CATALYST WITH A CORE-SHELL STRUCTURE FOR METHANE OXIDATION, METHOD OF PREPARING THE SAME AND METHOD OF OXIDIZING METHANE USING THE SAME

Abstract

A catalyst with a core-shell structure for methane oxidation, a method of preparing the catalyst, and a method of methane oxidation using the catalyst are disclosed. The catalyst includes a core structure consisting of a nano-support and core nanoparticles; and a shell coating layer coated on the core structure in which the core nanoparticles have a particle diameter smaller than that of the nano-support and are coated on the nano-support to form a core structure. The catalyst has excellent thermal stability during methane oxidation reaction at high temperature and an effect of increasing methane conversion and formaldehyde selectivity.

Claims

1. A catalyst for methane oxidation comprising: a core structure consisting of a nano-support and core nanoparticles; and a shell coating layer coated on the core structure, wherein the core nanoparticles have a particle diameter smaller than that of the nano-support and are coated on the nano-support to form a core structure.

2. The catalyst for methane oxidation of claim 1, wherein the nano-support is spherical nano-support.

3. The catalyst for methane oxidation of claim 1, wherein the nano-support comprises SiO.sub.2.

4. The catalyst for methane oxidation of claim 1, wherein the core nanoparticles coated on the nano-support comprise V.sub.2O.sub.5 having an average particle size of 10 to 100 nm.

5. The catalyst for methane oxidation of claim 1, wherein the shell coating layer coated on the core structure comprises Al.sub.2O.sub.3.

6. A method of preparing a catalyst for methane oxidation comprising: preparing a nano-supports comprising SiO.sub.2; preparing a core structure by hydrothermal reaction of V.sub.2O.sub.5 nanoparticles on the nano-supports; and forming a core-shell nanostructure by atomic layer deposition of Al.sub.2O.sub.3 on the core structure.

7. A method of preparing a catalyst for methane oxidation of claim 6, wherein the nano-support is spherical nano-support.

8. The method of preparing a catalyst for methane oxidation of claim 6, wherein the hydrothermal reaction is performed at 100 to 250° C. for 5 to 30 hours.

9. The method of preparing a catalyst for methane oxidation of claim 6, wherein the atomic layer deposition is performed for 1 to 100 cycles using trimethylaluminum and H.sub.2O.

10. A catalyst for methane oxidation, which is prepared by the method of preparing the catalyst for methane oxidation of claim 6.

11. A method of methane oxidation, comprising reacting methane and oxygen in the presence of the catalyst for methane oxidation of claim 1.

12. A method of methane oxidation for producing formaldehyde comprising producing formaldehyde by reacting methane and oxygen at 500 to 800° C. in the presence of the catalyst for methane oxidation of claim 1.

13. A method of methane oxidation, comprising reacting methane and oxygen in the presence of the catalyst for methane oxidation of claim 10.

14. A method of methane oxidation for producing formaldehyde comprising producing formaldehyde by reacting methane and oxygen at 500 to 800° C. in the presence of the catalyst for methane oxidation of claim 10.

Description

DESCRIPTION OF DRAWINGS

[0014] FIG. 1a shows schematic preparation of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures.

[0015] FIG. 1b, FIG. 1c, and FIG. 1d are transmission electron microscopy (TEM) images of SiO.sub.2 spheres, SiO.sub.2@V.sub.2O.sub.5, and SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures, respectively.

[0016] FIG. 2a is an scanning electron microscopy (SEM) image showing structural characterization of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures.

[0017] FIG. 2b is scanning TEM (STEM) images with a line-scan energy-dispersive X-ray spectroscopy (EDS) spectrum showing structural characterization of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell.

[0018] FIG. 3a is a schematic illustration of the ALD process used for multi-cycle coating of Al.sub.2O.sub.3 shells on SiO.sub.2@V.sub.2O.sub.5 nanostructures.

[0019] FIG. 3b shows X-ray diffraction (XRD) patterns of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(10, 30, 50, and 100) nanostructures.

[0020] FIG. 4a and FIG. 4b show in situ XRD patterns of SiO.sub.2@V.sub.2O.sub.5 and SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) nanostructures, respectively.

[0021] FIG. 5a shows methane oxidation performances of various SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures and supported V.sub.2O.sub.5/m-SiO.sub.2 catalysts at 600° C. in term of methane conversion and selectivity obtained for SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) nanostructures as a function of time-on stream.

[0022] FIG. 5b shows comparison of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(x) core@shell nanostructures in terms of achieved methane conversion and product yield.

[0023] FIG. 5c shows methane oxidation performances of V.sub.2O.sub.5/m-SiO.sub.2 catalysts with vanadium loadings of 1, 3, and 5 wt %.

[0024] FIG. 6 shows methane oxidation performances of selected vanadium-based catalysts obtained at a CH.sub.4/O.sub.2 ratio of 1:1 (v/v) and a reaction temperature of 600° C. (n.d.=not detected). Each reaction was conducted more than 3 times for reproducibility and the conversion and turnover frequency (TOF) are mean values and the deviation is within 15%.

[0025] FIG. 7a, FIG. 7b, and FIG. 7c show Raman spectra, H.sub.2 temperature programmed reduction (H.sub.2-TPR) curves, and UV-vis diffuse reflectance spectra of SiO.sub.2@V.sub.2O.sub.5 and SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures, and 3 wt % V.sub.2O.sub.5/m-SiO.sub.2, respectively.

[0026] FIG. 7d shows a formation of new T.sub.d vanadium species and V—O—Al bonds by a reaction between V.sub.2O.sub.5 and Al.sub.2O.sub.3 in the SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell catalyst.

BEST MODE

[0027] Hereinafter, the present invention will be described in detail.

[0028] The present inventors have prepared a nanostructure catalyst having a SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core-shell structure which is stable at a high temperature in methane oxidation reaction and excellent in conversion of methane and selectivity to formaldehyde and they have found out that the prepared catalyst has excellent thermal stability at high temperature by Al.sub.2O.sub.3 because the agglomeration and structural deformation of V.sub.2O.sub.5 nanoparticles was prevented and forms a new catalyst species between V.sub.2O.sub.5 and Al.sub.2O.sub.3 thereby having superior catalytic activity even at high temperatures and have completed the present invention.

[0029] The present invention provides a catalyst for methane oxidation comprising: a core structure consisting of a nano-support and core nanoparticles; and a shell coating layer coated on the core structure, wherein the core nanoparticles have a particle diameter smaller than that of the nano-support and are coated on the nano-support to form a core structure.

[0030] At this time, the nano-support may be spherical nano-support and comprise SiO.sub.2, the core nanoparticles coated on the nano-support may comprise V.sub.2O.sub.5 having an average particle size of 10 to 100 nm and the shell coating layer coated on the core structure may comprise Al.sub.2O.sub.3.

[0031] Also, the present invention provides a method of preparing a catalyst for methane oxidation comprising: preparing nano-supports comprising SiO.sub.2; preparing a core structure by hydrothermal reaction of V.sub.2O.sub.5 nanoparticles on the nano-supports; and forming a core-shell nanostructure by atomic layer deposition of Al.sub.2O.sub.3 on the core structure.

[0032] At this time, the nano-support may be spherical nano-support and the hydrothermal reaction may be performed at 100 to 250° C. for 5 to 30 hours, preferably at 220° C. for 24 hours.

[0033] At this time, when it fails to fall within the above conditions, the V.sub.2O.sub.5 nanoparticles are not sufficiently coated on the spherical SiO.sub.2, so that the interaction with the Al.sub.2O.sub.3 shell cannot be properly performed, resulting in poor catalytic activity or the yield of the V.sub.2O.sub.5 nanoparticle coating may be poor in respect of the reaction time, which may lead to an economical problem.

[0034] In addition, the atomic layer deposition may be performed by using trimethylaluminum and H.sub.2O for 1 to 100 cycles, preferably 50 cycles.

[0035] Furthermore, the present invention provides a catalyst for methane oxidation, which is prepared by the method of preparing the catalyst for methane oxidation.

[0036] In addition, the present invention provides a method of methane oxidation, comprising reacting methane and oxygen in the presence of the catalyst for methane oxidation.

[0037] In addition, the present invention provides a method of methane oxidation for producing formaldehyde comprising producing formaldehyde by reacting methane and oxygen at 500 to 800° C. in the presence of the catalyst for methane oxidation. Preferably, methane and oxygen are reacted at 600° C. in the presence of the catalyst for methane oxidation to produce formaldehyde.

[0038] Hereinafter, the present invention will be described in detail with reference to the following examples. It should be noted, however, that the examples of the present invention are provided to more specifically describe the present invention and are not intended to limit the scope of the present invention to those skilled in the art.

<Example 1> Preparation of SiO.SUB.2.@V.SUB.2.O.SUB.5 .Nanostructure

[0039] NH.sub.4OH (7.5 mL) and H.sub.2O (24 mL) were dispersed in ethanol (294 mL). Tetraethyl orthosilicate (TEOS; Aldrich, 98%, 15 mL) was dropwise added to the obtained solution, and the reaction mixture was further stirred for 24 h. The resulting opaque solution was filtered, and the filter cake was washed with ethanol and dried at 70° C. to afford silica spheres. To synthesize SiO.sub.2@V.sub.2O.sub.5 core@shell nanostructures, as-prepared silica spheres (0.3 g) were mixed with vanadyl acetylacetonate (VO(acac).sub.2; Sigma-Aldrich, 97%, 0.83 g) in dimethylformamide (40 mL) upon 3-h sonication. The obtained dispersion was placed in a 50-mL Teflon-lined autoclave reactor and heated at 220° C. for 24 h. The dark precipitate was separated by centrifugation, washed with ethanol, dried at 70° C., and calcined at 400° C. for 3 h to afford SiO.sub.2@V.sub.2O.sub.5 core@shell nanostructures.

<Example 2> Preparation of SiO.SUB.2.@V.SUB.2.O.SUB.5.@Al.SUB.2.O.SUB.3.-(x) (x=10, 30, 40, 50, 70, and 100) Core@Shell Nanostructures

[0040] Al.sub.2O.sub.3 shells were grown on SiO.sub.2@V.sub.2O.sub.5 core@shell structures in a rotary ALD reactor using a TMA (trimethylaluminum, Sigma-Aldrich, 97%; alumina precursor)-H.sub.2O—Ar sequence. First, SiO.sub.2@V.sub.2O.sub.5 powders were loaded into a porous stainless-steel cylinder that was rotated at 140 rpm inside the reaction chamber. For a single cycle of the ALD sequence, TMA introduced at a pressure of 1 Torr was deposited onto V.sub.2O.sub.5 surfaces at 180° C., and the chamber was subsequently evacuated to remove CH.sub.4 generated as a by-product and unreacted TMA. The chamber was filled with Ar to a pressure of 20 Torr and evacuated after several minutes. Then, H.sub.2O (1 Torr) was introduced to replace the methyl groups of the attached TMA with OH groups, and the chamber was evacuated to remove the produced CH.sub.4 and excess H.sub.2O and purged with Ar (20 Torr). For the second cycle, the above steps were repeated. The number of cycles was denoted as (x) and was found to be proportional to the thickness of Al.sub.2O.sub.3 shells. SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(x) core@shell nanostructures with controlled Al.sub.2O.sub.3 shell thickness were prepared using different numbers of ALD cycles (x=10, 30, 40, 50, 70, and 100).

<Example 3> Preparation of Mesoporous Silica-Supported V.SUB.2.O.SUB.5 .(V.SUB.2.O.SUB.5./m-SiO.SUB.2.) Catalysts

[0041] Conventional V.sub.2O.sub.5/m-SiO.sub.2 catalysts were prepared by incipient wetness impregnation. Mesoporous silica with a mesocellular structure (MCF-17) prepared by a previously described method was used as a support. Briefly, 1,3,5-trimethylbenzene (Sigma-Aldrich, 98%; 4 g) was dissolved in 75 mL of an aqueous solution containing 4 g of Pluronic P123 triblock copolymer (Aldrich, average Mw 5800 Da) and 10 mL of concentrated HCl. The reaction mixture was stirred at 40° C. for 2 h and then treated with TEOS (9.2 mL) and maintained for 5 min. The resulting solution was kept at 40° C. for 20 h without stirring, treated with NH.sub.4F (Sigma-Aldrich, 98%; 46 mg), and further aged in a closed bottle at 100° C. for another 24 h. The obtained white precipitate was filtered, washed with water and ethanol, and calcined in air at 600° C. for 6 h to afford mesoporous silica MCF-17. V.sub.2O.sub.5/m-SiO.sub.2 catalysts were prepared by exposing MCF-17 (1 g) to a solution of ammonium vanadium oxide (NH.sub.4VO.sub.3, Alfa Aesar, 99%) in the presence of oxalic acid dihydrate (C.sub.2H.sub.2O.sub.4.2H.sub.2O, Acros Organics, 99%) overnight. Centrifugation followed by drying afforded solid V.sub.2O.sub.5/m-SiO.sub.2 catalysts with vanadium precursor loadings of 1, 3, and 5 wt % after calcination at 350° C. for 4 h. Conventional V.sub.2O.sub.5/Al.sub.2O.sub.3 catalysts were also prepared by the same impregnation method in the presence of commercial Al.sub.2O.sub.3(Puralox SBa 200, Sasol) for comparison. For details, 1 g of Al.sub.2O.sub.3 was mixed with oxalic acid dihydrate in an ethanol solution of NH.sub.4VO.sub.3. After drying at 60° C. and calcination at 350° C. 4 h, 3 and 5 wt % of V.sub.2O.sub.5/Al.sub.2O.sub.3 catalysts were obtained.

<Example 4> Characterization

[0042] In situ XRD patterns were acquired in a 20 range of 20−80° (Cu Kα radiation, λ=1.5418 Å) using PAnalytical X'Pert Pro and Rigaku SmartLab X-ray diffractometers, respectively. Prior to measurements, samples were loaded on a holder and preheated at 150° C. for 30 min in an Ar atmosphere. In situ spectra were recorded for catalysts exposed to a heated gas mixture of 4% CH.sub.4, 4% O.sub.2, and balance Ar in steps of 50° C. (from 100 to 800° C.) using a specially constructed cell. Brunauer-Emmett-Teller (BET) surface areas were determined from N.sub.2 adsorption/desorption isotherms recorded on a microtrac BELsorp-Max analyzer. Pore size distributions were determined by the Barrett-Joyner-Halenda method. SEM imaging was performed using a Hitachi S-4800 microscope, and TEM imaging was performed using a JEOL JEM-2100F instrument operated at 200 kV. An EDS (energy-dispersive X-ray spectroscopy) analyzer was used for elemental analysis (Oxford instrument, X-Max 80 T). TPR (temperature-programmed reduction) was carried out on the Micromeritics AutoChem II 2920 instrument. Typically, a catalyst sample (100 mg) was loaded into a U-shaped quartz tube and outgassed under He flow at 150° C. for 30 min. Subsequently, the temperature was increased to 800° C. at a rate of 10° C. min.sup.−1 in a flow of 10% H.sub.2 in He (50 mL min.sup.−1). The amount of consumed H.sub.2 was determined by gas chromatography using a Delsi Nermag thermal conductivity detector. Diffuse reflectance UV-vis spectra were recorded at a scan step of 1 nm on an Agilent Cary 5000 UV-vis-NIR spectrophotometer operated in the region of 200-2200 nm. A halon white (PTFE) reflectance standard was used as a reference background. Raman spectra were collected utilizing a WITec alpha300 R spectrometer equipped with a 532-nm diode laser. The laser power was set to 0.1 mW. To obtain sufficient signal-to-noise ratios, spectra were obtained using CCD with 10-sec exposure and 10-fold accumulation.

<Example 5> Methane Oxidation Reaction

[0043] Catalytic methane oxidation was conducted in a laboratory-scale flow reactor at atmospheric pressure and a constant temperature of 600° C. As-synthesized vanadium-based catalysts were pelletized and sieved to a particle size of 150-250 μm. A 100 mg catalyst sample was loaded into a quartz tube (inner diameter=1 cm) together with 1 g of purified sand. CH.sub.4 (99.95%) and O.sub.2 (99.995%) in a 1:1 v/v ratio were fed from the top to the bottom of the catalyst bed at a rate of 40 sccm using mass flow controllers, and the gas hourly space velocity (GHSV) was maintained at 24,000 mL g.sub.cat.sup.−1 h.sup.−1. The reactor was heated to 600° C. in a furnace and equipped with an inserted thermocouple to monitor temperature. Products were monitored using an online gas chromatograph (YL6500) equipped with Porapak-N and molecular sieve columns connected to both thermal conductivity detector (TCD) and flame ionization detectors (FID) with a methanizer (Ar was flown in as a reference). HCHO, CO, CO.sub.2, and H.sub.2 were identified as the main reaction products. The products converted from methane were condensed and separated by a cold trap apparatus before entering the gas chromatography. This solution was mixed with 1 M Na.sub.2SO.sub.3 solution and the concentration of HCHO was determined by titrating with NaOH and H.sub.2SO.sub.4. Methane conversion was calculated as the ratio of consumed and original methane amounts using gas chromatography data for points in stabilized areas with maximum activity values. Selectivity was calculated as the ratio of product amount and total converted methane amount. The conversion of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(x) core@shell nanostructures (x=40, 50, and 70) was determined by the average value of methane conversions, in which each reaction was conducted more than 3 times for reproducibility. The turnover frequency (TOF.sub.HCHO) was calculated by the number of CH.sub.4 molecules reacted to HCHO on each available vanadium site per time. By assuming that an isolated vanadium species on the outermost surface of the V.sub.2O.sub.5 nanoparticles was contacted with the alumina shell, the total surface area of the core@shell catalyst was determined by the size and mass of the structure. The number of core@shell nanostructures was estimated by the mass of single nanoparticle, thus the total surface area and the isolated surface vanadium sites (7.3×10.sup.18) were finally determined for the TOFs.

<Experimental Example 1> Preparation of SiO.SUB.2.@V.SUB.2.O.SUB.5.@Al.SUB.2.O.SUB.3 .Core@Shell Catalysts

[0044] As a method of Example 2, SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures were prepared by hydrothermal synthesis followed by ALD (FIG. 1a), and SiO.sub.2 spheres with an average size of 150 nm were synthesized by the method of Example 1 (FIG. 1b). Discrete V.sub.2O.sub.5 nanoparticles with an average size of 35 nm were deposited on the surface of SiO.sub.2 spheres by a hydrothermal reaction in the presence of VO(acac).sub.2 (FIG. 1c). During the reaction, small vanadium clusters were first formed by nucleation, and then the vanadium species were mostly attached to SiO.sub.2 spheres, because of the hydrophilic nature of the SiO.sub.2 surface. By the subsequent ALD with the various number of repeating cycles, thin Al.sub.2O.sub.3 layers were deposited over SiO.sub.2@V.sub.2O.sub.5 core@shells with a controlled thickness. FIG. 1d shows a TEM image of representative SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures, unambiguously demonstrating the presence of Al.sub.2O.sub.3 layers coating the core structures.

[0045] The surface morphology of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures was investigated by SEM, scanning TEM (STEM), and EDS. FIG. 2a clearly demonstrates that outer Al.sub.2O.sub.3 layers were homogeneously deposited on the entire surface of SiO.sub.2@V.sub.2O.sub.5 nanostructures. STEM imaging and the corresponding elemental mappings with EDS line scanning (FIG. 2b) displayed that O and V (derived from V.sub.2O.sub.5) were uniformly dispersed in the shell, while Si (derived from silica spheres) was mainly located in the core. Moreover, the distribution of alumina over the whole core@shell nanostructures demonstrated that they were coated by thin Al.sub.2O.sub.3 shell layers. SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(10, 30, 50, and 100) core@shell nanostructures were also characterized by high resolution TEM, which revealed that 100 ALD cycles were sufficient to obtain full coverage by 20-nm-thick Al.sub.2O.sub.3 layers, while 10 cycles did not suffice for an effective coating.

[0046] The shell thickness of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures increased with the number of ALD cycles (FIG. 3a). The introduced TMA precursor was adsorbed on V.sub.2O.sub.5 surfaces to create Al—O bonds, and Al(OH).sub.4 units were finally produced upon the addition of water vapor. Subsequent ALD cycles resulted in the deposition of additional alumina layers over SiO.sub.2@V.sub.2O.sub.5. The XRD patterns of SiO.sub.2@V.sub.2O.sub.5 core@shell catalysts (FIG. 3b) revealed the presence of characteristic peaks of V.sub.2O.sub.5 (Pmmn, a=1.1516, b=0.3566, c=0.4372 nm). Application of the Scherrer equation to the (110) peak allowed the crystallite size of SiO.sub.2@V.sub.2O.sub.5 core@shell structures to be estimated as 40.1 nm, which agreed with values obtained by TEM and SEM. However, much weaker XRD peaks were observed for SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures (FIG. 3b), since the Al.sub.2O.sub.3 shell was not crystalline. XRD analysis of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(10, 30, 50, and 100) nanostructures revealed that as the number of ALD cycles increased from 10 to 100, the crystallite size (calculated as mentioned above) increased from 31.3 to 34.6 nm. From the results, (a) as-prepared V.sub.2O.sub.5 nanoparticles diffused to Al.sub.2O.sub.3 surfaces with decreased sizes of V.sub.2O.sub.5 and (b) X-ray diffraction from the V.sub.2O.sub.5 core exhibited a decreased intensity of peak because of Al.sub.2O.sub.3 shells obtained after an increased number of ALD cycles.

[0047] <Experimental Example 2> Thermal Stability of V.sub.2O.sub.5 Species in Core@Shell Nanostructures

[0048] The thermal stability of SiO.sub.2@V.sub.2O.sub.5 core@shell catalysts before/after Al.sub.2O.sub.3 deposition was probed by in situ XRD analysis at 100-800° C. in an atmosphere of 4% CH.sub.4, 4% O.sub.2, and balance Ar. FIG. 4a shows that the characteristic XRD peaks of V.sub.2O.sub.5 were preserved in SiO.sub.2@V.sub.2O.sub.5 core@shells, while the peak intensity increased with increasing temperature up to 750° C. The crystallite size calculated by the Scherrer equation for V.sub.2O.sub.5 nanoparticles increased from 50.8 nm at 100° C. to 77.9 nm at 750° C. At high temperature, the outer V.sub.2O.sub.5 nanoparticles gradually collapsed. Above 800° C., structural dissociation decreased XRD peak resolution, and only the main peaks were observed. Conversely, SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures maintained their XRD peak intensities up to 800° C., which demonstrated that the presence of Al.sub.2O.sub.3 shells prevented the aggregation of core V.sub.2O.sub.5 nanoparticles at high temperature (FIG. 4b).

[0049] Interestingly, new peaks are recognized in SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures beyond 700° C. (FIG. 4b). When the possibility of any other crystalline structure of either alumina or vanadium oxide was examined, however those were matched to neither crystalline aluminas such as alpha, gamma, and theta, nor vanadium oxides including V.sub.2O.sub.3, V.sub.4O.sub.7, and VO.sub.2 and the high-resolution TEM images, show that the thin Al.sub.2O.sub.3 shell did not show any crystallinity. Previous studies reported that AlVO.sub.4 phase formed from a solid-state reaction between V.sub.2O.sub.5 and Al.sub.2O.sub.3 beyond 570° C. and the additional XRD peaks in the range of 26−30° corresponded to the characteristic peaks of AlVO.sub.4. Based on these results, as the temperature increased, thin alumina shells were not crystallized but new AlVO.sub.4 species was generated resulting from a solid-state reaction between V.sub.2O.sub.5 and Al.sub.2O.sub.3 above 700° C.

<Experimental Example 3> Catalytic Oxidation of Methane to Formaldehyde

[0050] Methane oxidation over SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures with controlled Al.sub.2O.sub.3 shell thickness was carried out in a laboratory-scale flow reactor operated at 600° C. at a CH.sub.4/O.sub.2 ratio of 1:1 (v/v). FIG. 5a shows methane conversion as a function of time-on stream over SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) nanostructures at 600° C.

[0051] The initially observed gradual increase of conversion with time-on-stream was followed by an abrupt change at 6 h (at which point the product selectivity changed as well) and subsequent saturation to the maximum, which was ascribed to a structural rearrangement of the catalyst. Methane conversion of the SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) nanostructures reached ˜22.2%, and the corresponding HCHO, CO, and CO.sub.2 selectivities equaled 57.8, 27.4, and 14.8%, respectively (FIG. 6). Beyond 35 h, the overall conversion and selectivity stayed constant, demonstrating that the SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) nanostructures were thermally stable by having long-term stability in the high temperature methane oxidation. Additionally, methane oxidation was conducted over SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(x) nanostructures having different shell thicknesses (FIG. 5b). Notably, whereas the maximum conversion of methane observed for SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 (50) equaled 22.2%, negligible conversions were observed for x=0-30. Thus, the original SiO.sub.2@V.sub.2O.sub.5 core@shell structures did not show substantial methane oxidation activity because of the instability of V.sub.2O.sub.5 nanoparticles at 600° C. The protective effect of the Al.sub.2O.sub.3 shell was maximized in SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50), which featured strongly enlaced Al.sub.2O.sub.3 shells that still provided enough space for constant exchange of reactants and products, with further shell thickness increases resulting in deteriorated performance, e.g., a conversion of only 3.7% was observed for SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(100) (FIG. 5b and FIG. 6). FIG. 5c shows the methane oxidation performance of V.sub.2O.sub.5/m-SiO.sub.2 catalysts with vanadium loadings of 1, 3, and 5 wt %, revealing that methane conversions (5.5-5.6%) and HCHO selectivities (65.7-71.2%) obtained at 600° C. were in good agreement with the previous research. FIG. 6 summarizes the methane oxidation performances of core@shell nanostructures with controlled Al.sub.2O.sub.3 shell thicknesses and those of supported V.sub.2O.sub.5/M-S102 catalysts, demonstrating that the best methane conversion achieved for SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) achieved has never achieved before for any vanadium-based catalyst at 600° C.

[0052] Therefore, the SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) nanostructure of the present invention exhibited the best catalytic activity with CH.sub.4 conversion of 22.2% and HCHO selectivity of 57.8% under 24,000 mL g.sub.cat.sup.−1 h.sup.−1 at 600° C., over all the vanadium-based catalysts that convert known methane to HCHO.

<Experimental Example 4> Characterization of V.SUB.2.O.SUB.5 .in SiO.SUB.2.@V.SUB.2.O.SUB.5.@Al.SUB.2.O.SUB.3 .Core@Shell Catalysts

[0053] The catalytic activity of supported vanadium catalysts is known to depend on the dispersion of vanadium, the nature of vanadium active sites, and the metal-support interaction determined by the selection of suitable oxide supports. For many catalytic oxidations, including the partial oxidation of hydrocarbons, oxidative dehydrogenation of alkanes to alkenes, selective catalytic reduction of NO.sub.x, and the oxidation of SO.sub.2, isolated tetrahedral (T.sub.d) vanadium oxide species containing terminal V═O groups have been proposed as active sites. To characterize vanadium species in SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures and compare them to those in V.sub.2O.sub.5/m-SiO.sub.2 catalysts, the above materials were analyzed by Raman spectroscopy, H.sub.2-TPR, and diffuse reflectance UV-vis spectroscopy.

[0054] FIG. 7a shows Raman spectra of V.sub.2O.sub.5/m-SiO.sub.2 and SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell nanostructures at 600° C., revealing the presence of bands at 995 (V=0), 703, 406, 305, and 285 cm′ in all cases and thus indicating that all catalysts contained crystalline V.sub.2O.sub.5. Although the Raman spectra of 3 wt % V.sub.2O.sub.5/m-SiO.sub.2 were similar to those of core@shell catalysts prepared from crystalline V.sub.2O.sub.5, a shoulder peak at 1040 cm′ ascribed to the symmetric V═O stretch of isolated VO.sub.4 species was observed in the former case (FIG. 7a). Interestingly, as the vanadium content of V.sub.2O.sub.5/m-SiO.sub.2 decreased to 1 wt %, the above shoulder peak became dominant, which indicated that the relative content of crystalline V.sub.2O.sub.5 in V.sub.2O.sub.5/m-SiO.sub.2 catalysts decreased at low vanadium loadings.

[0055] The dispersion and type of active vanadium species were evaluated by H.sub.2-TPR. In previous reports, the low-temperature H.sub.2-TPR reduction peak observed at 460-500° C. was ascribed to the reduction of V.sup.5+ in highly dispersed monomeric species to V.sup.3+. As the vanadium loading increased, the reduction peaks shifted to higher temperatures as a consequence of reduction kinetics. The high-temperature reduction peak at −600° C. was assigned to the reduction of vanadium in polymeric and bulk-like V.sub.2O.sub.5 species. The TPR profiles in FIG. 7b show that 3 wt % V.sub.2O.sub.5/m-SiO.sub.2 contained highly disperse monomeric species as well as a small amount of V.sub.2O.sub.5 species, in good agreement with the results of Raman spectroscopy analysis. Pristine SiO.sub.2@V.sub.2O.sub.5 contained only bulk V.sub.2O.sub.5 species, which was ascribed to the size of V.sub.2O.sub.5 nanoparticles (35 nm). Conversely, the SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 (50) core@shell catalyst contained both V.sub.2O.sub.5 and highly disperse monomeric species, exhibiting two broad TPR bands at 550 and 620° C.

[0056] Finally, the dispersion of the vanadium-based catalyst and the active species structure were analyzed using a diffuse reflectance UV-vis spectrometer (FIG. 7c). The absorption band just above 3 eV was ascribed to VO.sub.x species with T.sub.d coordination, while that around 5.5 eV evidenced the presence of monomeric T.sub.d species. The absorption edge positions of 3 wt % V.sub.2O.sub.5/m-SiO.sub.2 (2.6 eV) and SiO.sub.2@V.sub.2O.sub.5/SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) (<2.4 eV) indicated that the former catalyst contained homogeneous T.sub.d VO.sub.x species with a smaller domain size than those of the other two catalysts. The low-energy shoulder observed for core@shell catalysts comprising 35-nm V.sub.2O.sub.5 nanoparticles was ascribed to the bimodal size distribution of crystalline V.sub.2O.sub.5 species that was not observed for V.sub.2O.sub.5/m-SiO.sub.2. Furthermore, the size distributions deduced from shoulder peaks were different for SiO.sub.2@V.sub.2O.sub.5 and SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) core@shell catalysts, demonstrating that the properties of crystalline V.sub.2O.sub.5 species are changed by the deposition of Al.sub.2O.sub.3 shells.

[0057] Since the interaction between V.sub.2O.sub.5 and Al.sub.2O.sub.3 influenced on the catalytic performance, methane oxidation was performed over conventional V.sub.2O.sub.5/Al.sub.2O.sub.3 catalysts. When V.sub.2O.sub.5/Al.sub.2O.sub.3 catalysts were prepared by the impregnation with different vanadium loading of 3 and 5 wt % and tested the reaction, negligible conversions were obtained (less than 2% of methane conversion) for both catalysts. These results were agreement with the previously conducted study.

[0058] From the above results, the V.sub.2O.sub.5 nanoparticles formed on the spherical SiO.sub.2 particles were identified as crystalline V.sub.2O.sub.5 species, and the Al.sub.2O.sub.3 shell of SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3-(50) promoted the interaction between V.sub.2O.sub.5 and Al.sub.2O.sub.3 during the ALD process, (FIG. 7d). Based on the fact that the AlVO.sub.4 phase is present in the SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructure at elevated temperatures, the interaction between V.sub.2O.sub.5 nanoparticles and Al.sub.2O.sub.3 creates a bridging VO—Al bond in AlVO.sub.4. Highly dispersed T.sub.d vanadium species with V—O—Al bonds in SiO.sub.2@V.sub.2O.sub.5@Al.sub.2O.sub.3 core@shell nanostructures did not appear in conventional V.sub.2O.sub.5/Al.sub.2O.sub.3 catalysts.

[0059] In conclusion, newly formed T.sub.d monomer vanadium species connected to V—O—Al bond could be used for methane oxidation reaction at 600° C. to obtain high methane conversion. In addition, the Al.sub.2O.sub.3 shell also protected the V.sub.2O.sub.5 nanoparticles from firing, and obtained a thermal stability effect.