of):
• an ammonium salt in water in a vessel with sufficient agitation and at a temperature and for a time period sufficient to form nanoparticles, the temperature 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 of at least 10 minutes, (or ranging from about 1 to about 200 hrs., or from about 10 to about 190 hrs., or from about 12 to about 192 hrs., or from about 24 to about 144 hrs., or from about 48 to about 96 hrs.);
• c) optionally contacting the nanoparticles of (b) with an inorganic salt precipitation solution (e.g. 1 M LiCl); and [0066] d) optionally filtering and drying the nanoparticles of (c) to form dried nanoparticles.
• an inorganic salt precipitation solution e.g. 1 M LiCl
• the “metal” (sometimes referred to herein as simply “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.
• the metal is at least one metal selected from the group consisting of Ti, Mn, Ni, Fe, and Mg, and combinations and mixtures thereof.
• the metal is at least one metal selected from the group consisting of Ti and Mg, and combinations and mixtures thereof.
• the metal can be at least one Group 4 metal, for example, Ti, Zr, and Hf, and combinations and mixtures thereof.
• the metal is at least one Group 5-12 metal, for example, 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.
• metal can be at least one Group 8 metal.
• M is at least one Group 8 metal.
• M can be at least one Group 4 metal.
• M is at least one Group 4 metal.
• 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.
• the metalloid (sometimes referred to herein as simply (“MD”) can comprise one or more MDs selected from the group consisting of B,
• MD is one or more metalloids selected from the group consisting of Si and Ge, and combinations and mixtures thereof.
• MD can comprise Si and one or more of B, Ge, As, Sb, Te, S and P, and combinations and mixtures thereof.
• 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.
• MD can comprise Si and any one or more of B and Ge, and combinations and mixtures thereof.
• metals can be bound to any one or more reactive nonmetals (C, O,
• metalloids can be bound to any one or more reactive nonmetals (C, O, N, F, P, S, Cl, Se, Br, and I).
• nanoparticles prepared according to the processes of the present disclosure are nanoparticles prepared according to the processes of the present disclosure.
• Certain process embodiments can use precursor non-nanomaterial(s) at least some of which have an anatase structure.
• Certain process embodiments can result in at least some of the nanoparticles having an anatase- like or rutile-like structure.
• Certain process embodiments can use solid phase precursor non-nanomaterial(s) at least some of which have an anatase-like or rutile-like structure, and result in forming nanoparticles, at least some of the nanoparticles having an anatase- like or rutile-like structure.
• Certain processes can be carried out at temperature 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, and for a time period of at least 10 minutes, or ranging from about 1 to about 200 hrs., or from about 10 to about 190 hrs., or from about 12 to about 192 hrs., or from about 24 to about 144 hrs., or from about 48 to about 96 hrs.
• the nanoparticles are produced using a so-called “one pot” process (synthesis carried out in a single reaction container or vessel); in other words, the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts, in water, for the times, temperature, and pressures indicated herein, produces the nanoparticles directly in one vessel, without any further changes and/or steps taught by the prior art.
• Certain processes can be carried out at pressures ranging from sub- atmospheric to above atmospheric, or from vacuum or near-vacuum pressure to several bar, or from atmospheric pressure to 10 bar, or from about 1 bar to about 5 bar.
• the nanoparticles of the present disclosure can be conducting, non conducting, semiconducting, porous, mesoporous (such as described in U.S. Patent No. 9,562,005), or non-porous, where “porous” includes mesoporous porosities and porosities above mesoporous, “non-porous” means porosity less than mesoporous, and “mesoporous” refers to porous materials having an average pore size in the range from about 2 to about 50 nanometers (nm).
• the solid phase precursor non-nanoparticles function as a source of metal (M) or metalloid (MD) and one or more reactive non-metals, for example, but not limited to O, C, B, S, P, Si, and N atoms, and combinations thereof, to produce the nanoparticles.
• Suitable solid phase precursor non-nanoparticles can be binary, ternary, quaternary or higher materials.
• the binary material can be, for example, but to limited to TiC, T1B2,
• Suitable other solid phase precursor non-nanoparticles can be ternary M-containing or ternary MD-containing materials.
• the ternary M-containing and/or MD-containing materials can be, for example, but not limited to Ti3AlC2, Ti3SiC2, Ti3GaC2, Ti2SbP, Mn5SiB2, Mn2AlB2, Fe5SiB2, Fe2AlB2, Zr3AlC5, V2AlC, Nb2AlC, and combinations and mixtures thereof.
• the onium salt (or its cation and/or anion) functions to chemically react with at least a portion of the solid phase precursor non-nanoparticles to induce formation of the nanoparticles.
• onium is also used for cations that would result from the substitution of hydrogen atoms in those ions by other groups, such as organic radicals, or halogens; such as tetraphenylphosphonium, (C 6 H 5 ) 4 P+.
• the substituent groups can be divalent or trivalent, yielding ions such as iminium and nitrilium.
• the onium ion of the onium salt can have a charge of +1, +2 (a double onium), +3 (a triple onium) and even larger.
• the onium cation can have monovalent substitutions or polyvalent substitutions.
• Suitable examples of monovalent substituted onium cations include, but are not limited to, primary onium cations within the formula RH3N+ (such as NH3OH+), secondary onium cations within the formula R 2 NH 2 + (such as (CH 3 ) 2 NH 2 +), tertiary onium cations within the formula R 3 NH+ (such as (CH 3 ) 3 NH+), and quaternary onium cations within the formula R4N+, where R in these formulas can be organic or inorganic moieties.
• RH3N+ such as NH3OH+
• secondary onium cations within the formula R 2 NH 2 + such as (CH 3 ) 2 NH 2 +
• tertiary onium cations within the formula R 3 NH+ such as (CH 3 ) 3 NH+
• quaternary onium cations within the formula R4N+ where R in these formulas can be organic or inorganic moieties.
• the onium ion can be derived from one or more onium salts, for example an ammonium salt.
• 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.
• TMAOH tetramethylammonium hydroxide
• TEAOH tetraethylammonium hydroxide
• TPAOH tetrapropylammonium hydroxide
• TSAOH tetrabutylammonium hydroxide
• NH4OH ammonium hydroxide
• TSAOH tetrahex
• the onium salt can be based on protonated pnictogens, protonated chalcogens, or protonated halogens.
• pnictogen onium cations include NH4 + (ammonium), PH4 + (phosphonium), AsH4 + (arsonium), SbH4 + (stibonium), and BiH 4 + (bismuthonium).
• chalcogen onium cations include 4876-6748-2918.1 (H3O + (oxonium), H3S + (sulfonium), H3Se + (selenonium), and H3Te + (telluronium).
• halogen onium cations include H 2 F + (fluoronium), H 2 Cl + (chloronium), H 2 Br + (bromonium), and H 2 I + (iodonium).
• pseudohalogen onium cations include H2N3 + (aminodiazonium) and HCNH + (either HC ⁇ CH + isomer, or C ⁇ CH2 + isomer, or both).
• Suitable carbon group onium cations include carbonium ions, for example, but not limited to alkanium cations, CnH2n+3 + (for example, but not limited to CH5 + (methanium), C 2 H 7 + (ethanium), C 3 H 9 + (propanium, which can be either propan-1-ylium isomer, or propan-2-ylium isomer, or both), C 4 H 11 + (butanium, one or more isomers, or combination of two or more isomers), C8H19 + (octonium, one or more isomers, or combination of two or more isomers), Si n H 2n+3 + (silaniums), germoniums such as GeH 5 + , stannoniums such as SnH 3 + , and plumboniums such as PbH 3 + .
• CnH2n+3 + for example, but not limited to CH5 + (methanium), C 2 H 7 + (ethanium), C 3
• onium cations include BH4 + (boronium cation) and protonated boranes of the formula BxHy + ; noble gas onium cations, such as HeH + (helonium), NeH + (neonium), ArH + (argonium), KrH + (kryptonium), XeH + (xenonium); and H 3 + (hydrogenonium, or trihydrogen cation).
• the onium ion can be selected from diquats, aliquats, polyquats, and other forms.
• diquats examples include, but are not limited to didodecyl dimethyl-gamma-diquaternium salts, N-dodecyl propylenediamine gamma- diquaternium bromide, and the like.
• aliquats examples 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), and the like.
• polyquats examples include, but are not limited to Ethanol, 2,2′,2 ′′ -nitrilotris-, polymer with 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] (known as polyquaternium-2), and the like (polyquaternium-X, where X ranges from 1 to 47 or higher, the number designating the order of registration under the International Nomenclature of Cosmetic Ingredients, assigned in accordance with rules established by the Personal Care Products Council (PCPC).
• PCPC Personal Care Products Council
• the onium salt can be accompanied by one or more oxidizing agents, for example, but not limited to, H2O2, halogens, such as fluorine (F 2 ), chlorine (Cl 2 ), and bromine (Br 2 ), and certain oxy anions, such as the permanganate ion (MnO4 ⁇ ) and the dichromate ion (Cr2O7 2 ⁇ ), and mixtures and combinations thereof.
• 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.
• the onium cation will be present in water, with the anion being the hydroxyl anion OH-, however, the anion of the onium salt is not limited to hydroxyl anion, and could be any organic or inorganic moiety, such as, but not limited to halogen anions (Fl-, Cl- and the like), complex halogen anions (for e.g., [FeBr4]- , and the like.
• Organic Solvents [0086] Organic solvents, if used, function to wash or cleanse the nanoparticles and remove excess water.
• the organic solvent can remove some or all of, for example, but not limited to non-reacted solid phase precursor materials, unreacted ammonium cations and anions, non-dissolved ammonium salts, and the like.
• Suitable organic solvents include liquid oxygenated hydrocarbons such as, but not limited to, alcohols, glycol ethers, and ketones.
• suitable alcohols include compounds such as, but not limited to, ethyl alcohol (or ethanol), propyl alcohol (or propanol), n-butyl alcohol, and t-butyl alcohol.
• 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. Normal, branched, and cyclic versions are included in these examples.
• Halogenated hydrocarbons solvents such as chlorobenzene, iodobenzene, and the like can 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.
• Inorganic Salt Solutions if used, also function to wash or cleanse the nanoparticles and remove excess water and/or dissolve other reaction products (but not the nanoparticles).
• Suitable inorganic salt solutions include, but are not limited to, solutions of salts of alkali metals and halogens, such as, but not limited to LiCl, NaCl, and LiBr, and mixtures of any two or more of these, in molarities ranging from 0.001 up to 10 M. HCl and other mild acids like citric, and the like, can be used at similar molarity ranges.
• the nanoparticles are centrifuged (and/or ultracentrifuged) one or more times until a clear supernatant is formed, then filtered.
• Suitable centrifuging techniques are well known and require little explanation. Bench-top and floor-standing centrifuges are available from companies such as Fisher Scientific, Eppendorf, Beckman Coulter and others. Commercial scale centrifuges, such as disc stack centrifuges, are available from companies such as Alfa Laval.
• Suitable filtering techniques include gravity filtration and vacuum filtration.
• Suitable commercial-scale filtration units can include rotary vacuum filters, chilling filters based on a refrigerant, and the like.
• Suitable vessels for use in processes of the present disclosure can be continuous, semi-continuous, batch or semi-batch reactors.
• the onium ion is derived from TMAOH
• polyethylene vessels polyethylene, or polyethylene-lined vessels
• Glass or glass-lined steel (or PTFE, or PFA, or tantalum) vessels can be usable in certain embodiments (for example with onium salts other than TMAOH).
• the vessel volumes can range from lab-scale (50 mL) up to commercial scale (10,000 L or more), and can include accessories, for example, but not limited to, pressure and temperature measurement devices, agitation devices, motors for running the agitators, one or more inlets and outlets for inert gas purging, heating and cooling facilities, timers, and one or more human/machine interfaces (HMIs).
• Certain vessels can include one or more process controllers, pressure relief valves, accessways for human or non-human inspection, sampling ports, pH probes, and the like. Suitable vessels should have the capability to withstand temperatures up to 200 °C and up to 2 bar pressure for up to 250 hours or more.
• inert gas blanketing for the vessels; in certain embodiments, however, it may be desired.
• suitable inert gases include, but are not limited to, nitrogen, argon, hydrogen, and mixtures thereof.
• the sources of inert gases can be one or more conduits, pipelines, storage facilities, or cylinders. Inert gases can be supplied from a pipeline, cylinder, storage facility, cryogenic separation unit, membrane permeation separator, or adsorption unit such as a vacuum swing adsorption unit.
• l is a high-level schematic process flow diagram of one process and system embodiment 100 in accordance with the present disclosure, including a vessel 2, an optional organic solvent washer 4, an optional inorganic salt solution washer 6, a water wash vessel 8, an optional centrifuge or shaker 10, and an optional filter 12.
• a solid phase precursor non-nanoparticle material 18 (for example solid TiC , TiN, TiC, S13N4, and MgO as described in the Examples herein) is routed to vessel 2, and an onium salt solution as well, 20.
• vessel 2 After raising the temperature and holding for a time as described in the Examples, vessel 2 produces a nanoparticle composition 22 which is optionally routed to organic solvent washer 4, as is an organic solvent 24.
• a nanoparticle composition with reduced water 26 is produced which can be routed to optional vessel 6, along with an optional inorganic salt solution 28 (for example a 1 M aqueous solution of LiCl).
• Optional vessel 6 and the optional inorganic salt can be used to further cleanse the nanoparticles.
• Nanoparticles 30 are then routed to vessel 8 for filling with water 32, and then through a conduit 33 to a centrifuge or shaker 10, where waste liquids and solids are removed (at 34).
• the supernatant fluid 35 is viewed (14) either by human or machine vision, or both, and if clear (Y) no more centrifuging or shaking is required, but if the supernatant is not clear (N), centrifuging or shaking is repeated until the supernatant is clear.
• a final water filled suspension of nanoparticles is then routed to a filter 12, forming a “filtered film” of nanoparticles 36 and a waste stream 38.
• FIG. 2 is a more detailed schematic process flow diagram of another process and system embodiment 200 in accordance with the present disclosure.
• Embodiment 200 differs from embodiment 100 in that stirrers or agitators 64, 66 are included in vessel 2 and optional organic solvent washer 4, respectively, as well as various pumps and control valves, and a chute 19 for transfer of solid phase precursor non nanoparticle material into vessel 2.
• Pump 68 transfers an aqueous onium solution 20 to vessel 2; pump 70 transfers nanoparticles from vessel 2 to optional organic solvent washer 4; pump 72 transfers nanoparticles from optional organic solvent washer 4 to optional vessel 6 for optional contact with an inorganic salt solution 28; pump 74 transfers the nanoparticles to water filling vessel 8, where additional water is added for centrifuging or shaking and the material is routed by pump 82 to centrifuge or shaker 10. After the supernatant is clear, as viewed by human or machine vision at 14, the nanoparticles are routed to filter 12.
• a series of control valves 76, 78, 80, 84, 86, 88, and 90 (some of which are optional) control flows from pumps 68, 70, 72, 74, and 82, respectively, controlled by one or more supervisory controllers 92 (such as a supervisory computer) that can operate via wired or wireless control signals to operate the control valves, pumps, agitators, and other equipment.
• supervisory controllers 92 such as a supervisory computer
• sensors are not displayed that would be included in certain industrial embodiments, such as mass flow sensors or meters, temperature sensors, pressure sensors, pH sensors, weight sensors, and the like.
• One or more of these sensors or meters could be controllers as well, such as temperature-indicating-controllers, pressure-indicating controllers, and the like. These sensors are not illustrated in FIG. 2 for brevity.
• FIGS. 3 and 4 are logic diagrams of two process embodiments 300, 400 in accordance with the present disclosure.
• Process embodiment 300 includes contacting a solid phase precursor non-nanoparticle material with an onium ion derived from an ammonium salt in deionized water in a vessel at atmospheric pressure with sufficient agitation and at a temperature and for a time sufficient to form a nanoparticle composition, the temperature ranging from about 0 °C to about 100 °C, the time period of 10 minutes or greater, box 302.
• Process embodiment 300 further includes optionally contacting the nanoparticle composition with an organic solvent to form a reduced water nanoparticle composition, box 304, followed optionally by contacting the reduced water nanoparticle composition with an inorganic salt solution, box 306.
• Process embodiment 300 continues with centrifuging, box 308, and filtering the nanoparticle composition, box 310.
• Process embodiment 400 includes contacting a solid phase precursor non nanoparticle Ti0 2 , TiN, or TiC with tetramethylammonium hydroxide (TMAOH) in deionized water in a vessel at atmospheric pressure with sufficient agitation and at a temperature and for a time sufficient to form TiCh, TiN, or TiC nanoparticles, the temperature ranging from about 35 °C to about 80 °C, the time ranging from about 12 hrs. to about 192 hrs., box 402.
• TMAOH tetramethylammonium hydroxide
• Process embodiment 400 further optionally includes contacting the T1O2, TiN, or TiC nanoparticle composition with an optional organic solvent to form a reduced water T1O2, TiN, or TiC nanoparticle composition, box 404, followed optionally by contacting the reduced water T1O2, TiN, or TiC nanoparticle composition with a LiCl solution to form a T1O2, TiN, or TiC nanoparticle composition, box 406.
• Process embodiment 400 continues with centrifuging, box 408, and filtering the TiC , TiN, or TiC nanoparticle composition, box 410.
• TMAOH refers to tetramethyl ammonium hydroxide.
• TAAOH refers to tetrabutylammonium hydroxide.
• XRD patterns on wet and dry samples were acquired using a powder diffractometer (Rigaku SmartLab) setup in the Bragg-Brentano geometry with Cu Ka radiations in the 2 - 65° 2Q range using a 0.02° step size and a dwell time of 1 s/step.
• XPS was performed using a spectroscope (VersaProbe 5000, Physical Electronics, Chanhassen, Minnesota). Monochromatic A1-Ka X-rays with 200 pm spot size were used for analysis. A pass energy of 23.5 eV was used for all scans, with an energy step of 0.05 eV, and a step time of 0.5 s was used to gather the high-resolution spectra. The number of repeats per scan was set to 10. The XPS spectra were calibrated by setting the C-C peak to 285.0 eV. The peaks were fit using asymmetric Gaussian/Lorentzian line shape. The background was determined using the Shirley algorithm. All samples were mounted on the XPS stage using carbon tape.
• FIGS.5A, 5B, 6A, 6B, 7A, and 7B are photographs of the laboratory experiments and nanoparticle compositions from the Examples in accordance with the present disclosure.
• FIG.5A shows a suspension of nanoparticulate TiO2
• FIG.5B shows a filtered film of nanoparticulate TiO 2 formed by reacting non-nanoparticulate TiO 2 with TMAOH at 35°C for 144 hrs., washed with ethanol, filled with DI water, centrifuged, then filtered.
• FIG.6A shows a suspension of nanoparticulate TiC
• FIG.6B shows a suspension of nanoparticulate TiC
• FIG.6C shows a filtered film of nanoparticulate TiC formed by reacting solid phase non-nanoparticulate TiC with TMAOH at 80°C for 120 hrs., washed with ethanol, LiCl, shook, then filtered.
• FIG.7A shows a suspension of FeB nanoparticles
• FIG.7B shows a filtered film of nanoparticulate FeB formed by reacting solid phase non-nanoparticulate FeB with TMAOH at 50°C for 48h, washed with ethanol, filled with DI water, centrifuged, then filtered.
• FIGS.8, 9, 10 ,11, 12, 13, 14, 15, 16, 17, 18, and 19 are the powder XRD graphs of the nanoparticle samples produced in accordance with Examples 7, 8, 9, 4876-6748-2918.1 10, 11, 12, 15, 16, 17, 19, and 20, respectively. The broadening of at least some of the peaks verified the presence of nanoparticles.
• reaction temperature can be controlled by monitoring one or more parameters selected from temperature, mass and/or volume flow rate of reactants, temperature, mass and/or volume flow rate of the reaction products, and combinations thereof.
• Certain apparatus and processes of this disclosure can also measure and/or monitor feed rate of feed materials, such as precursor materials, onium, and water, and use these measurements for control purposes.
• Flow diverter positions can be adjusted or controlled to increase heat transfer in heat transfer substructures.
• conduits such as feedstock supply conduits, inert gas conduits, heat-transfer fluid supply and return conduits, as well as vessels of the present disclosure can be comprised of polymer (for example polyethylene) or polymer-lined metal or glass, or combination thereof.
• a process comprising: contacting a solid phase precursor (which can optionally be a non-nanoparticle) that comprises any one or more of: oxides of metals, oxides of metalloids, carbides of metals, carbides of metalloids, nitrides of metals, nitrides of metalloids, borides of metals, borides of metalloids, silicides of metals, silicides of metalloids, phosphides of metals, phosphides of metalloids, sulfides of metals, sulfides of metalloids, and mixtures thereof, with one or more onium ions derived from one or more onium salts, in water, in a vessel with sufficient agitation and at a temperature and for a time period sufficient to form nanoparticles, the temperature ranging from about 0 °C to about 100 °C for a time period of at least about 10 minutes, e.g., from about 10 minutes to about
• Aspect 2 The process of Aspect 1 wherein the metals are selected from the group consisting of transition metals (the elements in Groups 3 - 12 of the Periodic Table) and mixtures and combinations thereof.
• Aspect 3 The process of Aspect 2, wherein the transition metals are selected from the group consisting of Fe, Mn, Co and Ti, and mixtures and combinations thereof.
• Aspect 4 The process of Aspect 1, wherein the metals are selected from the group consisting of one or more alkaline earth metals, and mixtures and combinations thereof.
• Aspect 5 The process of Aspect 4 wherein the alkaline earth metal is
• Aspect 6 The process of Aspect 1, wherein the metalloids are selected from the group consisting of Si, B, As, Ge, Sb, P, and Te, and mixtures and combinations thereof.
• Aspect 7 A composition, comprising: nanoparticles produced by the process of Aspect 1, the nanoparticles having the same crystalline structure as the solid phase precursor as determined by XRD and/or TEM.
• Aspect 8 The process of Aspect 1, wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting a material comprising Ti with the one or more onium ions derived from one or more onium salts.
• Aspect 9 The process of Aspect 1, wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting a binary material with the one or more onium ions derived from one or more onium salts. [00128] Aspect 10.
• contacting of the binary material with the one or more onium ions derived from one or more onium salts comprises contacting one or more of TiC, TiB 2 , TiN, TiC, Si 3 N 4 , MgO, Ti 5 S 3 , TiAl 3 , TiO 2 , MnB, Mn3O4, Mn2O3, FeB, Fe2O3, ZrC, Si3N4, Co(OH)2, and SiC or any mixture or combination thereof with the one or more onium ions derived from one or more onium salts.
• Aspect 1 wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting an M-ternary material with the one or more onium ions derived from one or more onium salts.
• contacting of the M- ternary material with the one or more onium ions derived from one or more onium salts comprises contacting one or more of Ti 3 AlC 2 , Ti 3 SiC 2 , Ti 3 GaC 2 , Ti 2 SbP, Mn 5 SiB 2 , Mn2AlB2, Fe5SiB2, Fe2AlB2, Zr3AlC5, V2AlC, and Nb2AlC, or any mixture or combination thereof with the one or more onium ions derived from one or more onium salts.
• Aspect 1 wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting an MD-binary or MD-ternary material with the one or more onium ions derived from one or more onium salts.
• Aspect 14 The process of Aspect 1, wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting a quaternary M-containing material that comprises more than one metal element with the one or more onium ions derived from one or more onium salts.
• Aspect 1 wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting the solid precursor non-nanoparticle with: [00134] (a) one or more of TMAOH, TEAOH, TPAOH, TBAOH, NH4OH, or THAOH, or any combination thereof; [00135] (b) one or more amine derivatives of one or more of TMAOH, TEAOH, TPAOH, TBAOH, NH4OH, or THAOH, or any combination thereof; or [00136] (c) any combination of (a) and (b). 4876-6748-2918.1 [00137] Aspect 16.
• Aspect 17 The process of Aspect 15, wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle with ammonium ions derived from TBAOH.
• Aspect 18 The process of Aspect 1, wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle with a composition comprising ammonium ions derived from TMAOH.
• Aspect 19 The process of Aspect 1, wherein the temperature ranges from about 35 °C to about 80 °C.
• Aspect 20 The process of Aspect 1, wherein the metals are selected from the group consisting of Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, Group 11, and Group 12 metals, and mixtures and combinations thereof.
• Aspect 21 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 4 metals and mixtures and combinations thereof.
• Aspect 22 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 5 metals and mixtures and combinations thereof.
• Aspect 23 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 6 metals and mixtures and combinations thereof.
• Aspect 24 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 7 metals and mixtures and combinations thereof.
• Aspect 25 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 8 metals and mixtures and combinations thereof.
• Aspect 26 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 9 metals and mixtures and combinations thereof.
• Aspect 27 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 10 metals and mixtures and combinations thereof.
• Aspect 28 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 11 metals and mixtures and combinations thereof.
• Aspect 29 The process of Aspect 20, wherein the metals are selected from the group consisting of Group 12 metals and mixtures and combinations thereof.
• Aspect 30 The process of Aspect 15, wherein the metalloids are selected from the group consisting of Si, B, As, Ge, Sb, P, and Te, and mixtures and combinations thereof.
• Aspect 31 The process of Aspect 1, wherein the process is a one-pot process, i.e., a process performed in a single vessel.
• Aspect 32 A composition, comprising nanoparticles prepared according to the process of any one of Aspects 20 to 31.
• Aspect 33 A composition, comprising: nanoparticles prepared according to the process of any one of Aspects 20 to 31 comprising a substantially anatase and/or substantially rutile structure.
• the disclosed technology can also include any one or more of the following Elements.
• Element 1 Processes wherein the metals are transition metals, the elements in Groups 3 - 12 of the Periodic Table.
• Element 2 Processes wherein the transition metals are selected from Mn and Ti an Fe, Cr, Ni.
• Element 3 Process wherein the metal is one or more alkaline earth metals.
• Element 4 Process wherein the alkaline earth metal is Mg.
• Element 5 Processes wherein the metalloid is selected from Si, B, As, Ge, Sb, P, and Te, and mixtures thereof.
• Element 6 Processes wherein the contacting of the solid phase precursor non-nanoparticles with the one or more onium ion derived from one or more onium salts comprises contacting a material comprising Ti with the one or more onium ions derived from one or more onium salts.
• Element 7 Processes wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting a binary material with the one or more onium ions derived from one or more onium salts .
• Element 8 Processes wherein the contacting of the binary material with the one or more onium ions derived from one or more onium salts comprises contacting one or more of TiC, TiB 2 , TiN, TiC, Si 3 N 4 , MgO, Ti 5 S 3 , TiA1 3 , Ti0 2 , MnB, Mn 3 0 4 , FeB, Fe 2 0 3 , ZrC, Si 3 N 4 , and SiC or any mixture or combination thereof with the one or more onium ions derived from one or more onium salts.
• Element 9 Processes wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting an M-temary material with the one or more onium ions derived from one or more onium salts.
• Element 10 Processes wherein the contacting of the M-temary material with the one or more onium ions derived from one or more onium salts comprises contacting one or more of Ti 3 A1C 2 , Ti 3 SiC 2 , Ti 3 GaC 2 , Ti 2 SbP, MnsSiB 2 , Mn 2 A1B 2 , Fe5SiB 2 , Fe 2 A1B 2 , Zr 3 A1Cs, V 2 A1C, and Nb 2 A1C, or any mixture or combination thereof with the one or more onium ions derived from one or more onium salts.
• Element 11 Processes wherein the contacting of the solid phase precursor non-nanparticle with the one or more onium ions derived from one or more onium salts comprises contacting an MD-binary or MD-ternary material with the one or more onium ions derived from one or more onium salts.
• Element 12 Processes wherein the contacting of the solid phase precursor non-nanoparticle with the one or more onium ions derived from one or more onium salts comprises contacting a quaternary M-containing material that comprises more than one metal element with the one or more onium ions derived from one or more onium salts.
• Element 13 Processes wherein the contacting of the solid phase precursor non-nanoparticle material with the one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle material with: (a) one or more of TMAOH, TEAOH, TPAOH, TBAOH, NH 4 OH, or THAOH, or any combination thereof; (b) one or more amine derivatives of one or more of TMAOH, TEAOH, TPAOH, TBAOH, NH 4 OH, or THAOH, or any combination thereof; or (c) any combination of (a) and b).
• Element 14 Processes wherein the contacting of the solid phase precursor non-nanoparticle material with the one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle material with TMAOH.
• Element 15 Processes wherein the contacting of the solid phase precursor non-nanoparticle material with the one or more onium ions derived from one or more onium salts comprises contacting the solid phase precursor non-nanoparticle material with TBAOH.
• Element 16 Processes wherein the contacting of the solid phase precursor non-nanoparticle material with the 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.
• Element 17 Processes wherein the temperature ranges from about 35 °C to about 80 °C.
• Element 18 Processes wherein the metal is at least one Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, Group 11, or Group 12 metal.
• Element 19 Processes wherein the metal is at least one Group 4 metal.
• Element 20 Processes wherein the metal is at least one Group 5 metal.
• Element 21 Processes wherein the metal is at least one Group 6 metal.
• Element 22 Processes wherein the metal is at least one Group 7 metal.
• Element 23 Processes wherein the metal is at least one Group 8 metal.
• Element 24 Processes wherein the metal is at least one Group 9 metal.
• Element 25 Processes wherein the metal is at least one Group 10 metal.
• Element 26 Processes wherein the metal is at least one Group 11 metal.
• Element 27 Processes wherein the metal is at least one Group 12 metal.
• Element 28 Compositions prepared according to the processes of any one of Elements 1-27.
• Element 29 Compositions prepared according to the processes of any one of Elements 1-27 having an anatase-like and/or rutile-like structure.
• Element 30 Processes where the production of nanoparticles is a one- pot process.
• vessels and processes described herein can be batch, semi -batch, continuous, or combination thereof in any particular embodiment (for example, a first batch vessel where a first batch of nanoparticles is produced, followed by a second vessel operated continuously to produce a second nanoparticle composition).
• One, two, or more than two different solid phase non-nanoparticle precursors can be used in a first vessel (for example a binary precursor in a first vessel, and a ternary precursor in a second vessel).
• a first vessel for example a binary precursor in a first vessel, and a ternary precursor 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 this disclosure as defined in the following claims.

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