CN110368963B - Ti ion doped TaO2Preparation method of F nano material - Google Patents
Ti ion doped TaO2Preparation method of F nano material Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910004160 TaO2 Inorganic materials 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- -1 fluorine ions Chemical class 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000002073 nanorod Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 241000257465 Echinoidea Species 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910010342 TiF4 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- AYZLTBRUKNUWNP-UHFFFAOYSA-N fluoro hypofluorite tantalum Chemical compound [Ta].FOF AYZLTBRUKNUWNP-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910002785 ReO3 Inorganic materials 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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Abstract
The invention discloses a method for preparing Ti ion-doped TaO with a three-dimensional sea urchin-shaped nano structure2The method of F has great application prospect in the field of photo/electro-catalysis. Belongs to the technical field of nano material preparation. The raw materials comprise tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water; (1) dissolving tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the tantalum powder to the titanium powder is 1 (0.1-1) to 1-11; (2) mixing acetic acid and water according to a volume ratio (0.4-10): 1, uniformly mixing; and adding the solution into the solution containing tantalum, titanium and fluorine ions obtained in the step (1); (3) and (3) putting the solution into a reaction kettle by a hydrothermal method, transferring the solution into an oven, heating to 160-200 ℃, and preserving heat for 3-48 hours. (4) Cooling the reaction kettle to room temperature, washing the obtained product with water and ethanol, centrifuging and drying to obtain the Ti ion doped TaO2F, nano-materials.
Description
Technical Field
The invention relates to Ti ion doped TaO with a three-dimensional sea urchin-shaped nano structure2A preparation process of F material belongs to the technical field of nano material preparation.
Background
TaO2F has a cubic ReO3A structure wherein a = b = c =3.9 a, α = β = γ =90 °; belong toPm-3m space group; ABX considered undistorted3Perovskite structure, the A site is the vacancy, and O and F atom occupy the same crystallographic position. TaO (TaO)2The density of the F material is very low, only 6.51g/cm3(ii) a Its thermal expansion coefficient is close to zero. Furthermore, TaO2The F material has no absorption band in the middle infrared region (3-5 mm), so that the F material can be used as a wave-transmitting material in the infrared band. TaO (TaO)2The forbidden band width of the F material is 4.1 eV, and the F material is a wide band gap semiconductor; the method can be applied to the fields of light-emitting diodes, photoelectric detectors, piezoresistors, gas sensors and the like.
Due to environmental pollution and increasing demand for energy, the conversion of solar energy and the related research on sustainable production of green energy have attracted great attention. Tantalum oxide has a suitable energy band structure, excellent chemical stability and photo-etching properties, and thus is widely used as a photocatalytic material for hydrogen production. In particular TaO having a cubic crystal structure2The F material is beneficial to the separation of photo-generated charge carriers and charge transfer; because it has an A-site vacancy and the Ta-O (F) -Ta bond angle is close to 180 deg.. In addition, the doping of F ions can change the electronic structure of the tantalum oxide, promote the photo-excited electrons to have stronger reduction capability, and improve the photocatalytic activity of the tantalum oxide in an ultraviolet-visible light region. Xu et al in the paper "Complex-media synthesis of tandum oxygen fl horizontal nanostructures for highly e ffi peripheral photocatalytic hydrogen evolution" by TaF5Isopropanol and deionized water as raw materials, and preparing amorphous tantalum oxyfluoride spheres and single crystal TaO by a hydrothermal method within the range of 100-220 DEG C2The average grain diameter of the spherical grading nanometer structure formed by the F nanometer rod is about 300 nm. And TaO2F nanorods nucleated on the surface of amorphous tantalum oxyfluoride spheres and run along [100 ]]Growing; the structure has a high specific surface area (152.4 m)2 g−1). The experiment of simulating the sunlight irradiation shows that the prepared TaO2The F nano composite material has excellent photocatalytic property, and the photocatalytic hydrogen production efficiency reaches 1.95 mmol h without the assistance of any cocatalyst−1 g−1(ii) a And exhibits good photocatalytic stability.
In addition, the electrolytic water reaction is considered to be one of the most efficient methods for producing hydrogen. Currently, the noble metals platinum and ruthenium oxide are the most efficient HER and OER electrocatalysts, but their limited reserves and high prices limit commercial applications. Therefore, the development of the non-noble metal electrocatalyst with high efficiency and low price has very important significance. TaO (TaO)2F is a very stable transition metal oxyfluoride and can be used as an electrocatalyst of an alkaline medium OER. Xin Yue et al in the article "high dry table and effective non-previous metallic analytes of tantalum dioxide use for the oxygen evolution reaction" show that TaO2The F material shows effective electrocatalytic activity and excellent stability; is an electro-catalyst candidate material with great potential.
On the one hand, TaO can be further improved by doping with transition metal ions2F material photo/electrocatalytic activity; according to the hybridization orbit theory and the atom doping theory, the specific transition metal ions can be in TaO2A large number of specific electrons are generated in the F system, and the photo/electro-catalytic activity of the material can be enhanced by regulating the electronic structure of the material. The transition metals titanium and tantalum have similar atomic structures, so that doping with Ti ions can maintain TaO2High stability of F. In addition, since the outermost electron numbers of the titanium and tantalum elements are different, Ti ion doping will cause TaO according to the electron occupying effect2The occupancy rate of the F electron orbit is changed, the forbidden band width is adjusted, and the light absorption wave band is changed, so that the photocatalysis performance is improved. On the other hand, by lifting TaO2The specific surface area or crystallinity of the F material can increase the surface active sites and/or accelerate charge separation; the photoelectrocatalysis activity for hydrogen production can be further improved; the specific surface area of the material is usually increased by synthesizing micro-or nano-structures.
Based on the description, the invention adopts a hydrothermal method to prepare Ti ion-doped TaO2F, and enabling the material to have a three-dimensional sea urchin-shaped nano structure. Ti ion doped TaO prepared by the method2The F material has smaller grain diameter, is not easy to agglomerate, has large specific surface and successfully reduces TaO2The forbidden band width of the F material; the above characteristics are helpfulImproving the catalytic activity and maintaining the catalytic stability. Thus Ti ion-doped TaO2The F material has great research and application prospects.
Disclosure of Invention
The invention aims to solve the problem of the original TaO2The F material has the problems of large particle size, small specific surface area, low purity, single structure, large forbidden band width and the like. Reduction of TaO by doping Ti ions2The forbidden band width of the F material; and the microstructure is adjusted to make it have three-dimensional sea urchin-shaped nanometer structure; so as to increase the specific surface area of the material; thus improving the photo/electrocatalytic activity. The technical scheme is as follows: the adopted raw materials are metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1 (0.1-1) to (1-11), and stirring by magnetic force to obtain a uniform solution; (2) mixing acetic acid and deionized water according to the volume ratio of (0.4-10): 1 mixing to obtain a uniform acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 160-200 ℃, and preserving heat for 3-48 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, carrying out centrifugal separation to obtain a white product; then washing with water and ethanol, centrifuging and drying to obtain the Ti ion-doped TaO with the three-dimensional sea urchin-shaped nano structure2And F, materials.
The working principle of the invention is as follows: firstly, dissolving tantalum powder in hydrofluoric acid to generate H2TaF7And hydrogen (as shown in equation (1)); dissolving metal titanium powder in hydrofluoric acid to generate TiF4And hydrogen (as shown in equation (2)):
2Ta(s) + 14HF(l)=2H2TaF7(l)+5H2(g) (1)
Ti(s) + 4HF(l)=TiF4(l)+2H2(g) (2)
wherein s, l and g each represent the solid stateLiquid and gaseous; h formation from metallic Ta on exposure to excessive HF acid2TaF7(ii) a After acetic acid is added, the whole system is acidic; and in a high-temperature high-pressure environment (hydrothermal reaction), H2TaF7Hydrolysis to form TaO2F and HF, the reaction of which is shown below:
H2TaF7(l)+2H2O(l)= TaO2F(s)+6HF(l) (3)
meanwhile, in a high-temperature and high-pressure environment, titanium ions can be successfully doped into TaO2F lattice and form cubic (Ta)(1-x)Ti5/4x)O2F (x=0.1-0.5) 。
First Ti is doped with TaO2F（(Ta(1-x)Ti5/4x)O2F (x = 0.1-0.5)) devitrified and served as nucleation point and then followed by [100 []Crystal phase growth to form Ti-doped TaO2F nanorods, Ti doped TaO in many different directions2The F nanorods constitute a unique three-dimensional echinoid nanostructure.
The preparation method has the advantages of simple preparation process, short preparation period and easily obtained required raw materials, and the prepared Ti-doped TaO2The F nano material has a three-dimensional sea urchin-shaped nano structure. The product has high purity and good dispersibility, is a good photocatalyst and electrocatalyst, and has great research and application prospects.
Drawings
FIG. 1 is a Ti-doped TaO process for preparing three-dimensional sea urchin-like nanostructures in example 12XRD spectrum of material F.
FIG. 2 is Ti-doped TaO prepared in example 12SEM pictures and EDS spectra of the F material.
FIG. 3 is Ti-doped TaO prepared in example 12TEM photograph of material F.
FIG. 4 is the Ti-doped TaO prepared in example 22XRD spectrum of material F.
FIG. 5 is Ti-doped TaO prepared in example 22SEM picture of material F.
FIG. 6 is Ti-doped TaO prepared in example 32XRD spectrum of material F.
FIG. 7 is Ti-doped TaO prepared in example 42XRD spectrum of material F.
Detailed Description
Example 1:
the adopted raw materials are metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1:0.3:11, and magnetically stirring to obtain a uniform solution; (2) mixing acetic acid and deionized water according to the volume ratio of 0.4: 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 180 ℃, and preserving heat for 24 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, carrying out centrifugal separation to obtain a white precipitate; then washing with water and ethanol, centrifuging and drying to obtain the Ti ion-doped TaO with the three-dimensional sea urchin-shaped nano structure2And F, materials.
Ti doped TaO prepared by hydrothermal method2The powder F is subjected to X-ray diffraction phase analysis (XRD), and an XRD spectrogram obtained by the test is shown in figure 1. The main diffraction peak is located at 22.65 o、32.47 o、46.21oAnd 52.48 oRespectively corresponding to cubic TaO2The (100), (110), (200) and (210) crystal planes of the F phase; the corresponding powder diffraction card is PDF-01-076-. The spectrum has no other crystal impurity phase; this indicates that the prepared Ti ion-doped TaO2The F material is single-phase and high-purity.
FIG. 2 is a schematic diagram of the Ti-doped TaO prepared2Typical Scanning Electron Microscope (SEM) image of F material has sea urchin-like morphology with average diameter of about 0.5-1 μm, and sea urchin structure is TaO doped with one-dimensional Ti ions2F, nano rods. Analyzing the chemical composition of the prepared powder by using an energy spectrometer (EDS) equipped on a scanning electron microscope, wherein the spectrum is shown in figure 2 (d); the sample contains four elements of Ta, Ti, O and F, which indicates that Ti ions are successfully dopedHetero-entry TaO2F in the crystal lattice.
Prepared Ti-doped TaO2The Transmission Electron Microscope (TEM) test was performed on F, and the microscopic morphology and the high-resolution photograph thereof are shown in FIG. 3. FIG. 3(a) illustrates the Ti-doped TaO prepared2The material F shows a sea urchin-like shape; FIG. 3(b) shows that the diameter of the sea urchin structure is about 1 μm and the TaO is doped with Ti whose root is pointed2F nano-rod; the boundary among the nano rods is clear. FIG. 3 (c)) is an enlarged TEM picture of the black rectangular box region of FIG. 3(a), Ti-doped TaO2The width of the F nano rod is about 20-30 nm. FIG. 3(d) shows a single Ti-doped TaO2HRTEM image of F nanorod shows Ti-doped TaO2The F nanorod had good crystallinity, the spacing of the measured facets was about 0.3896 nm, corresponding to cubic TaO2The (100) crystal plane of the F phase; this illustrates Ti-doped TaO during hydrothermal processing2F nano-rod edge [100 ]]And (4) growing in a crystal direction.
Prepared Ti-doped TaO2Testing the F powder by using a solid ultraviolet-visible diffuse reflection spectrum, wherein the calculated forbidden band width (Eg) of the F powder is 3.56 eV; with pure TaO2Compared with the F material (4.1 eV), the energy gap of the F material is narrowed, and the absorption waveband range of the F material to ultraviolet-visible light is enlarged. Therefore, the material has very wide application prospect in the field of photocatalysis.
Example 2:
the preparation raw materials comprise metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1:0.3:7, and magnetically stirring to obtain a uniform solution; (2) mixing acetic acid and deionized water according to a volume ratio of 1.3: 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the transparent tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 180 ℃, and preserving heat for 24 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, carrying out centrifugal separation to obtain a white precipitate; then washing with water and ethanol, centrifugingDrying to obtain Ti ion doped TaO with three-dimensional sea urchin-shaped nano structure2And F, materials.
White Ti-doped TaO prepared by a hydrothermal method2The powder F was subjected to X-ray diffraction phase analysis (XRD), and the XRD spectrum obtained was as shown in FIG. 4. The main diffraction peak is located at 22.65 o、32.47 o、46.21oAnd 52.48 oRespectively corresponding to cubic TaO2The (100), (110), (200) and (210) crystal planes of the F phase; the corresponding powder diffraction card is PDF-01-076-. No other impurity phase exists in the map; this indicates that the prepared Ti ion-doped TaO2The F material is single-phase and high-purity.
FIG. 5 is a schematic diagram of the Ti-doped TaO prepared2Typical Scanning Electron Microscope (SEM) images of the F material show that the material has a sea urchin-like shape, the average diameter of the material is about 0.5-1 mu m, and the sea urchin structure is formed by doping TaO with one-dimensional Ti ions2F, nano rods.
Testing the prepared material by using a solid ultraviolet-visible diffuse reflection spectrum, and calculating that the forbidden band width (Eg) of the material is 3.69 eV; with pure TaO2Compared with the F material (4.1 eV), the energy gap of the F material is narrowed, and the absorption waveband range of the F material to ultraviolet-visible light is enlarged.
Example 3:
the preparation raw materials comprise metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1:0.5:5, and magnetically stirring to obtain a uniform solution; (2) mixing acetic acid and deionized water according to a volume ratio of 1.3: 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 24 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, obtaining white precipitate through centrifugal separation; then washing with water and ethanol, centrifuging and drying to obtain sea urchin shape with three-dimensional structureNanostructured Ti ion doped TaO2And F, materials.
White Ti-doped TaO prepared by a hydrothermal method2The powder F was subjected to X-ray diffraction phase analysis (XRD), and the XRD spectrum obtained was as shown in FIG. 6. The main diffraction peak is located at 22.65 o、32.47 o、46.21o、52.48 oAnd 57.93 oRespectively corresponding to cubic TaO2The (100), (110), (200), (210) and (211) crystal planes of the F phase; the corresponding powder diffraction card is PDF-01-076-. The spectrum has no other crystal impurity phase; this indicates that TaO was produced2The F material is single-phase and high-purity.
Example 4:
the preparation raw materials comprise metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1:0.25:5, and magnetically stirring to obtain a uniform solution; (2) mixing acetic acid and deionized water according to a volume ratio of 1.3: 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 160 ℃, and preserving heat for 24 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, obtaining white precipitate through centrifugal separation; then washing with water and ethanol, centrifuging and drying to obtain the Ti ion doped TaO2And F, materials.
White Ti-doped TaO prepared by a hydrothermal method2The powder F was subjected to X-ray diffraction phase analysis (XRD), and the XRD spectrum obtained was as shown in FIG. 7. Its main diffraction peak is at 22.65 oAnd 46.21oRespectively corresponding to cubic TaO2The (100) and (200) crystal planes of the F phase; the corresponding powder diffraction card is PDF-01-076-. The spectrum has no other crystal impurity phase; this indicates that TaO was produced2The F material is single-phase and high-purity.
Example 5:
preparation of originalThe material comprises metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1:0.1:1, and magnetically stirring to obtain a uniform solution; (2) mixing acetic acid and deionized water according to the volume ratio of 10: 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 160 ℃, and preserving heat for 48 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, obtaining white precipitate through centrifugal separation; then washing with water and ethanol, centrifuging and drying to obtain the Ti ion doped TaO2And F, materials.
Example 6:
the preparation raw materials comprise metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water. (1) Dissolving metal tantalum powder and titanium powder in hydrofluoric acid, wherein the molar ratio of the metal tantalum powder to the titanium powder is 1:1:11 respectively, and magnetically stirring to obtain a uniform solution; (2) mixing acetic acid and deionized water according to the volume ratio of 0.4: 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) and (3) putting the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle to 200 ℃, and preserving heat for 3 hours. (5) Stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, obtaining white precipitate through centrifugal separation; then washing with water and ethanol, centrifuging and drying to obtain the Ti ion doped TaO2And F, materials.
Claims (1)
1. Preparation of three-dimensional sea urchin-shaped nano Ti-doped TaO2A method of F material, characterized by: the preparation raw materials comprise metal tantalum powder, titanium powder, hydrofluoric acid with the mass fraction of 40%, analytically pure acetic acid and deionized water; (1) dissolving tantalum powder and titanium powder in hydrofluoric acid according to the molar ratio of the tantalum powder to the titanium powderRespectively 1 (0.1-1) and 1-11, and obtaining uniform colorless transparent liquid by magnetic stirring; (2) mixing acetic acid and deionized water according to the volume ratio of (0.4-10): 1, uniformly mixing to obtain an acetic acid solution; (3) adding the acetic acid solution obtained in the step (2) into the tantalum, titanium and fluorine ion-containing solution obtained in the step (1) in the stirring process; (4) placing the mixed solution into a hydrothermal reaction kettle by a hydrothermal method, moving the hydrothermal reaction kettle to an oven, heating the hydrothermal reaction kettle to 160-200 ℃, and preserving heat for 3-48 hours; (5) stopping heating; after the hydrothermal reaction kettle is cooled to room temperature, carrying out centrifugal separation to obtain a white precipitate; then washing with water and ethanol, centrifuging and drying to obtain the Ti ion-doped TaO with the three-dimensional sea urchin-shaped nano structure2And F, materials.
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