# Patent

## Title
Mesoporous metal oxides and processes for preparation thereof

## Abstract

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.

## Background
RELATED APPLICATIONS
This application claims the benefit of U.S. Patent Application Ser. No. 61/705,370, filed Sep. 25, 2012, which is incorporated herein by reference. This application is related to U.S. Patent Application Ser. No. 61/705,372, filed Sep. 25, 2012, which is incorporated herein by reference.


This Invention was supported by the Department of Energy, under Grant No. DE-FG02-86ER13622. This government has certain rights in the invention.


BACKGROUND
1. Field of the Disclosure
This disclosure relates to mesoporous metal oxides and processes for making mesoporous metal oxides, in particular, the synthesis of thermally stable mesoporous metal oxides with controllable nano-sized wall crystallinity and mesoporosity. This disclosure also relates to a method of tuning structural properties of mesoporous metal oxides, and a method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides.
2. Discussion of the Background Art
Porous transition metal oxides consist of micropores (<2 nm), mesopores (2-50 nm), macropores (>50 nm) and sometimes combinations of these. Considerable interest in the control of pore sizes and pore size distributions of such materials has been a focus for quite some time. The control of particle size in particular in the nanometer regime in the synthesis of nano-size metal oxides is also currently being pursued. Nano-size materials can have markedly different properties than similar compositions that are bulk size (m and above). Control of morphologies of porous transition metal oxides such as hollow spheres, rods, helices, spirals, and many other shapes has been a major focus of researchers over at least the last 10 years.
Such control comes from specific synthetic methods such as use of templates, structure directors, surfactants, core shell, self assembly, epitaxial growth, size reduction, capping agents, sol gel, and other methods. Morphologies can be controlled by compositions including dopants. The conditions during syntheses such as use of heat, light, pH, point of zero charge, stirring, high pressure, and others are also important.
Mesoporous materials with varied pore sizes and pore size distributions can be obtained for some systems such as silicon and titanium based oxide materials. However, control of pore size distributions to make single size pores and to systematically control such pore sizes and uniformity is difficult, especially with transition metal oxide systems. Control of the structure of the material is also an issue. Many systems have both micropores and mesopores and pore interconnectivity is of interest with these materials. Enhanced mass transport for catalytic reactions might be realized by fine-tuning the porosity of such systems. Incorporation of biomolecules larger than the micropore regime also might be done using well ordered crystalline mesoporous materials.
Most studies of mesoporous transition metal oxide (MTMO) materials have focused on groups I-IV including Y, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W. These have low angle X-ray diffraction peaks indicative of mesostructural ordering and Type IV isotherms. These syntheses have focused on use of water or water plus a base or urea with various amine and carboxyl containing surfactants (S). There are either strong Coulombic interactions (S+,I−; S−I+; S+X−I+; S−X+I−) or strong ligand metal interactions (I:S<2, very thin walls), and such systems have limited thermal stability and amorphous walls, where I=inorganic species, and X is a mediator. Such syntheses are open to air and various aging times and environmental conditions can influence the porosity of these materials.
Water content is a critical parameter with the synthesis of porous transition metal oxides. Water competes with ethoxy and other alkoxy groups for coordination to the metal and also significantly affects hydrolysis and condensation rates. Since most syntheses are open to the air the water content is very difficult to control. On the other hand, water is essential for reaction. When the number of water molecules per metal atom (H) is >1 then phase separation and nonporous oxides result. When H is <1, ordered mesoporous materials are formed when the metal has empty t2g orbitals. These materials obtain water from the environment during synthesis. When H is <<1, strong surfactant/transition metal interactions occur with weak surfactant interactions and there is no reaction.
Thermodynamic interactions in such syntheses and factors influencing each term are given in Table 1 below. Table 1 sets forth thermodynamic parameters of surfactant (S) transition metal (M) mesopore syntheses.







TABLE 1





DGm = DGorg + DG1 + DGinter + DGsol [1]


















S-S Interaction
High Lewis
Strong S-M
Unknown and


determines
acidity
interaction at
unpredictable


mesostructure
Unsaturated
interface



formed
Coordination
(Coulombic,



(Lamellar,
H (Hydrolysis
Covalent



Hexagonal,
Ratio H << 1),
bonding,



Cubic)
Condensation
Hydrogen




hindering
bonding)




molecules





(carboxyl, amine,





ethylene glycol.)









In Equation 1 above, DGm is the formation energy of the mesostructured material; DGorg is the surfactant-surfactant interaction; DG1 is the metal-metal interaction; DGinter is the surfactant-metal interaction; and DGsol is the solvent interaction. It would be desirable to develop a process that minimizes the last 2 terms, DGinter and DGsol, in order to make well ordered MTMO materials. The absence of totally empty d orbitals restricts the strong interaction between surfactant and metal (ligand to metal charge transfer) which is generally accepted as essential for the formation of ordered materials. Filled t2g orbitals such as in systems containing Mn, Fe, Co, and other oxides make synthese using the above methods difficult since charge transfer reactions do not occur.
The present disclosure provides many advantages over the prior art, which shall become apparent as described below.
SUMMARY OF THE DISCLOSURE
This disclosure relates in part to a process for preparing a mesoporous metal oxide, said process comprising:
providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and
heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide.
This disclosure also relates in part to a mesoporous metal oxide produced by a process comprising:
providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and
heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide.
This disclosure further relates in part to a method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides, said method comprising:
providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and
heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides.
This disclosure yet further relates in part to a mesoporous metal oxide particulate having nano-sized wall crystallinity, a particle size between about 1 and about 500 nm, a BET surface area between about 50 and about 1000 m2/g, a pore volume (BJH) between about 0.05 and about 2 cm3/g, a monomodal pore size (BJH desorption) distribution between about 1 and 25 nm, and optionally a wall thickness (2d/√3−PD, where d is the d-spacing and PD is the pore diameter) between about 2 and about 20 nm; wherein the mesoporous metal oxide particulate exhibits thermal stability up to a temperature of about 550° C.
This disclosure also relates in part to a method of tuning structural properties of mesoporous metal oxides, said method comprising:
providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and
heating the acidic mixture at a temperature and for a period of time sufficient to form a dried powder, and
heating the dried powder at a temperature and for a period of time sufficient to tune the structural properties of the mesoporous metal oxides.
Several advantages result from the processes of this disclosure. This disclosure provides a unique approach and method for the synthesis of thermally stable mesoporous metal (e.g., Mn, Fe, Co, Ni, Cu, Zn, Ti, Zr, Si, Ce, Sm and Gd) oxides with controllable mesopore size (e.g., 2 nm-13 nm) and nano-sized crystalline walls for various sorptive, conductive, structural, catalytic, magnetic and optical applications. This disclosure not only makes the synthesis of mesoporous (metal, transition metal, Lanthanide metal, post-transition metal, metalloid) oxides possible, but also allows one to precisely tune the structural properties of synthesized porous materials with simple heat treatment cycles. Moreover, the method of this disclosure is applicable to all transition metals, Lanthanide metals, post-transition metals and metalloids with modifications as appropriate in the synthesis procedure.
Further objects, features and advantages of the present disclosure will be understood by reference to the following drawings and detailed description.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts (a) low angle powder X-ray diffraction (PXRD) of as synthesized (fresh) and mesoporous Mn2O3 materials heated at different temperatures, and (b) a graph showing change of unit cell dimensions by heat treatment, as prepared in Examples 1 and 2.
FIG. 2 depicts wide angle PXRD of mesoporous Mn2O3 samples recorded for powders at different final heat treatment temperatures, as prepared in Examples 1 and 2.
FIG. 3 depicts (a) nitrogen sorption isotherms of mesoporous Mn2O3 materials heated to different final temperatures, and (b) a BJH desorption pore size distribution graph of corresponding samples, as prepared in Examples 1 and 2.
FIG. 4 depicts scanning electron microscope (SEM) images of mesoporous Mn2O3 samples with final heat treatment temperature of 450° C., as prepared in Examples 1 and 2.
FIG. 5 depicts the nitrogen sorption isotherm of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3.
FIG. 6 depicts the Barret-Joyner-Halenda (BJH) desorption pore size distribution of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3.
FIG. 7 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3.
FIG. 8 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3 (a=162).
FIG. 9 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3 (a=130).
FIG. 10 depicts the powder X-ray diffraction (PXRD) pattern of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3.
FIG. 11 depicts a high resolution transmission electron microscope (TEM) image of mesoporous MnO3 synthesized with Pluronic® F127 surfactant prepared in Example 3.
FIG. 12 depicts a high resolution transmission electron microscope (TEM) image of mesoporous Mn2O3 synthesized with Pluronic® F127 surfactant prepared in Example 3.
FIG. 13 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous ZnC2O4 synthesized with Pluronic® P123 surfactant prepared in Example 3 (surface area=70 m2/g).
FIG. 14 depicts the powder X-ray diffraction (PXRD) pattern of mesoporous ZnC2O4 synthesized with Pluronic® P123 surfactant prepared in Example 3 (surface area=70 m2/g).
FIG. 15 depicts the nitrogen sorption isotherm of mesoporous ZnC2O4 synthesized with Pluronic® P123 surfactant prepared in Example 3 (surface area=70 m2/g).
FIG. 16 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous CuO synthesized with Pluronic® P123 surfactant prepared in Example 3. The mesoporous CuO has a surface area (BET) of 47.5 m2/g at 150° C. and 21.8 m2/g at 250° C. The CuO is mesostructured but not porous. The pores are likely blocked.
FIG. 17 depicts the powder X-ray diffraction (PXRD) pattern of mesoporous CuO synthesized with Pluronic® P123 surfactant prepared in Example 3. The mesoporous CuO has a surface area (BET) of 47.5 m2/g at 150° C. and 21.8 m2/g at 250° C. The CuO is mesostructured but not porous. The pores are likely blocked.
FIG. 18 depicts the nitrogen sorption isotherm of mesoporous CuO synthesized with Pluronic® P123 surfactant prepared in Example 3. The mesoporous CuO has a surface area (BET) of 47.5 m2/g at 150° C. and 21.8 m2/g at 250° C. The CuO is mesostructured but not porous. The pores are likely blocked.
FIG. 19 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous CeO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 20 depicts the nano-particle size of mesoporous CeO2 synthesized with Pluronic® P123 surfactant versus heat treatment prepared in Example 3. The particle size was calculated by the Scherrer equation and the low angle powder X-ray signal position.
FIG. 21 depicts the powder X-ray diffraction (PXRD) pattern of mesoporous CeO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 22 depicts the nitrogen sorption isotherm of mesoporous CeO2 synthesized with Pluronic® P123 surfactant prepared in Example 3. The mesoporous CeO2 has a surface area (BET) of 97.5 m2/g at 150° C., 152.3 m2/g at 250° C., 173.4 m2/g at 350° C., 149.9 m2/g at 450° C., 127.3 m2/g at 550° C., and 71.6 m2/g at 600° C.
FIG. 23 depicts the Barret-Joyner-Halenda (BJH) desorption pore size distribution of mesoporous CeO2 synthesized with Pluronic® P123 surfactant prepared in Example 3. The mesoporous CeO2 has a surface area (BET) of 97.5 m2/g at 150° C., 152.3 m2/g at 250° C., 173.4 m2/g at 350° C., 149.9 m2/g at 450° C., 127.3 m2/g at 550° C., and 71.6 m2/g at 600° C.
FIG. 24 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous TiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 25 depicts the powder X-ray diffraction (PXRD) pattern of mesoporous TiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 26 depicts the nitrogen sorption isotherm of mesoporous TiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 27 depicts the Barret-Joyner-Halenda (BJH) desorption pore size distribution of mesoporous TiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 28 depicts the low angle powder X-ray diffraction (PXRD) pattern of mesoporous SiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 29 depicts the powder X-ray diffraction (PXRD) pattern of mesoporous SiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 30 depicts the nitrogen sorption isotherm of mesoporous SiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3. The mesoporous SiO2 had a surface area of 434.9 m2/g.
FIG. 31 depicts the density functional theory (DFT) pore size distribution of mesoporous SiO2 synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 32 depicts the low angle powder X-ray diffraction (PXRD) pattern of microporous aluminosilicate (Al:Si=1:5) synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 33 depicts the powder X-ray diffraction (PXRD) pattern of microporous aluminosilicate (Al:Si=1:5) synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 34 depicts the nitrogen sorption isotherm of microporous aluminosilicate synthesized with Pluronic® P123 surfactant prepared in Example 3. The microporous aluminosilicate had a surface area of 384.9 m2/g.
FIG. 35 depicts the density functional theory (DFT) pore size distribution of microporous aluminosilicate synthesized with Pluronic® P123 surfactant prepared in Example 3.
FIG. 36 depicts pore size distribution data (left) and field emission scanning electron microscopy (FESEM) micrograph (right) for mesoporous Fe2O3 prepared in Example 3.
FIG. 37 depicts low angle (left) and high angle (right) x-ray diffraction (XRD) data for mesoporous Co3O4 prepared in Example 3.
FIG. 38 depicts the sol gel micelle process for preparing well ordered metal oxide mesoporous materials with monomodal uniform pore sizes in accordance with this disclosure.
FIG. 39 depicts a proposed mechanism for the formation of highly ordered mesoporous Mn2O3 in accordance with this disclosure.
FIG. 40 depicts a Hantzsch reaction catalyzed by mesoporous iron oxide.
FIG. 41 sets forth the conditions and results generated from the Hantzsch reaction catalyzed by mesoporous iron oxide depicted in FIG. 40.
FIG. 42 depicts an adamantane oxidation reaction catalyzed by mesoporous manganese oxide.
FIG. 43 sets forth the conditions and results generated from the adamantane oxidation reaction catalyzed by mesoporous manganese oxide depicted in FIG. 42.
FIG. 44 depicts a hydration reaction catalyzed by mesoporous cerium oxide.
FIG. 45 sets forth the conditions and results generated from the hydration reaction catalyzed by mesoporous cerium oxide depicted in FIG. 44.
FIG. 46 depicts a hydrogenation reaction of methyl levulinate catalyzed by mesoporous cerium oxide supported nano-noble metals.
FIG. 47 depicts the conversion of a sugar (i.e., D-fructofuranose) to methyl levulinate.
FIG. 48 sets forth the conditions and results generated from the conversion reaction depicted in FIG. 47.
FIG. 49 depicts data showing properties of mesoporous zirconium oxide in comparison with sulfated mesoporous zirconium oxide.
FIG. 50 depicts a benzyl alcohol oxidation reaction catalyzed by mesoporous manganese oxide.
FIG. 51 sets forth the conditions and results from the benzyl alcohol oxidation reaction catalyzed by mesoporous manganese oxide depicted in FIG. 50.
FIG. 52 depicts what is believed to be the mechanism for HNO3 activity.
FIG. 53 depicts a proposed mechanism for the formation of highly ordered mesoporous metal oxide in accordance with this disclosure



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
The process of the present disclosure for making mesoporous metal oxides affords a high degree of control with respect to nano-sized wall crystallinity and mesoporosity. The mesoporous metal oxides are useful in various applications including, but not limited to, catalytic, magnetic and optical applications. In particular, the mesoporous metal oxides are useful as catalysts, sensors, batteries and energy production, optical displays, environmental and sorbent applications.
This disclosure offers a new type of porous metal oxide family. The disclosure not only makes use of a wide range of metals. e.g., transition metals, Lanthanide metals, post-transition metals and metalloids, but also provides more control on the structural properties of synthesized mesoporous metal oxides.
The method of this disclosure eliminates contribution of critical thermodynamic parameters such as strength of interaction at interface, hydrolysis and condensation rates of metal precursor and water content of reaction medium, thereby yielding totally reproducible porous metal oxides. For example, solvation by water is eliminated or minimized by eliminating or minimizing the amount of water in the system. This in turn limits hydrolysis.
The present disclosure provides a simple wet-chemical process that enables the synthesis of nanometer-sized particles (50-300 nm) with tunable pore sizes in the range of 2-30 nm, preferably 2-20 nm, and more preferably 2-13 nm. This surfactant-mediated synthesis may be generalized to achieve various pore structures, including 3-D cubic 1 m-3 m, 3-D cubic Fm-3 m, 2-D hexagonal p6 m, foam-like and worm-like pores, as well as different material compositions. The synthesis can produce ultrafine particles with well-defined mesopores, regular particle morphology and excellent pore accessibility. The mesopores are adjustable in size and have high structural ordering. The process uses a surfactant that may act as a supramolecular template for formation of the periodic mesostructure.
One of the unique features of the porous materials synthesized with this method is the tunable porosity. The pore diameter can be controlled between super micropore range (e.g., about 2 nm) and mid-mesopore range (e.g., about 13 nm) without losing available pore volume. A pore size of 13 nm is quite unusual for the mesoporous materials synthesized with various surfactant systems. The pore size of the synthesized materials increases with heat treatments applied which is also a unique discovery of this disclosure. This is a contradiction of pore size by heat treatment because of further condensation of wall structure and collapse of the structure with increased heat treatment duration and temperature applied. Tunable pore size might be useful for various catalytic applications in terms of size selective reactions and enhanced ion mobility for battery applications, etc.
Another unique advantage of this method is controlling the crystal structure of the nano-sized metal oxide walls. For instance, amorphous, bixbyite, hausmannite and manganite structures can be obtained for the manganese system. That makes possible the synthesis of target crystal structure for specific applications. Different crystal structures of metals show different optic, magnetic and catalytic properties which indicate that the method described herein is highly desirable for designing unique porous materials.
Other illustrative crystal structures of the nano-sized metal oxide walls include, for example, CeO2, Mn2O3, Mn3O4, Fe2O3, Co3O4, ZnO, CuO, TiO2 (Anatase), ZrO2, NiOOH, and the like. The method of this disclosure provides for controllable nano-sized wall crystallinity and the synthesis of target crystal structures for specific applications.
In accordance with this disclosure, well ordered crystalline mesoporous metal oxide systems can be prepared that can result in enhanced sorptive, conductive, structural, catalytic, magnetic and optical properties, in particular, enhanced catalytic activity and selectivity from better transport properties.
The process of this disclosure involves a sol-gel micelle based method as depicted in FIG. 38. In an embodiment, the process for preparing Mn2O3 uses HNO3 at low pH to increase metal precursor solubility, stabilize lower oxidation states, and hydrate the core of the micelles. Mn oxo clusters are stabilized in the 2+ oxidation state. Stronger hydrogen bonding interactions with surfactants occur. In FIG. 38, the surfactant species is Pluronic® P123, which is also the reaction medium. Minimization of water in these syntheses limits the aggregation of metal oxide clusters and confines the entire reaction to the core. An interface modifier like butanol hinders the condensation and limits oxidation of surfactant molecules present in the micelle once the critical micelle concentration (CMC) has been reached. The hydrotropic nitrate ion increases solubility of the Pluronic® P123 surfactant, penetrates into the micelle and decreases the aggregation number (AN), pulls the positively charged manganese oxide clusters into the micelle and balances charge. Referring to Equation 1 herein above, in these syntheses, ΔGinter (everything is in the micelle) and ΔGsol (no solvent) are not a concern, ΔG1 is controlled (confinement in the micelle), and AG, is adjusted with NO3− and butanol. The NO3− ion is critical and can be monitored with Fourier Transform Infrared (FTIR) spectroscopy. On coordination of NO3− to Mn2+, symmetry is lowered from D3h to C3v, the asymmetric stretching mode (E′) splits and a stretching mode at 1060 cm−1 appears that is also Raman active. In free nitrate, the asymmetric stretching mode of water is near 1360 cm−1. In solid environments, nitrate ions balance positive charges and shifts to lower frequencies. This also brings a further stability to formed nano-crystals by covering the surface of these particles.
During this process, surfactant is oxidized at long reaction times and formed carboxyl groups coordinated to oxomanganese clusters and competes with nitrate to exist in the micelles, although in some systems this is not the case. All samples regardless of reaction time show thermal stability up to 250° C. During the synthesis, carboxylate bands increase while nitrate bands decrease. Spectra are normalized with respect to the Mn—O stretching band (584 cm−1). The surfactant C—O stretching mode is between 1050 cm−1-1200 cm−1. The carboxyl groups are formed due to oxidation of the surfactant at long reaction times. These carboxyl groups are oxidized at 150° C. with a concomitant color change of the solution from black to brown. NO3− ions do not fully disappear until 200° C. The carboxyl groups need to be removed to preserve the mesoporous structure. Failure to remove the carboxylate groups leads to unstable mesoporous materials. Depending on reaction conditions, different manganese oxide structures (crystalline walls) can be formed.
In accordance with this disclosure, during thermal treatment, the d-spacings increase. The unit cell expands during heat treatment. The exact position of the d(100) peak depends on the heating temperature and time. Corresponding BET surface area (100-200 m2/g), pore size distributions, and pore volumes (up to 0.22 cc/g) show that mesoporous materials are produced with excellent control of pore size distributions (monomodal). These materials are stable up to 550° C. Such control of pore size distribution, enhanced pore volumes, and thermal stabilities are significant advantages afforded with metal oxide mesoporous compositions prepared in accordance with the process of this disclosure.
As used herein, “thermal stability” means no, or essentially no, degradation of structure at a designated temperature. As used herein, “monomodal” means one, or essentially one, mode as in pore size distribution. As used herein, “control of mesoporosity” means uniform, or essentially uniform, control of pore size, pore size distribution, and shape.
Referring to FIG. 39, a proposed mechanism of formation of ordered mesopores is shown. There is pore expansion up to 350° C. Mesopores merge to form larger ordered mesoporous materials between 350° C. and 450° C. The crystalline walls are made up of nanoparticles of manganese oxide that order as observed by X-ray diffraction (XRD), transmission electron microscopy (TEM), and electron diffraction (ED) methods.
In the process of this disclosure, the acidic mixture may comprise water, and may be an aqueous mixture. The mixture may be a solution, a dispersion or an emulsion, a micellar solution, and may be a microemulsion. The mixture may have a pH between about 0.5 and about 5, or between about 1 and about 3. The surfactant may be anionic, cationic, non-ionic, zwitterionic, or mixtures thereof. The surfactant may be a polymeric surfactant, and may be a copolymer surfactant, for example a block copolymer surfactant. The surfactant may be an alkylene oxide block copolymer surfactant, e.g. an EO/PO block copolymer surfactant. The surfactant may be miscible or immiscible with the interface modifier.
The metal precursors useful in the processes of this disclosure can be any water soluble metal salt, preferably metal salts with hydrotropic counter anions and alkoxide sources of any metal. The metal precursors also exhibit moderate alcohol solubility. The metal precursors are conventional materials known in the art and are commercially available.
Illustrative metal precursors include, for example, metal nitrates, metal alkoxides, metal halides, metal phosphates, metal acetates, and MxOy oxides that are capable of dissolving in HNO3. More particularly, metal precursors include, for example, M(NO3)x.yH2O (M=Mn, Fe, Co, Cu, Zn, Si), tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), titanium butoxide, zirconium n-propoxide, zirconium butoxide, Ce(NO3)3.6H2O, Gd(NO3)3.6H2O, Sm(NO3)3.6H2O, and the like.
Other metal precursors useful in the process of this disclosure include, for example, metal Cl−, I−, SCN−, SO42−, F− salts, and the like. Preferably, any metal and metal oxide which HNO3 can dissolve can be used. Any metal salt which does not form insoluble nitrate salts can be used.
The metal precursors useful in the process of this disclosure include precursors of transition metals, Lanthanide metals, post-transition metals, metalloids, and mixtures thereof. For example, the transition metal precursors comprise Group 3-12 transition metal precursors, in particular, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg precursors. In an embodiment, the transition metal precursors are selected from Group 6-12 transition metal precursors including Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni. Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg precursors. Preferably, the Group 6-12 transition metal precursors include Mn, Fe, Co, Ni, Cu and Zn precursors. The Lanthanide metal precursors include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu precursors, or any mixture thereof. The post-transition metal precursors include Al, Ga, In, Tl, Sn, Pb and Bi precursors, or any mixture thereof. The metalloid precursors include B, Si, Ge, As, Sb, Te, Po and At precursors, or any mixture thereof.
The concentration of the metal precursors used in the process of this disclosure can vary over a wide range and need only be at a concentration sufficient to form the mesoporous metal oxides. The metal precursors can be present in a molar concentration ratio of from about 1×10−2M to about 10M, preferably from about 1×10−1M to about 5M, and more preferably from about 5×10−1M to about 1M (based on a total volume of 10 milliliters).
The interface modifiers useful in the processes of this disclosure can be any aliphatic, alicyclic or aromatic hydrocarbons of between about 1 and about 20 carbon atoms, e.g., butanol. The interface modifiers are conventional materials known in the art and are commercially available. Any organic solvents that allow the surfactant to organize itself into inverse micelles are useful in the processes of this disclosure.
Illustrative interface modifiers include, for example, aliphatic, alicyclic and aromatic hydrocarbons of between about 1 and about 20 carbon atoms, including mixtures thereof. The aliphatic hydrocarbons may be branched or straight chain. The aliphatic, alicyclic and aromatic hydrocarbons include, for example, n-butanol, pentanol, hexanol, higher carbon-containing alcohols, trimethyl benzene (TMB), acetylacetonate, lauric acid, toluene, benzene, cyclohexene, any carboxylic group containing organic molecule such as glucose, terpene, terpenoid hydrocarbons, citrus terpenes, d-limonene, and the like, and mixtures thereof. The aliphatic, alicyclic and aromatic hydrocarbons may have between 1 and 20, 1 and 18, 1 and 16, 1 and 12, 1 and 10, or 1 and 8 carbon atoms.
The concentration of the interface modifiers used in the process of this disclosure can vary over a wide range and need only be at a concentration sufficient to form the mesoporous metal oxides. The interface modifiers can be present in a molar concentration ratio of from about 1 M to about 40 M, preferably from about 2 M to about 15 M, and more preferably from about 5 M to about 10 M (based on a total volume of 10 milliliters).
The concentration of the interface modifiers used in the process of this disclosure can vary over a wide range depending on the interface modifier type. More hydrotropic ions should be used in smaller amounts of interface modifiers and vice versa. This ratio can reach 5-50 M since the interface modifier is evaporated and its upper limit can be varied. Also, scaling up the reaction can be done by varying this ratio.
The hydrotropic ion precursors useful in the processes of this disclosure can be any hydrotropic anion beyond chloride in the Hoffmeister series, including mixtures thereof. The hydrotropic ion precursors are conventional materials known in the art and are commercially available.
Illustrative hydrotropic ion precursors include, for example, HNO3, NaNO3, KNO3, metal halides (e.g., metal iodides), metal thiocyanides, and the like. Illustrative hydrotropic ions include, for example, NO3−, SCN−, Br−, I−, an organic modifier such as ethylene glycol, and the like. A modifier can be used to modify the hydrotropic part such as F, 3,3′,5,5′-tetramethylbenzidine (TMB), aromatic compounds, Cl−, SO42−, and the like.
The concentration of the hydrotropic ion precursors used in the process of this disclosure can vary over a wide range and need only be a concentration sufficient to form the mesoporous metal oxides. The hydrotropic ion precursors can be present in a molar concentration ratio of from about 1×10−2 M to about 15 M, preferably from about 1×10−1 M to about 10 M, and more preferably from about 1 M to about 5 M (based on a total volume of 10 milliliters).
One or more acids may be used in the process of this disclosure to prepare the acidic mixture. As described herein, the acidic mixture may have a pH between about 0.5 and about 5, or between about 1 and about 3. The pH of the mixture can be adjusted by the addition of an acid. The acid and the hydrotropic ion precursor can be the same or different. For example, the acid and the hydrotropic ion precursor can both be HNO3. Illustrative acids useful in the process of this disclosure include, for example, HNO3. If the hydrotropic ion precursor is an acid, e.g., HNO3, then the addition of an acid may not be needed. High pH systems can be used with metals that show high solubility at low and high pH values.
The concentration of the acid used in the process of this disclosure can vary over a wide range and need only be at a concentration sufficient to impart to the mixture a pH between about 0.5 and about 5, or between about 1 and about 3.
The replacement of nitrate ions with a material that can gradually decrease the pH under process conditions may be useful in the process of this disclosure. Atmospheres of urea vapor or ammonia or other volatile bases may be useful in accomplishing the above.
Hydrocyanation may be used, or HF or other acids. The concepts of the use of an acid or a base and controlling pH are embodiments of this disclosure.
The surfactants useful in the processes of this disclosure can be any anionic, cationic, non-ionic, zwitterionic surfactant, or mixtures thereof. The surfactants are conventional materials known in the art and are commercially available.
Illustrative surfactants include, for example, anionic, cationic, non-ionic, zwitterionic, or mixtures thereof. The surfactant may be a polymeric surfactant, and may be a copolymer surfactant. The copolymer surfactant may be a block copolymer, or may be a random copolymer, an alternating copolymer or some other type of copolymer. The block copolymer may be a diblock, triblock or other copolymer. The block copolymer may have between 2 and 5 blocks or more than 5 blocks. The block copolymer may have an odd or an even number of blocks, and may have 2, 3, 4 or 5 blocks. The block copolymer may have hydrophilic blocks alternating with hydrophobic blocks. The terminal blocks may be hydrophobic, or may be hydrophilic, or one may be hydrophilic and one hydrophobic. The copolymer surfactant may have 2, 3, 4, 5 or more than 5 different types of blocks (i.e. different monomers). The surfactant may be an alkylene oxide block copolymer surfactant. The surfactant may be an EO/PO copolymer surfactant, e.g. an EO/PO block copolymer surfactant. Suitable surfactants include Pluronic® P65 (EO20PO30EO20), Pluronic® P85 (EO26PO40EO26), Pluronic® 25R4, Pluronic® F108 (EO129PO56EO129), Pluronic® P123 (EO20PO70EO20) and Pluronic® F127 (EO97PO69EO97). The surfactant may be miscible or immiscible, or may be partially miscible, with the interface modifier.
Other illustrative surfactants useful in the process of this disclosure include, for example, a Triton® surfactant, a Tween® surfactant, glucose, or an AB or BC polymer surfactant, wherein A is polyisoprene butylene, B is styrene, and C is selected from glucose, amine, carboxyl group-containing compound, and polyethylene glycol (PEG).
Still other illustrative surfactants include an ethoxylated Castor oil, an ethoxylated coconut fatty acid, or an amidified, ethoxylated coconut fatty acid.
An ethoxylated castor oil can include, for example, a polyoxyethylene (20) castor oil, CAS No. 61791-12-6, PEG (polyethylene glycol)-10 castor oil, PEG-20 castor oil, PEG-3 castor oil, PEG-40 castor oil, PEG-50 castor oil, PEG-60 castor oil, POE (polyoxyethylene) (10) castor oil, POE(20) castor oil; POE (20) castor oil (ether, ester); POE(3) castor oil, POE(40) castor oil, POE(50) castor oil, POE(60) castor oil, or polyoxyethylene (20) castor oil (ether, ester).
An ethoxylated coconut fatty acid can include, for example, CAS No. 39287-84-8, CAS No. 61791-29-5, CAS No. 68921-12-0, CAS No. 8051-46-5, CAS No. 8051-92-1, ethoxylated coconut fatty acid, polyethylene glycol ester of coconut fatty acid, ethoxylated coconut oil acid, polyethylene glycol monoester of coconut oil fatty acid, ethoxylated coco fatty acid. PEG-15 cocoate, PEG-5 cocoate, PEG-8 cocoate, polyethylene glycol (15) monococoate, polyethylene glycol (5) monococoate, polyethylene glycol 400 monococoate, polyethylene glycol monococonut ester, monococonate polyethylene glycol, monococonut oil fatty acid ester of polyethylene glycol, polyoxyethylene (15) monococoate, polyoxyethylene (5) monococoate, or polyoxyethylene (8) monococoate.
An amidified, ethoxylated coconut fatty acid can include, for example, CAS No. 61791-08-0, ethoxylated reaction products of coco fatty acids with ethanolamine, PEG-11 cocamide, PEG-20 cocamide, PEG-3 cocamide, PEG-5 cocamide, PEG-6 cocamide, PEG-7 cocamide, polyethylene glycol (11) coconut amide, polyethylene glycol (3) coconut amide, polyethylene glycol (5) coconut amide, polyethylene glycol (7) coconut amide, polyethylene glycol 1000 coconut amide, polyethylene glycol 300 coconut amide, polyoxyethylene (11) coconut amide, polyoxyethylene (20) coconut amide, polyoxyethylene (3) coconut amide, polyoxyethylene (5) coconut amide, polyoxyethylene (6) coconut amide, or polyoxyethylene (7) coconut amide.
The surfactant can be, for example, one or more of Alfoterra® 123-8S, Alfoterra® 145-8S, Alfoterra® L167-7S, Ethox® HCO-5, Ethox® HCO-25, Ethox® CO-40, Ethox® ML-5, Ethal® LA-4, AG-6202, AG-6206, Ethox® CO-36, Ethox® CO-81, Ethox® CO-25, Ethox® TO-16, Ethsorbox® L-20, Ethox® MO-14, S-MAZ 80K, T-MAZ 60 K 60, Tergitol® L-64, Dowfax® 8390, Alfoterra® L167-4S, Alfoterra® L123-4S, and Alfoterra® L145-4S.
The surfactant can be, for example, one or more of castor oil, cocoa oil, cocoa butter, coconut oil, soy oil, tallow oil, cotton seed oil, a naturally occurring plant oil and a plant extract. Further, the surfactant can be, for example, one or more of an alkyl polyglucoside or an alkyl polyglucoside-based surfactant, a decyl polyglucoside or an alkyl decylpolyglucoside-based surfactant.
The concentration of the surfactant used in the process of this disclosure can vary over a wide range and need only be a concentration sufficient to form the mesoporous metal oxides. The surfactant can be present in a molar concentration ratio of from about 1×10−5 M to about 1 M, preferably from about 1×10−4 M to about 1×10−1 M, and more preferably from about 1×10−3 M to about 1×10−2 M (based on a total volume of 10 milliliters).
The step of preparing the acidic mixture may comprise combining the metal precursor with an interface modifier, a hydrotropic ion precursor, and a surfactant. The mixture may be a solution, a micellar solution, a microemulsion, an emulsion, a dispersion or some other type of mixture. The ratio of metal precursor to surfactant may be between about 1:100 and about 1:2 on a w/w, v/v or w/v basis, and may be about 1:20. Before, during and/or after the combining, the acidic mixture may be agitated, e.g. shaken, stirred, swirled, sonicated or otherwise agitated. The mixture may have a pH between about 0.5 and about 5, or between about 1 and about 3.
The metal precursor, interface modifier, hydrotropic ion precursor, and surfactant may be added to the mixture in any combination or at any stage during the process of preparing the acidic mixture. The metal precursor, interface modifier, hydrotropic ion precursor, and surfactant may be added with or without agitation. Ti and Zr are exceptions. In these preparations, HNO3 is first diluted in butanol.
The process may comprise the step of agitating the acidic mixture to form a solution, a dispersion or an emulsion. The emulsion may be a microemulsion. The agitating may be vigorous, moderate or mild. It may comprise shaking, stirring, sonicating, ultrasonicating, swirling or some other form of agitation. The step of reacting may comprise the step of agitating the acidic mixture or the step of agitating the acidic mixture may be a separate step conducted before the step of reacting.
In accordance with the process of this disclosure, the acidic mixture is heated at a temperature and for a period of time sufficient to form the mesoporous metal oxide. In particular, the acidic mixture is heated at a temperature and for a period of time sufficient to form a dried powder. The dried powder is first washed with an alcohol, e.g., ethanol, to remove organic components, e.g., surfactant, and then heated at a temperature and for a period of time sufficient to form the mesoporous transition metal oxide. The heating may be in air, or in some other gas, for example, oxygen, nitrogen, carbon dioxide, helium, argon or a mixture of any two or more of these.
The acidic mixture is heated sequentially in the following manner. The acidic mixture can be first heated at a temperature from about 75° C. to about 150° C., preferably from about 85° C. to about 140° C., and more preferably from about 90° C. to about 130° C., for a period from about 1 to about 12 hours, preferably from about 1 to about 10 hours, and more preferably from about 1 to about 8 hours. Thereafter, the acidic mixture can be heated at a temperature from about 40° C. to about 80° C., preferably from about 45° C. to about 75° C., and more preferably from about 50° C. to about 70° C., for a period from about 1 to about 12 hours, preferably from about 1 to about 10 hours, and more preferably from about 1 to about 8 hours, to form the dried powder. This sequential heating is carried out in a manner sufficient to remove chemisorbed and/or physisorbed NO3 and any left over NOx.
The dried powder is heated sequentially in the following manner. Firstly, the dried powder is heated at a temperature from about 100° C. to about 200° C., preferably from about 125° C. to about 175° C., and more preferably from about 140° C. to about 160° C., for a period from about 2 to about 20 hours, preferably from about 4 to about 18 hours, and more preferably from about 6 to about 16 hours. Secondly, the dried powder is heated at a temperature from about 200° C. to about 300° C., preferably from about 225° C. to about 275° C., and more preferably from about 240° C. to about 260° C., for a period from about 1 to about 10 hours, preferably from about 2 to about 8 hours, and more preferably from about 2 to about 6 hours. Thirdly, the dried powder is heated at a temperature from about 300° C. to about 400° C., preferably from about 325° C. to about 375° C., and more preferably from about 340° C. to about 360° C., for a period from about 1 to about 8 hours, preferably from about 1 to about 7 hours, and more preferably from about 1 to about 6 hours. Fourthly, the dried powder is heated at a temperature from about 400° C. to about 500° C., preferably from about 425° C. to about 475° C., and more preferably from about 440° C. to about 460° C., for a period from about 0.5 to about 5 hours, preferably from about 1 to about 4 hours, and more preferably from about 1 to about 3 hours. Fifthly, the dried powder is heated at a temperature from about 500° C. to about 600° C., preferably from about 525° C. to about 575° C., and more preferably from about 540° C. to about 560° C., for a period from about 0.1 to about 2 hours, preferably from about 0.25 to about 2 hours, and more preferably from about 0.5 to about 2 hours.
In an embodiment, the acidic mixture is heated sequentially as follows: at a temperature of about 100° C.-120° C. for a period of about 2-7 hours; and at a temperature of about 60° C. for a period of about 8-12 hours (e.g., overnight). In another embodiment, the dried powder is heated sequentially as follows: at a temperature of about 150° C. for a period of about 12 hours; at a temperature of about 250° C. for a period of about 4 hours; at a temperature of about 350° C. for a period of about 3 hours; at a temperature of about 450° C. for a period of about 2 hours; and at a temperature of about 550° C. for a period of about 1 hour.
The process of this disclosure can be conducted at a pressure sufficient to form the mesoporous metal oxide materials. Positive or negative pressures may be useful in the process of this disclosure. Suitable combinations of pressure, temperature and contact time may be employed in the process of this disclosure, in particular, temperature-pressure relationships that give mesoporous metal oxide materials having desired properties and/or characteristics. The pressure may range between about ambient and about 50 atmospheres, preferably between about ambient to about 40 atmospheres, and more preferably between about ambient to about 25 atmospheres. Normally the process is carried out at ambient pressure.
The process may additionally comprise washing the dried powder, e.g., nanoparticulates, for a period of time sufficient to remove organic components therefrom. The washing liquid may be water, or an aqueous liquid, or with a non-aqueous liquid, or an organic liquid (e.g., ethanol), or some combination of these. The particles may be washed once or more than once, and may be washed between 1 and about 10 times or more. Each wash may be with the same washing liquid as any other wash, or may be with a different washing liquid. The washing may comprise exposing the nanoparticulates to the washing liquid, e.g. suspending the nanoparticulates in the washing liquid, and then separating the nanoparticulates from the washing liquid, using any of the separating processes described herein. In particular, the dried powder is washed with ethanol for a period of time sufficient to remove surfactant therefrom.
The process may additionally comprise at least partially separating the nanoparticulates from a fluid (e.g., washing fluid) in which they are located (optionally suspended or dispersed). This may comprise filtering, settling, decanting, centrifuging, vacuum filtering, dialysis, membrane filtering, magnetic separation, or some other suitable process, and may comprise more than one of these.
In an embodiment, the mesoporous metal oxides can be nanoparticulates having a particle size between about 1 and about 500 nm, or between about 50 and about 300 nm, and a mean pore size between about 1 and about 50 nm, or between about 1 and about 30 nm or greater than 2 nm, or between about 2 and 13 nm. The nanoparticulates may have a 3-D cubic or 3-D foam-like mesostructure, or may have a 2-D hexagonal or wormlike mesostructure. The mesoporous nanoparticulates may comprise mesoporous transition metal oxides, Lanthanide metal oxides, post-transition metal oxides and metalloid oxides. The mesoporous metal oxides may be doped with other elements, for example titanium, aluminum or zirconium. The mesoporous nanoparticulates may be spherical or some other regular shape. There is also provided a plurality of mesoporous nanoparticulates. The mean particle size of the nanoparticulates may be between about 1 and about 500 nm. The particle size distribution may be broad or narrow. There may be less than about 50% of nanoparticulates having a particle size more than 10% different from (greater than or less than) the mean particle size.
The mesoporous metal oxides prepared by the process of this disclosure include oxides of transition metals, Lanthanide metals, post-transition metals, metalloids, and mixtures thereof. For example, the transition metal oxides comprise Group 3-12 transition metal oxides, in particular, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni. Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg oxides. In an embodiment, the transition metal oxides are selected from Group 6-12 transition metal oxides including Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu. Ag, Au, Zn, Cd and Hg oxides. Preferably, the Group 6-12 transition metal oxides include Mn, Fe, Co, Ni, Cu and Zn oxides. The Lanthanide metal oxides include La, Ce. Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu oxides, or any mixture thereof. The post-transition metal oxides include Al, Ga, In, TI, Sn, Pb and Bi oxides, or any mixture thereof. The metalloid oxides include B, Si, Ge, As, Sb, Te, Po and At oxides, or any mixture thereof.
The surface area of the mesoporous metal oxide particulates, e.g. BET surface area, maybe between about 50 and about 1000 m2/g, and may be between about 60 and 500, 70 and 200 and 80 and 190, m2/g, and may be about 50, 75, 100, 125, 150, 175 or 200 m2/g.
The pore volume (BJH) may be between about 0.05 and about 2 cm3/g, or between about 0.075 and 2, and 0.1 and 2 cm3/g, and may be about 0.05, 0.1, 0.15, 0.2 or 0.25 cm3/g.
The pore size (diameter), e.g., BJH desorption, may be between about 1 and 50 nm, or between about 1.5 and 50 nm, 1.5 and 20 nm, 2 and 15 nm, and 2 and 13 nm, and may be about 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 0.5.0, 5.5 and 6 nm.
The wall thickness (2d/43−PD, where d is the d-spacing and PD is the pore diameter) may be between about 2 and about 20 nm, or between about 3 and about 16 nm, 4 and 14 nm, or 5 and 12 nm, and may be about 5.0 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 and 10.0 nm. The formula applies to 2-dimensional hexagonal materials.
The crystal structures of the nano-sized metal oxide walls include, for example, CeO2, Mn2O3, Mn3O4, Fe2O3, Co3O4, ZnO, CuO, TiO2 (Anatase), ZrO2, NiOOH, and the like.
The mesoporous particulates may be round or spherical, or may be oblate spherical, rod-like, aggregated, ellipsoid, ovoid, a modified oval shape, dome shaped, hemispherical; a round ended cylinder, capsule shaped, discoid, prismatic, acicular or polyhedral (either regular or irregular) such as a cube, a rectangular prism, a rectangular parallelepiped, a triangular prism, a hexagonal prism, rhomboid or a polyhedron with between 4 and 60 or more faces, or may be some other shape, for example an irregular shape.
The mesoporous metal oxides of this disclosure exhibit properties that are advantageous for specific applications. For example, the mesoporous metal oxides can exhibit thermal stability up to a temperature of about 350° C., preferably up to a temperature of about 450° C., and more preferably up to a temperature of about 550° C. Also, the mesoporous metal oxides can exhibit high pore volume after heat treatment cycles. For example, the unit cell expansion and pore-size increase do not cause a significant change at pore volume. In other words, ideally for a given material, one can change the pore size from the super micropore region (about 2 nm) to the mid mesopore region (about 20 nm) by preserving pore volume. Further, the mesoporous metal oxides can exhibit physicochemical properties after catalytic reactions under high pressure and temperature. For example, catalytic tests done on mesoporous ZrO2 and CeO2 under 20 bar pressure of N2 or H2 at 150° C. did not cause any change of physicochemical properties of the materials.
The mesoporous metal oxide nanoparticulates, or a plurality thereof, can be useful for a variety of applications including, for example, catalysis, gas adsorption, synthesis of quantum dots and magnetic nanoparticles in functional materials and bioimaging applications, and as carriers for drugs, genes and proteins for biomedical applications. In particular, the mesoporous metal oxides are useful as catalysts, sensors, batteries and energy production, optical displays, environmental and sorbent applications.
There are several advantages afforded by the method of this disclosure including, for example, control of the crystal structure of the wall during heating, the possibility of synthesis without surfactant, precise control of pore size, and the method can be extended to a variety of transition metal oxides, Lanthanide oxides, post-transition metal oxides and metalloid oxides. The Pluronic® P123 surfactant is non-ionic and low foaming. Other advantages of the process of this disclosure for the synthesis of mesoporous metal oxides are that H+ is not a concern, in principle the process is applicable to all transition metals, Lanthanide metals, port-transition metals and metalloids, different types of surfactants can be used, gelation is not required, the crystal structure (i.e., for manganese oxides, Hausmannite, Pyrolusite, Bixbyite) can all be formed, thickness of walls can be controlled, fine tuning of magnetic and optical properties is possible, and pore expansion on heat treatment of the mesoporous materials occurs. Highly optically pure glass materials, light sensitive lenses and ultra violet absorbing lenses for plastic or glass materials may be made in accordance with the process of this disclosure.
In the above detailed description, the specific embodiments of this disclosure have been described in connection with its preferred embodiments. However, to the extent that the above description is specific to a particular embodiment or a particular use of this disclosure, this is intended to be illustrative only and merely provides a concise description of the exemplary embodiments. Accordingly, the disclosure is not limited to the specific embodiments described above, but rather, the disclosure includes all alternatives, modifications, and equivalents falling within the true scope of the appended claims. Various modifications and variations of this disclosure will be obvious to a worker skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the claims.
All reactions in the following examples were performed using as-received starting materials without any purification.
Example 1
Synthesis of Mesoporous Transition Metal Oxides
Various transition metal oxides were synthesized by following procedure. 0.01 mol M(NO3)x.yH2O (M=Mn, Fe, Co, Cu, Zn), 0.09-0.18 mol n-butanol (7-14 grams), 0.016-0.032 mol HNO3 (1-2 grams) and 1 gram of surfactant (Pluronic® P123 or Pluronic® F127) were mixed in a 50 milliliter beaker and homogenized by stirring at room temperature. The resulting clear solution was directly put in an oven running at 100° C.-120° C. (depending on metal system studied) and kept at that temperature for 2-7 hours (variations of concentrations, temperature and duration of experiment depend on the metal system studied). Synthesized materials were washed with ethanol several times to remove organic components and dried in an oven running at 60° C. overnight.
Dry powders were heated in an oven at the following temperatures and time intervals; 150° C. (12 hours), 250° C. (4 hours), 350° C. (3 hours), 450° C. (2 hours) and finally at 550° C. (1 hour) (all heating steps applied in this order).
Example 2
Characterization of Nanocomposite Materials
The mesostructure of synthesized and heat treated materials was determined by low angle powder X-ray diffraction (PXRD). The crystal structure of materials was characterized by PXRD technique. Pore structural properties were determined by nitrogen sorption. Surface areas were determined by the BET (Brunauer-Emmett-Teller) method and pore sizes are determined from the desorption branch of the corresponding isotherm by the BJH (Barret-Joyner-Halenda) method. SEM (scanning electron microscopy) and TEM (transmission electron microscopy) were collected in order to determine particle, surface morphologies and mesopores respectively.
FIG. 1 shows the low angle PXRD data of Mesoporous Manganese Oxide (MMO) and unit cell expansion by heat treatment. As seen from the data, diffraction lines gets sharper and shift to lower angles throughout heat treatment indicating an increase in order of mesoporous material and expansion in unit cell dimensions. FIG. 2 shows the wide angle PXRD patterns of MMO materials treated at different final temperatures. Up to 450° C. diffraction patterns show broad diffraction lines indicating that materials are not well ordered (or amorphous) or consist of nano-sized crystalline domains. However, MMO materials have well defined crystal structures above this temperature. Diffraction lines for these materials can be indexed to the Mn2O3 (Bixbyite) crystal structure. FIG. 3 shows nitrogen sorption isotherm of MMO samples with different final heat treatment temperatures and corresponding BJH desorption pore size distributions. All MMO materials have type IV isotherms regardless of the final heat treatment temperature applied. As seen from the pore size distributions, pore size expands constantly with increased temperature. As stated before pore size expansion has not been observed for either heat treated or calcined samples. FIG. 4 shows scanning electron microscope (SEM) images of MMO samples with final heat treatment temperature of 450° C.
The structural parameters of the MMO samples obtained by combining the PXRD and nitrogen sorption data are given in Table 2 below.











TABLE 2







Pore Volume
Pore Diameter



Δ (max)
SA (BET)
(BJH)
(BJH des)
Wall thickness*







250 C.°
200 m2\g
0.153 cc\g
2.8 nm
4.7 nm


350 C.°
191 m2\g
0.224 cc\g
3.7 nm
5.2 nm


450 C.°
100 m2\g
0.200 cc\g
5.3 nm
8.0 nm


550 C.°
 35 m2\g
0.125 cc\g
12.3 nm 
7.9 nm





Wall Thickness = (2d/√3 − PD, where d is the d-spacing and PD is the pore diameter)






Example 3
Other mesoporous transition metal oxides were prepared in a manner similar to MMO in Example 1. The conditions for the preparation of these mesoporous transition metal oxides are set forth in Table 3 below. As used in Table 3, TEOS is tetraethyl orthosilicate Si(OC2H5)4 and Ti(OCH(CH3)2)4 is tetra-isopropoxide titanium or titanium isopropoxide.













TABLE 3












Reaction




Metal



Temperature
Traction


Metal
Amount (mol)
Butanol (g-mol)
HNO3 (g-mol)
P123 (g-mol)
T ° C.
time t (h)

















Manganese
0.01 mol
7 g-0.094 mol
1 g-0.016 mol
1 g-1.7 * 10−4 mol
120°
4
h


Mn(NO3)2•4H2O









Iron
0.01 mol
8.5 g-0.115 mol
1.2 g-0.019 mol
1.2 g-2.04 * 10−4 mol
100°
2-3
h


Fe(NO3)3•6H2O









Cobalt
0.01 mol
8.5 g-0.115 mol
1.2 g-0.019 mol
1.2 g-2.04 * 10−4 mol
120°
4-6
h


Co(NO3)2•6H2O









Nickel
0.01 mol
10 g-0.135 mol
1.2 g-0.019 mol
1.2 g-2.04 * 10−4 mol
120°
4
h


Ni(NO2)3•6H2O









Copper
2 g-0.01
7 g-0.094 mol
1 g-0.016 mol
1.5 g-2.6 * 10−4 mol
120°
2-3
h


Cu(NO3)2•XH2O
mol








Zinc
0.01 mol
7 g-0.094 mol
1 g-0.016 mol
1.5 g-2.6 * 10−4 mol
120°
5-6
h


Zn(NO3)2•6H2O









Ceria
0.01 mol
7 g-0.094 mol
1 g-0.016 mol
1.5 g-2.6 * 10−4 mol
120°
6
h


Ce(NO3)2•6H2O









Silica
0.0099 mol 
7 g-0.094 mol
7 g (Butanol)| +
1 g-1.7 * 10−4 mol
120°
4-6
h


TEOS


1 g-0.016 mol









(HNO3)






Titanium
0.0094 mol 
7 g-0.094 mol
7 g (Butanol)| +
1 g-1.7 * 10−4 mol
120°
3-5
h


Ti(OCH(CH3)2)4


1 g-0.016 mol









(HNO3)






Aluminum
0.0099 mol
7 g-0.094 mol
7 g (Butanol)| +
1 g-1.7 * 10−4 mol
120°
4-6
h


Silicate
(TEOS)

1 g-0.016 mol






Al:Si = 1:5
0.0018 mol

(HNO3)






TEOS and
(Aluminum








Al(NO3)2 9H2O
nitrate)














Metal
Heating Cycles
Observations






Manganese
150° C. (12 h)-250° C. (4 h)-
Yellow gel after 1 h. Exactly 4 h reaction



Mn(NO3)2•4H2O
350° C. (3 h)-450° C. (2 h)-





550° C. (1 h)




Iron
150° C. (12 h)-250° C. (4 h)-
Red gel after mixing. Dark red gel after 1 h.



Fe(NO3)3•6H2O
350° C. (3 h)-450° C. (2 h)-
No longer than 3 h (after nonporous Iron




550° C. (1 h)
Oxide)



Cobalt
150° C. (12 h)-250° C. (4 h)-
Low yield, 150° C. yields magnetic Cobalt



Co(NO3)2•6H2O
350° C. (3 h)-450° C. (2 h)-
Oxide (mesostructured)




550° C. (1 h)




Nickel
150° C. (12 h)-250° C. (4 h)-
Low yield



Ni(NO2)3•6H2O
350° C. (3 h)-450° C. (2 h)-





550° C. (1 h)




Copper
150° C. (12 h)
Not Thermally Stable-mesostructured but not



Cu(NO3)2•XH2O

porous



Zinc
150° C. (12 h)
Not Thermally Stable-mesostructured but not



Zn(NO3)2•6H2O

porous



Ceria
150° C. (12 h)-250° C. (4 h)-
Yield depends on the amount of surfactant



Ce(NO3)2•6H2O
350° C. (3 h)-450° C. (2 h)-
used. Crystalline solid and particle size is




550° C. (1 h)-600° C. (1 h)
consistent with the crystal size.



Silica
450° C. (4 h) (1° C./min
Yellow transparent film. Directly calcined



TEOS
heating rate)
@ 450° C. for 4 h (microporous)



Titanium
400° C., 450° C. or 500° C. (4 h)
Orange transparent film. Directly calcined



Ti(OCH(CH3)2)4
(1° C./min heating rate)
@ 450° C. for 4 h



Aluminum
450° C. (4 h) (1° C./min
Microporous, slightly brownish powder



Silicate
heating rate)




Al:Si = 1:5





TEOS and





Al(NO3)2 9H2O









Mesoporous transition metal oxides were prepared in accordance with the conditions set forth in Table 3. A listing of the prepared mesoporous transition metal oxides is set forth in Table 4 below including properties exhibited by these mesoporous transition metal oxides. FIGS. 5-35 depict properties exhibited by these mesoporous transition metal oxides.













TABLE 4







Max Heat


Low-Angle XRD





Treatment T
Surface Area
BJH Des. Pore
peak position



Metal
Nomenclature
(° C.)
(m2/g)
Diameter (nm)
(nm)
Crystal Structure





















Manganese
UCT-1
150
255
2.0*
3.1
Amorphous




250
200
2.8
6.7
Amorphous




350
191
3.7
7.7
Amorphous



UCT-2
450
100
5.3
11.5
Mn2O3




550
35
12.3
17.5
Mn2O3


Iron
UCT-5
150
124
1.54*
4.2
Amorphous




250
225
2.2
5.0
Amorphous



UCT-6
350
167
3.4
7.9
Fe2O3




450
46
9.6
24.5
Fe2O3


Cobalt
UCT-7
150
9
Non-porous
9.3
Co3O4 & C4H8








Co3O4•4H2O



UCT-8
250
129
5.7
12.2
Co3O4




350
110
7.8
14.5
Co3O4


Nickel
UCT-9
150
20
Non-porous
6.6
(H3O)2NiO2 &








NiOOH &








Ni(OH)2•0.75H2O



UCT-10
250
195
5.5
7.4
Ni15O16




350
81
9.7
9.6
Ni15O16




450
60
9.7
9.8
Ni15O16


Copper
UCT-11
150
48
Non-porous
5.4
Cu2(NO3)(OH)3




250
22
Non-porous
12.1
CuO




350
11
Non-porous
6.1
CuO


Zinc
UCT-12
150
70
Non-porous
6.6
ZnC2O4


Titanium
UCT-13
 450  
103
3.5
8.8
TiO2 (Anatase)


Silica
UCT-14
 450  
435
1.4*
4.6
Amorphous


Aluminum
UCT-15
 450  
385 (1:5) 
1.2*
6.5
Amorphous


silicate

 450  
326 (1:10)
1.2*
—
Amorphous


(Al:Si = 1:5, 10,

 450  
308 (1:20)
1.2*
—
Amorphous


20, 50)

 450  
397 (1:50)
1.2*
—
Amorphous




 550  
325 (1:20)
1.2*
—
Amorphous




 550  
401 (1:50)
1.2*
—
Amorphous


Ceria
UCT-16
150
98
Non-porous
2.9
CeO2




250
152
1.1*
3.2
CeO2




350
173
1.1*
3.4
CeO2




450
150
1.3*
3.7
CeO2




550
127
1.6
5.1
CeO2




600
72
1.9
7.1
CeO2


Manganese
UCT-3
350
160
3.5
9.3
Mn2O3


(F127)

450
68
4.5
11.3
Mn2O3


Manganese
UCT-4
150 (24 h)
—
—
7.7
Mn3O4


(long








reaction








time)





*DFT pore size distribution. Cylindrical pore model nitrogen on carbon.


 Direct calcination to final temperature with 1° C./min heating rate.






Table 4 above describes 16 new families of materials identified with acronyms UCT-#. For example, UCT-1 represents amorphous manganese oxide materials that have controllable pore sizes. One can further delineate these materials from Table 4 as UCT-1-150, UCT-1-250, and UCT-350 representing materials with the same basic amorphous structure but with different pore sizes. UCT-2 represents mesoporous crystalline Mn2O3 materials. Table 4 shows that UCT-2-450 heated to 450° C. has the Mn2O3 structure with specific pore diameter of 5.3 nm and surface area of 100 m2/g. UCT-2-550 has the same Mn2O3 structure but different surface properties. The other materials from UCT-3 through UCT-16 are summarized accordingly in Table 4.
Referring to FIGS. 5 and 6, a comparison of structural parameters of mesoporous Mn2O3 synthesized with two different Pluronic® surfactants is set forth in Table 5 below.












TABLE 5








Pore







Volume
Pore Diameter
Wall



Δ (max)
SA (BET)
(BJH)
(BJH des)
thickness*























 350 C.°
 160 m 2 /g
 0.160 cc/g
 3.5 nm
 7.8 nm


F127
 {open oversize brace} 









 450 C.°
  68 m 2 /g
 0.116 cc/g
 4.5 nm
 9.5 nm




 350 C.°
 191 m 2 /g
 0.224 cc/g
 3.7 nm
 5.2 nm


P123
 {open oversize brace} 









 450 C.°
 100 m 2 /g
 0.200 cc/g
 5.3 nm
 8.0 nm









Referring to FIGS. 16-18, a comparison of surface area (BET) of mesoporous CuO at different temperatures is set forth in Table 6 below.









TABLE 6






Δ (max)
SA (BET)








150 C.°
47.5 m2\g



250 C.°
21.8 m2\g









Referring to FIGS. 22 and 23, a comparison of surface area (BET) of mesoporous CeO2 at different temperatures is set forth in Table 7 below.









TABLE 7






Δ (max)
SA (BET)








150 C.°
 97.5 m2\g



250 C.°
152.3 m2\g



350 C.°
173.4 m2\g



450 C.°
149.9 m2\g



550 C.°
127.3 m2\g



600 C.°
 71.6 m2\g









FIG. 40 depicts a Hantzsch reaction catalyzed by mesoporous iron oxide. The Hantzsch reaction was conducted in accordance with the conditions set forth in FIG. 41. Conversions and selectivities are set forth in FIG. 41. Compound 1 is a pharmaceutical compound.
FIG. 42 depicts an adamantane oxidation reaction catalyzed by mesoporous manganese oxide. The adamantane oxidation reaction was conducted in accordance with the conditions set forth in FIG. 43. Conversions and selectivities are set forth in FIG. 43.
FIG. 44 depicts a hydration reaction catalyzed by mesoporous cerium oxide. The hydration reaction was conducted in accordance with the conditions set forth in FIG. 45. Conversions and selectivities are set forth in FIG. 45.
FIG. 46 depicts a hydrogenation reaction of methyl levulinate catalyzed by mesoporous cerium oxide supported nano-noble metal. The noble metal loading was about 2%. The conversion was 100%. The selectivity to γ-valerolacetone (GVL) was 52% and the selectivity to 5-hydroxypentan-2-one was 42%. The noble metal was added by deposition to the mesoporous material. Enhanced activity was observed in this biomass conversion reaction.
FIG. 47 depicts the conversion of a sugar (i.e., D-fructofuranose) to methyl levulinate. The conversion was conducted in accordance with the conditions set forth in FIG. 48. The particular catalyst, temperature, conversions, selectivities and yields are set forth in FIG. 48. The mesoporous catalysts maintained high activity with no leaching of metal or sulfate into solution.
FIG. 49 depicts data showing properties of mesoporous zirconium oxide in comparison with sulfated mesoporous zirconium oxide. The sulfated mesoporous zirconium oxide leads to a stable material. Sulfating often enhances acidity.
FIG. 50 depicts a benzyl alcohol oxidation reaction catalyzed by mesoporous manganese oxide. The benzyl alcohol oxidation reaction was conducted in accordance with the conditions set forth in FIG. 51. Conversions and selectivities are set forth in FIG. 51.
FIG. 52 depicts what is believed to be the mechanism for HNO3 activity. FIG. 53 depicts a proposed mechanism for the formation of highly ordered mesoporous metal oxide in accordance with this disclosure.
All patents and patent applications, test procedures (such as ASTM methods, UL methods, and the like), and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this disclosure and for all jurisdictions in which such incorporation is permitted.
When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the disclosure have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present disclosure, including all features which would be treated as equivalents thereof by those skilled in the art to which the disclosure pertains.
The present disclosure has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Also, the subject matter of the appended dependent claims is within the full intended scope of all appended independent claims.

## Claims

1. A process for preparing a mesoporous metal oxide said process comprising:
providing an acidic inverse micellar mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant, wherein water is eliminated or minimized to prevent aggregation of metal oxide clusters; and
heating the acidic mixture at a temperature and for a period of time sufficient to form nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxide,
wherein the mesoporous metal oxide has nano-sized wall crystallinity.

2. The process of claim 1, wherein the heating step comprises:
heating the acidic mixture at a temperature and for a period of time sufficient to form a dried powder; and
heating the dried powder at a temperature and for a period of time sufficient to form nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxide.

3. The process of claim 2, wherein the acidic mixture is heated sequentially as follows: at a temperature from about 75° C. to about 150° C. for a period from about 1 to about 12 hours; and at a temperature from about 40° C. to about 80° C. for a period from about 1 to about 12 hours.

4. The process of claim 2, wherein the dried powder is heated sequentially as follows: at a temperature from about 100° C. to about 200° C. for a period from about 2 to about 20 hours; at a temperature from about 200° C. to about 300° C. for a period from about 1 to about 10 hours; at a temperature from about 300° C. to about 400° C. for a period from about 1 to about 8 hours; at a temperature from about 400° C. to about 500° C. for a period from about 0.5 to about 4 hours; and at a temperature from about 500° C. to about 600° C. for a period from about 0.1 to about 2 hours.

5. The process of claim 2, wherein the dried powder is heated sequentially as follows: at a temperature of about 150° C. for a period of about 12 hours; at a temperature of about 250° C. for a period of about 4 hours; at a temperature of about 350° C. for a period of about 3 hours; at a temperature of about 450° C. for a period of about 2 hours; and at a temperature of about 550° C. for a period of about 1 hour.

6. The process of claim 2, further comprising washing the dried powder with an alcohol for a period of time sufficient to remove organic components therefrom.

7. The process of claim 1, wherein the metal precursor is selected from the group consisting of a transition metal precursor, a Lanthanide metal precursor, a post-transition metal precursor, a metalloid precursor, and mixtures thereof.

8. The process of claim 7, wherein the transition metal precursor comprises a Group 3-12 transition metal precursor selected from the group consisting of a Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg precursor.

9. The process of claim 7, wherein the Lanthanide metal precursor is selected from the group consisting of a La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu precursor.

10. The process of claim 7, wherein the post-transition metal precursor is selected from the group consisting of an Al, Ga, In, Tl, Sn, Pb and Bi precursor.

11. The process of claim 7, wherein the metalloid precursor is selected from the group consisting of a B, Si, Ge, As, Sb, Te, Po and At precursor.

12. The process of claim 1, wherein the metal precursor is selected from the group consisting of metal nitrates, metal alkoxides, metal halides, metal phosphates, metal acetates, and MxOy oxides that are capable of dissolving in HNO3.

13. The process of claim 1, wherein the metal precursor is selected from the group consisting of M(NO3)x.yH2O (M=Mn, Fe, Co, Cu, Zn), tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), titanium butoxide, zirconium n-propoxide, zirconium butoxide, Ce(NO3)3.6H2O, Gd(NO3)3.6H2O, and Sm(NO3)3.6H2O.

14. The process of claim 1, wherein the interface modifier comprises an aliphatic, alicyclic or aromatic hydrocarbon, oxygenated hydrocarbon or terpenoid hydrocarbon, of between about 1 and about 20 carbon atoms, or mixtures thereof, that allows the surfactant to organize itself into inverse micelles.

15. The process of claim 1, wherein the hydrotropic ion precursor comprises HNO3, NaNO3, KNO3, metal halides, metal thiocyanides, or mixtures thereof.

16. The process of claim 1, wherein the surfactant comprises an anionic, cationic, non-ionic, or zwitterionic surfactant, or mixtures thereof.

17. The process of claim 1, wherein the surfactant comprises an EO/PO copolymer surfactant.

18. The process of claim 1, wherein the surfactant comprises Pluronic® P65 (EO20PO30EO20), Pluronic® P85 (EO26PO40EO26), Pluronic® 25R4, Pluronic® F108 (EO129PO56EO129), Pluronic® P123 (EO20PO70EO20) or Pluronic® F127 (EO97PO69EO97).

19. The process of claim 1, wherein the surfactant comprises a Triton® surfactant, a Tween® surfactant, glucose, or an AB or BC polymer surfactant, wherein A is polyisoprene butylene, B is styrene, and C is selected from glucose, amine, carboxyl group-containing compound, and polyethylene glycol (PEG).

20. The process of claim 1, wherein the mesoporous metal oxide has a pore size (diameter) between about 1.5 nanometers and about 50 nanometers.

21. The process of claim 1, which is conducted under process conditions sufficient to control pore size and pore size distribution of the metal oxide and crystal structure of nano-sized metal oxide walls.

22. The process of claim 1, wherein the mesoporous metal oxide is selected from the group consisting of a transition metal oxide, a Lanthanide metal oxide, a post-transition metal oxide, a metalloid oxide, and mixtures thereof.

23. The process of claim 22, wherein the transition metal oxide comprises a Group 3-12 transition metal oxide selected from the group consisting of a Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg oxide.

24. The process of claim 22, wherein the Lanthanide metal oxide is selected from the group consisting of a La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu oxide.

25. The process of claim 22, wherein the post-transition metal oxide is selected from the group consisting of an Al, Ga, In, Tl, Sn, Pb and Bi oxide.

26. The process of claim 22, wherein the metalloid oxide is selected from the group consisting of a B, Si, Ge, As, Sb, Te, Po and At oxide.

27. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides, said method comprising:
providing an acidic inverse micellar mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant, wherein water is eliminated or minimized to prevent the aggregation of metal oxide clusters; and
heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides;
wherein the mesoporous metal oxides have nano-sized wall crystallinity.

28. A method of tuning structural properties of crystalline mesoporous metal oxides, said method comprising:
providing an acidic sol-gel micellar mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant, wherein water is eliminated-or minimized to prevent the aggregation of metal oxide clusters;
heating the acidic mixture at a temperature and for a period of time sufficient to form a dried powder; and
heating the dried powder at a temperature and for a period of time sufficient to tune the structural properties of the mesoporous metal oxides;
wherein the mesoporous metal oxides have nano-sized wall crystallinity.