Method of producing a porous crystalline material with a highly uniform structure

Abstract

Described herein is a scalable, economic, energy and time efficient method for the synthesis of a crystalline uniform nanoporous oxide material by utilizing colloidal particles in solution combustion synthesis. By removing colloids from nanocomposite via chemical etching crystalline uniform porous oxide is prepared with tailored porosity. The produced oxides have high specific surface area, high pore volume, uniform pore structure and high crystallinity. Properties of the oxide can be tuned by the concentration and size of colloids added, which affects the porous structure (mesopore diameter, pore wall thickness, surface area, and pore volume). In principle, this method can be applied to synthesize different high porosity crystalline metal oxides and nanocomposites.

Claims

1. A method of synthesizing a porous material via combustion of a colloidal solution comprising: a) preparing a colloidal solution by dissolving in water a fuel and an oxidant and dispersing colloidal particles, wherein the fuel comprises amino acid, amide, thioamide, citrate, oxalate, alcohol, hydrazine or its derivative, or amine or combinations thereof; b) heating the solution to ignition and initiate a combustion to produce a composite material comprising colloidal particles via an exothermic process; and c) dissolving the colloidal particles to create uniform porosity.

2. The method of claim 1 further comprising a metal precursor, wherein the oxidant is the metal precursor.

3. The method of claim 2 wherein the amino acid is one or more of glycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, proline, or tryptophan; and/or wherein the amide is formamide, ethanamide, propanamide, or butanamide; and/or wherein the thioamide is thioformamide, thioethanamide, thiopropanamide, or thiobutanamide; and/or wherein the citrate is citric acid, trisodium citrate, or ammonium citrate; and/or wherein the oxalate is oxalic acid, or dimethyl oxalate; and/or wherein the alcohol is ethylene glycol, glycerol or furfuryl alcohol; and/or wherein the hydrazine and its derivative is hydrazine hydrate, hydrazine hydrochloride, acetyl hydrazine, 1,2,4-triazole, 2-amino1,2,4-triazole, or 4-amino1,2,4-triazole; and/or wherein the amine is ethylene diamine.

4. The method of claim 1 wherein the colloidal particle comprises an oxide or a metal or combinations thereof.

5. The method of claim 4 wherein the oxide is one or more of SiO.sub.2, Al.sub.2O.sub.3, CeO.sub.2, Fe.sub.2O.sub.3, TiO.sub.2, ZrO.sub.2, Fe.sub.3O.sub.4, ZnO, WO.sub.3, CuO, Cu.sub.2O, MoO.sub.3, Y.sub.2O.sub.3, Sm.sub.2O.sub.3, Gd.sub.2O.sub.3, or Co.sub.3O.sub.4; and/or wherein the metal is one or more of Ag, Au, Pt, Pd, Ru, Rh, Ni, Co, Fe, Cu, Zr or Ti; and/or wherein diameter of the oxide is in a range from 5 to 200 nm; and/or wherein diameter of the metal is in a range from 2 to 200 nm.

6. The method of claim 1 wherein the oxidant is a nitrate; and/or wherein the oxidant comprises one or more of Ce(NO.sub.3).sub.3, Cu(NO.sub.3).sub.2, Pd(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, AgNO.sub.3, Zn(NO.sub.3).sub.2, TiO(NO.sub.3).sub.2, ZrO(NO.sub.3).sub.2, Ni(NO.sub.3).sub.2, Co(NO.sub.3).sub.2, Mg(NO.sub.3).sub.2, Sr(NO.sub.3).sub.2, Ba(NO.sub.3).sub.2, Y(NO.sub.3).sub.3, LiNO.sub.3, NaNO.sub.3, KNO.sub.3, Cr(NO.sub.3).sub.3, Mn(NO.sub.3).sub.2, Bi(NO.sub.3).sub.3, Mg(NO.sub.3).sub.2, Pb(NO.sub.3).sub.2, La(NO.sub.3).sub.3, NH.sub.4NO.sub.3, Ce(NH.sub.4).sub.2(NO.sub.3).sub.6, Pr(NO.sub.3).sub.3, Sm(NO.sub.3).sub.3, Eu(NO.sub.3).sub.3, In(NO.sub.3).sub.3, Gd(NO.sub.3).sub.3, Sc(NO.sub.3).sub.3 or Tb(NO.sub.3).sub.3; and/or wherein the ratio of oxidant to fuel is 5:1 to 0.2:1; and/or wherein the ratio of oxidant to dispersing colloidal particles is 1:0.2 to 1:5; and/or wherein the step of heating comprises removing water from the colloidal solution to obtain a gel; and/or wherein during removing water from the colloidal solution to obtain a gel, the heating rate is between 0.1 degree Celsius per minute and 50 or 100 degree Celsius per minute up to ignition of the gel in open air, wherein after the ignition the reaction is exothermic yielding oxide/colloid composite material; and/or wherein the colloidal particle is removed by chemical etching to produce uniform porous oxide, wherein chemical etching comprising of etching of colloid by NaOH, KOH, HF, HCl, HNO.sub.3, H.sub.2SO.sub.4, KCN, or CH.sub.3COOH or combinations thereof; and/or wherein the pore diameter of porous oxide has a size from 2 nm to 200 nm; and/or wherein the method comprises using a produced uniform porous oxide of the porous material in a coating, polishing slurry or paste, a catalyst, a gas sensing device, an optical device, a battery device, a storage device, a ceramic, or a magnetic device; and/or further comprising a metal precursor, the metal precursor comprises metal chloride, metal sulfate, or metal sulfide; and/or the metal precursor does not support combustion of the fuel and become a dopant or active component in the porous material.

7. A method of synthesizing a composite material via combustion of a colloidal solution comprising: a) preparing a colloidal solution by dissolving in water a fuel and an oxidant, and dispersing colloidal particles, wherein the fuel comprises amino acid, amide, thioamide, citrate, oxalate, alcohol, hydrazine or its derivative, or amine or combinations thereof; and b) heating the solution to ignition and initiate a combustion to produce a composite material comprising colloidal particles within an oxide via an exothermic process for applications as a coating, polishing slurry or paste, a catalysis, a gas sensing device, an optical device, a battery device, a storage device, a ceramic, or a magnetic device.

8. A method of making a porous nanomaterial, comprising: combining colloidal nanoparticles with a nitrate and a fuel in an aqueous solution; heating the aqueous solution to form a gel; permitting an exothermic reaction to proceed to form a nanocomposite material; and removing colloidal nanoparticles from the nanocomposite material to provide a porous nanomaterial.

9. The method of claim 8, wherein the nanocomposite material comprises colloidal nanoparticles embedded therein; and/or wherein the porous nanomaterial comprises a porous crystalline nanomaterial; and/or wherein the porous nanomaterial comprises pores having a diameter from 2 to 200 nm or 2 to 100 nm; and/or wherein the colloidal nanoparticles are removed from the nanocomposite material by chemical etching.

10. The method of claim 7, wherein the colloidal solution is prepared by dissolving in water the fuel, the oxidant, and a metal precursor.

11. The method of claim 10 wherein the oxidant is the metal precursor.

12. The method of claim 8, wherein the colloidal solution is prepared by dissolving in water the fuel, the oxidant, and a metal precursor.

13. The method of claim 12 wherein the oxidant is the metal precursor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1. Schematic of synthesizing crystalline nanocomposite or uniform nanoporous oxide with tailored porosity: (a) colloidal solution (b) gel (c) combustion confined by colloids (d) nanocomposite with periodically arranged colloids (e) highly nanoporous oxide after etching of colloidal particles in accordance with the invention.

(2) FIG. 2. TEM image of initial colloidal SiO.sub.2.

(3) FIG. 3. SEM image of CeO.sub.2 after etching of SiO.sub.2.

(4) FIG. 4. TEM images of ceria-3.

(5) FIG. 5. HRTEM image of ceria-3.

(6) FIG. 6. BJH pore size distribution plots for different CeO.sub.2 samples.

(7) FIG. 7. N.sub.2 sorption isotherms vertically shifted for clarity for different CeO.sub.2 samples.

(8) FIG. 8. XRD patterns for different CeO.sub.2 samples of the invention.

(9) FIG. 9. Temperature-time profiles for different CeO.sub.2 samples.

(10) FIG. 10. BJH pore size distribution curve and TEM image (inset: SAED) of CuO synthesized in accordance with the methods described herein.

DETAILED DESCRIPTION

(11) With reference to FIG. 1, the invention provides scalable method of manufacturing uniform porous nanomaterials by using colloidal particles as a template in solution combustion synthesis wherein the colloids have uniform arrangement in nanocomposite produced and nanocomposite composed of oxide/oxide, oxide/metal or metal/oxide possessing unique nanostructure. The preparation method of uniform porous crystalline nanomaterial by using colloidal nanoparticles is provided and method comprises of the following steps. First, colloidal nanoparticles are added to an aqueous solution of nitrate and fuel. Upon heating and water evaporation, a gel is formed between assembled colloids followed by self-ignition. After ignition, the reaction is exothermic resulting in the formation of nanocomposite material with embedded colloidal nanoparticles having a uniform arrangement. The colloidal particles then can be removed by a chemical etching to yield a uniform porous crystalline nanomaterial.

(12) The fuel used in this embodiment may be a glycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, proline, tryptophan, formamide, ethanamide, propanamide, butanamide, thioamide, thioformamide, thioethanamide, thiopropanamide, thiobutanamide, citric acid, trisodium citrate, ammonium citrate, oxalic acid, dimethyl oxalate, ethylene glycol, glycerol, furfuryl alcohol, hydrazine hydrate, hydrazine hydrochloride, acetylhydrazine, 1,2,4-triazole, 2-amino1,2,4-triazole, 4-amino1,2,4-triazole, or ethylenediamine and combinations thereof.

(13) The metal nitrate used in this embodiment may be a Ce(NO.sub.3).sub.3, Cu(NO.sub.3).sub.2, Pd(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, AgNO.sub.3, Zn(NO.sub.3).sub.2, TiO(NO.sub.3).sub.2, ZrO(NO.sub.3).sub.2, Ni(NO.sub.3).sub.2, Co(NO.sub.3).sub.2, Mg(NO.sub.3).sub.2, Sr(NO.sub.3).sub.2, Ba(NO.sub.3).sub.2, Y(NO.sub.3).sub.3, LiNO.sub.3, NaNO.sub.3, KNO.sub.3, Cr(NO.sub.3).sub.3, Mn(NO.sub.3).sub.2, Bi(NO.sub.3).sub.3, Mg(NO.sub.3).sub.2, Pb(NO.sub.3).sub.2, La(NO.sub.3).sub.3, NH.sub.4NO.sub.3, Ce(NH.sub.4).sub.2(NO.sub.3).sub.6, Pr(NO.sub.3).sub.3, Sm(NO.sub.3).sub.3, Eu(NO.sub.3).sub.3, In(NO.sub.3).sub.3, Gd(NO.sub.3).sub.3, Sc(NO.sub.3).sub.3, or Tb(NO.sub.3).sub.3. and combinations thereof.

(14) The colloid used in this embodiment may be a SiO.sub.2, Al.sub.2O.sub.3, CeO.sub.2, Fe.sub.2O.sub.3, TiO.sub.2, ZrO.sub.2, Fe.sub.3O.sub.4, ZnO, WO.sub.3, CuO, Cu.sub.2O, MoO.sub.3, Y.sub.2O.sub.3, Sm.sub.2O.sub.3, Gd.sub.2O.sub.3, Co.sub.3O.sub.4, Ag, Au, Pt, Pd, Ru, Rh, Ni, Co, Fe, Cu, Zr or Ti and combinations thereof.

(15) The diameter of colloids used is in the range of 2-200 nm and hence the pores formed after the chemical etching have the size in the same range.

(16) The pores in the uniform porous material can have a spherical, polyhedral, conical, cylindrical, ellipsoidal, and/or combinations thereof. The diameter can refer to an average interal diameter, the smallest internal diameter, or the largest interal diameter. In one embodiment, 95% of the pores in the uniform porous material have the same shape. In another embodiment, 99% of the pores in the uniform porous material have the same shape.

(17) To investigate the effect of colloidal template on CSCS, and to explore the tunability of porous structures formed, four samples of CeO.sub.2 were synthesized by discovered method with incremental amount of SiO.sub.2 added. Table 1 below shows the volume of colloidal silica added to 5 ml of aqueous CH.sub.2NH.sub.2COOH/Ce(NO.sub.3).sub.3 solution. The resulting samples are denoted as ceria-0, ceria-1, ceria-2, and ceria-3. FIGS. 2 and 4 show typical TEM images of the colloidal SiO.sub.2 particles and corresponding synthesized CeO.sub.2 product of ceria-3. A highly porous CeO.sub.2 with uniform spherical cavities is clearly visible in FIGS. 4 and 5. From the TEM and SEM images of FIGS. 3 and 5, the pore size is approximately 20-22 nm. The size and uniformity is consistent with the sharp peak in the BJH pore size distribution determined by N.sub.2 sorption measurement shown in FIG. 6 and is in agreement with the size of the colloidal particles shown in FIG. 2. X-ray diffraction (XRD) patterns of the CeO.sub.2 samples in FIG. 8 have well-defined peaks that can be indexed to the face-centered cubic phase of CeO.sub.2 (Fm3m, JCPDS, file No. 34-0394). The peaks broaden successively from ceria-0 to ceria-3, with each additional amount of SiO.sub.2 colloid added into the precursor, indicating a corresponding decrease in size of CeO.sub.2 nanocrystals (Table 1). The average crystalline size of ceria-3 sample calculated from Scherrer equation using (111) peak was found to be 4.1 nm, in good agreement with what is observed in the TEM images.

(18) As shown in Table 1 below, pore volume and surface area of the product increases monotonically with addition of SiO.sub.2 colloids. Ceria-3 has a very large pore volume of 0.6 ml/g, in contrast to 0.06 ml/g for ceria-0 synthesised by conventional SCS. The porosity estimated from pore volume of 0.6 ml/g and CeO.sub.2 density (7.28 g/ml) is 81%, which is higher than the theoretical limit (74%) of closed packed spherical cavities. The additional porosity above the closed packed spheres limit may come from micropores between the CeO.sub.2 nanocrystals since the measured micropore volume is 0.075 ml g.sup.1 equivalent to 12.5% porosity. (The presence of micropores corresponds to the steep rise in the N.sub.2 isotherm (FIG. 7) at low pressure (<0.01). The estimated porosity of 81% approaches the value (>90%) of common aerogels which are open frameworks formed by networked nanoparticles. FIG. 4 also shows open porous structures formed by connected nanoparticles, features which are similar to those of aerogels. The CeO.sub.2 from invented method, however, have uniform spherical cavities that are partially ordered, as opposed to unorganized and irregular pores in aerogels. The CSCS prepared CeO.sub.2 give the highest values of pore volume compared to other literature values of hard template synthesized CeO.sub.2. Close examination of the TEM image reveals that the pore wall is about 5 nm thick and is made up of crystalline CeO.sub.2 particles 3 to 4 nm in diameter.

(19) Special operating conditions of the invented method help to avoid coagulation of SiO.sub.2 colloids, which is necessary for forming a uniform and high porosity product. The colloids can be stabilized by surface charges, according to the Derjaguin, Landau, Verwey and Overbeek (DLVO) theory. The presence of deprotonated surface silanol groups is confirmed by measured zeta-potential of 25.8 mV. After addition into Ce(NO.sub.3).sub.3 and CH.sub.2NH.sub.2COOH mixture, the zeta potential becomes positive (12.9 mV) due to adsorption of Ce.sup.3 cations. The charge reversal of SiO.sub.2 surface maintains electrostatic repulsion and prevents coagulation, as similarly reported for trivalent cations adsorbed onto SiO.sub.2. Glycine molecules are also positively charged in the acidic solution of pH 4.5 and when adsorbed further contribute to repulsion by charge as well as steric hindrance.

(20) Mechanistic details of combustion in a colloidal SiO.sub.2 matrix can be very complicated as heat transfer, gas evolution, expansion, compression, nucleation and solid growth occur in a very short time in nanoscale volume between SiO.sub.2 colloids. The uniformity of cavities (FIG. 4 and FIG. 5) demonstrates the absence of colloids coagulation and no collapse of pores during SiO.sub.2 removal. In contrast, though conventional SCS have the same chemistry, the heat transfer, gas evolution and nucleation and growth occur in an unorganized manner over a large length scale, without the regulation of a colloidal SiO.sub.2 matrix. Typical temperature-time profiles of the different CeO.sub.2 samples are shown in FIG. 9. The maximum temperature decreases from 510 C. for ceria-0 to 295 C. for ceria-3, as shown in FIG. 9. The presence of SiO.sub.2 colloids promotes formation of small nanocrystals due to confinement of combustion and alteration of temperature profile. At the same time dispersed rigid spherical colloids create physical barriers that prevent contact and agglomeration of nanocrystals.

(21) With the presence of a colloid, SCS is significantly modified in several fundamental aspects. Results for synthesized CeO.sub.2 by invented method demonstrate 6-fold increase in surface area, 10-fold increase in pore volume, a narrow pore size distribution, partially ordered porosity, and 5-fold smaller particle size.

(22) Discovered method can be generally applied to synthesize metal oxides with similar properties and results of synthesized CuO are shown in FIG. 10 with uniform pores of 22 nm, high pore volume, and high surface area.

(23) The following examples illustrate the subject invention. Unless otherwise indicated in the following examples and elsewhere in the application text, all parts and percentages are by weight, all temperatures are in degrees Centigrade, and pressure is at or near atmospheric pressure.

EXAMPLES

Example 1

(24) Synthesis of Uniform Mesoporous CeO.sub.2 with Uniform 22 nm Pores

(25) The typical synthesis method of the CeO.sub.2/SiO.sub.2 nanocomposite is outlined below. For each experiment, 10 g of Ce(NO.sub.3).sub.3.6H.sub.2O, 2 g of CH.sub.2NH.sub.2COOH were dissolved in 30 ml of water and varying amounts of colloidal silica (LUDOX TMA) 22 nm dia. were added (Table 1). In the following, the samples synthesized will be referred to as CeO.sub.2-0, CeO.sub.2-1 etc. according to Table 1 below. The solution was transferred into the beaker (volume 100 ml) and heated at 200 C. on a hot plate. After several minutes, combustion occurred with a rapid increase in temperature due to the exothermic reaction between the Ce(NO.sub.3).sub.3 and CH.sub.2NH.sub.2COOH yielding CeO.sub.2/SiO.sub.2 nanocomposite. The resulting powder obtained was immersed in 2 M NaOH at 80 C. for 6 h. The samples were subsequently washed with water and ethanol three times and dried at 120 C. to obtain pure mesoporous CeO.sub.2.

(26) TABLE-US-00001 TABLE 1 Textural parameters of produced different CeO.sub.2 samples. Sample ceria-0 ceria-1 ceria-2 ceria-3 Volume of SiO.sub.2 added (mL) 0 0.2 0.5 1 T.sub.max ( C.) 510 379 315 295 S.sub.BET (m.sup.2/g) 13.7 39.3 62.8 81.7 BJH Pore volume (ml/g) 0.06 0.23 0.41 0.6 Average pore size (nm) 9.6 13.6 21.7 22 XRD particle size (nm) 12.1 7.6 5 4.1

(27) TABLE-US-00002 TABLE S1 Amount of SiO.sub.2 colloids added for preparation of different CeO.sub.2 samples. Sample ceria-0 ceria-1 ceria-2 ceria-3 Volume of colloidal SiO.sub.2 0 0.2 0.5 1 solution added (ml) Volume of 5 5 5 5 Ce(NO).sub.3CH.sub.2NH.sub.2COOH aq. Solution (ml)
Characterization

(28) K-type thermocouples with 0.1 mm diameter were used to monitor the temperature of the reaction over time. The output signals of the thermocouples were passed to a computer using a multichannel data acquisition line (Data Translation Inc.) with a monitoring frequency of 1 kHz using Quick DAC software. At least three measurements were performed to obtain the data. The compositions of as-synthesized powders were determined using powder X-ray diffraction (XRD) with CuK.sub. radiation at 40 kV and 40 mA (D8 Advance, Bruker). The powder microstructures were examined by scanning electron microscopy (SEM) (Hitachi S-4800 with an accelerating voltage of 7 kV). Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies were conducted to characterize the structure and composition of the reaction products (Phillips Tecnai 20 with an accelerating voltage of 200 kV). A Micromeritics ASAP 2020 analyzer was used to obtain the Brunauer-Emmet-Teller (BET) surface areas and Barrett-Joyner-Halenda (BJH) pore size distributions of oxides using nitrogen as the adsorbent gas at 77K. Oxide powders were degassed at 473K and 10.sup.6 Torr overnight under the vacuum prior to the analysis. Zeta potential was measured by Zetasizer (Malvern UK).

Example 2

(29) Synthesis of Uniform Mesoporous CuO with Uniform 22 nm Pores

(30) The typical synthesis method of the CuO/SiO.sub.2 nanocomposite is outlined below. For each experiment, 10 g of Cu(NO.sub.3).sub.2.2H.sub.2O, 2.19 g of CH.sub.2NH.sub.2COOH were dissolved in 30 ml of water and 5 ml of colloidal silica (LUDOX TMA) 22 nm dia. were added. The solution was transferred into the beaker (volume 100 ml) and was heated at 200 C. on a hot plate. After several minutes, combustion occurred with a rapid increase in temperature due to the exothermic reaction between the Cu(NO.sub.3).sub.2 and CH.sub.2NH.sub.2COOH yielding CuO/SiO.sub.2 nanocomposite. The resulting powder obtained was immersed in 2 M NaOH at 80 C. for 6 h. The samples were subsequently washed with water and ethanol three times and dried at 120 C. to obtain pure mesoporous CuO.

Example 3

(31) Synthesis of Uniform Mesoporous NiO with uniform 22 nm pores

(32) The typical synthesis method of the NiO/SiO.sub.2 nanocomposite is outlined below. For each experiment, 20 g of Ni(NO.sub.3).sub.2.2H.sub.2O, 3.1 g of CH.sub.2NH.sub.2COOH were dissolved in 50 ml of water and 10 ml of colloidal silica (LUDOX TMA) 22 nm dia. were added. The solution was transferred into the beaker (volume 100 ml) and was heated at 200 C. on a hot plate. After several minutes, combustion occurred with a rapid increase in temperature due to the exothermic reaction between the Ni(NO.sub.3).sub.2 and CH.sub.2NH.sub.2COOH producing NiO/SiO.sub.2 nanocomposite. The resulting powder obtained was immersed in 1 M NaOH at 80 C. for 10 h. The samples were subsequently washed with water and ethanol three times and dried at 120 C. to obtain pure mesoporous NiO.

Example 4

(33) Synthesis of Uniform Mesoporous CeO.sub.2 with uniform 12 nm pores

(34) The typical synthesis method of the CeO.sub.2/SiO.sub.2 nanocomposite is outlined below. For each experiment, 15 g of Ce(NO.sub.3).sub.3.6H.sub.2O, 2.25 g of CH.sub.2NH.sub.2COOH were dissolved in 40 ml of water and 23 ml of colloidal silica (LUDOX CL) 12 nm dia. were added No data is added in Table 1. The solution was transferred into the beaker (volume 100 ml) and heated at 200 C. on a hot plate. After several minutes, combustion occurred with a rapid increase in temperature due to the exothermic reaction between the Ce(NO.sub.3).sub.3 and CH.sub.2NH.sub.2COOH yielding CeO.sub.2/SiO.sub.2 nanocomposite. The resulting powder obtained was immersed in 2 M NaOH at 80 C. for 6 h. The samples were subsequently washed with water and ethanol three times and dried at 120 C. to obtain pure mesoporous CeO.sub.2.

(35) With respect to any figure or numerical range for a given characteristic, a figure or a parameter from one range may be combined with another figure or a parameter from a different range for the same characteristic to generate a numerical range.

(36) Other than in the operating examples, or where otherwise indicated, all numbers, values and/or expressions referring to quantities of precursors, reaction conditions, etc., used in the application text are to be understood as modified in all instances by the term about.

(37) It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.