CN111137920A - Black Ta2O5And preparation method and application thereof - Google Patents
Black Ta2O5And preparation method and application thereof Download PDFInfo
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- CN111137920A CN111137920A CN201911354588.XA CN201911354588A CN111137920A CN 111137920 A CN111137920 A CN 111137920A CN 201911354588 A CN201911354588 A CN 201911354588A CN 111137920 A CN111137920 A CN 111137920A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 61
- 229910004537 TaCl5 Inorganic materials 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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 claims abstract description 28
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 25
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 7
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 230000032900 absorption of visible light Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910052593 corundum Inorganic materials 0.000 description 12
- 239000010431 corundum Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a black Ta2O5The preparation method comprises the following steps: adding TaCl5Dissolving in absolute ethyl alcohol, adding acetylacetone stabilizer, and magnetically stirring to obtain TaCl5Sol precursor; adding TaCl5Aging the sol precursor in an oven, taking out the block-shaped solid at the bottom, transferring the block-shaped solid to a ball milling tank, and carrying out ball milling to obtain tantalum oxide gel powder; feeding the tantalum oxide gel powder into a muffle furnace for heating and preserving heat to obtain white Ta2O5Powder; white Ta2O5Powder, NaBH4Mixing, grinding, annealing in a tube furnace under protective atmosphere, and coolingTo obtain black Ta2O5. The invention is achieved by reacting Ta2O5Incorporating Ta in lower valence state into crystal lattice4+The ions and oxygen vacancies are used for improving the absorption of visible light, enhancing the separation efficiency of photoproduction electrons and holes, realizing the high-efficiency photocatalytic degradation of methylene blue pollutants in water, not using toxic and harmful reagents, having short period and being capable of simply, rapidly and massively producing black Ta on a large scale2O5A novel method of photocatalytic materials.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to black Ta2O5A preparation method and application of the photocatalyst.
Background
The environmental pollution problem in the world is more and more emphasized, governments in various countries put higher requirements on the treatment of harmful substances and establish stricter standards, but the satisfactory effect is not achieved for various reasons. Therefore, development of a new and practical environmental treatment technology is necessary. With the progress of research, people find that the semiconductor photocatalysis technology can be widely applied to the fields of purification of water and air, killing of bacteria and viruses, control of peculiar smell, water cracking, nitrogen fixation and the like due to good light stability and high efficiency. Especially, the heterogeneous photocatalytic oxidation has obvious effect of removing various pollutants in water and atmospheric environment, has wide application prospect and draws high attention of all countries in the world.
In recent years, Ta2O5Photocatalytic materials have attracted a wide range of attention. Compared with common TiO2Photocatalyst, Ta2O5The conduction band position is lower and the valence band position is higher, which results in Ta2O5TiO 22The catalytic reaction for preparing hydrogen by photolysis of water and degrading organic pollutants is easier to carry out. But due to Ta2O5Has a wide band gap (about 4.0eV) and therefore can only respond to ultraviolet light, resulting in that 52% of the visible light in the solar spectrum cannot be absorbed and utilized. Only Ta developed to be able to respond to visible light2O5The photocatalyst can effectively utilize solar energy.
To lift Ta2O5The response of the photocatalyst to visible light makes much work on the research personnel of all countries in the world to expand the absorption spectrum. The patent publication No. CN 104874415BA nitrogen-doped hollow TaON structure is provided, but electrostatic spinning equipment and technology are used during preparation, so that the production cost is high, and the process is relatively complex. Patent publication No. CN104826643B reports an N-doped Ta that can work under visible light2O5And a CdS heterostructure, a certain visible light catalytic effect is obtained, but toxic and harmful metal ions Cd are used in the preparation process of the material2+Limiting its large-scale application. Therefore, Ta with high visible light catalytic efficiency, which is simple in development process flow and environmentally friendly2O5Catalysts remain a formidable challenge.
Through relevant literature reports and patent findings about tantalum oxide nano materials at home and abroad by investigation, no black Ta exists at present2O5Preparation of (2) and precedent of photocatalytic application under the drive of visible light.
Disclosure of Invention
Based on the technical problems in the background introduction, the invention provides a black Ta2O5And a preparation method and application thereof; aiming at the technical problems of the existing tantalum oxide photocatalytic material in preparation and practical application, the invention adopts Ta as the material2O5Incorporating Ta in lower valence state into crystal lattice4+The preparation method has the advantages that the ions and oxygen vacancies are used for improving the absorption of visible light, simultaneously enhancing the separation efficiency of photoproduction electrons and holes, and finally realizing the high-efficiency photocatalytic degradation of methylene blue pollutants in the water body.
The invention provides a black Ta2O5The preparation method is characterized by comprising the following steps:
s1 preparation of TaCl5Sol precursor
Adding TaCl5Dissolving in absolute ethyl alcohol, adding acetylacetone stabilizer, and stirring to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven, taking out the massive solid at the bottom, and ball-milling to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Delivering the tantalum oxide gel powder into a muffle furnace, heating to 600-800 ℃, and preserving heat to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
White Ta2O5Powder, NaBH4Uniformly mixing and grinding, placing in a tube furnace, annealing at a temperature of more than or equal to 400 ℃ in a protective atmosphere, and cooling to obtain black Ta2O5。
The preparation process comprises the following steps:
1. firstly, TaCl is added5Dissolving in a glass beaker filled with absolute ethyl alcohol, adding acetylacetone stabilizer, and magnetically stirring to obtain sol.
2. And (3) aging the clear transparent sol obtained in the last step in an oven, obtaining gel block-shaped solid after the ethanol solvent is completely volatilized, and fully grinding the solid into fine powder through ball milling treatment.
3. Taking out the tantalum oxide gel powder, putting the tantalum oxide gel powder into a corundum crucible, putting the corundum crucible into a muffle furnace, and annealing at high temperature to obtain white Ta2O5And (3) powder.
4. Under a protective atmosphere, by NaBH4Strong chemical reduction in white Ta2O5Incorporating Ta into the crystal lattice4+Ion and oxygen vacancy expand the absorption spectrum range to finally obtain black Ta2O5。
Preferably, in S1, TaCl5And the weight volume ratio g of the absolute ethyl alcohol is as follows: ml is 3-10: 30.
preferably, in S1, TaCl5And the weight volume ratio g of acetylacetone is as follows: ml is 3-10: 2-5.
Preferably, in S2, the oven temperature is 60 ℃.
Preferably, in S2, the ball milling treatment time is more than or equal to 24 h.
Preferably, in S3, the temperature increase rate of the muffle furnace is controlled to be 5-10 deg.C/min.
Preferably, in S4, NaBH4With white Ta2O5The mass ratio of the powder is more than or equal to 1: 1.
preferably, in S4, the annealing treatment is performed under a protective atmosphere, and the protective gas is argon and/or nitrogen.
Preferably, in S4, the annealing time is 0.5-1 h.
Preferably, in S4, the temperature reduction further includes a post-treatment, in which the excess unreacted NaBH is removed by washing with deionized water and methanol 3 times respectively4。
The invention provides a black Ta2O5Using the above-mentioned black Ta2O5The preparation method is as follows.
The above-mentioned black Ta2O5The application in photocatalytic reaction.
Black Ta with high visible light catalytic efficiency2O5A method for preparing nano material. Mainly adopts a sol-gel method to prepare a tantalum oxide precursor, and the precursor is calcined in the air at high temperature to prepare white Ta2O5Then NaBH is added4As a reducing agent to prepare black Ta2O5A photocatalytic material. The specific principle is that by adding Ta2O5Introduction of low-valence Ta into crystal lattice4+Ions and oxygen vacancy defects narrow the band gap width, thereby enhancing its absorption of visible light. The invention has simple preparation process, uniform product particle size, no use of toxic and harmful raw materials, and suitability for large-scale industrial production. Under visible light irradiation, black Ta2O5Photo-generated electrons with strong reducibility and holes with strong oxidizing property are generated on the surface, and the removal rate of methylene blue pollutants with the concentration of 10ppm in the water body within 2 hours reaches 98.5 percent.
Black Ta prepared by the invention2O5The photocatalyst has the following advantages:
1. the raw materials used in the synthesis process have no biological toxicity and environmental toxicity;
2. the preparation process is simple, and the large-scale preparation can be realized by industrial equipment;
3. obtained black Ta2O5The catalyst has strong absorption to visible light and can effectively catalyze and degrade methylene blue pollutant molecules in water.
Drawings
FIG. 1 is white Ta prepared in example 52O5And black Ta2O5A photograph of the sample of (1);
FIG. 2 is the black Ta prepared in example 52O5A TEM photograph of;
FIG. 3 is the black Ta prepared in example 52O5The absorption spectrum of the powder;
FIG. 4 is the black Ta prepared in example 52O5Electron paramagnetic resonance spectroscopy of (1);
FIG. 5 is the black Ta prepared in example 52O5The methylene blue dye in the water body is catalytically degraded under the irradiation of visible light.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Black Ta2O5The preparation method comprises the following steps:
s1 preparation of TaCl5Sol precursor
3g of TaCl5Dissolving in a glass beaker filled with 30mL of absolute ethanol, slowly adding 5mL of acetylacetone stabilizer, and magnetically stirring for 3h to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven at the temperature of 80 ℃, taking out the massive solid at the bottom of the beaker after the ethanol solvent is completely volatilized, transferring the massive solid into a ball milling tank, and performing ball milling for 24 hours to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Placing the tantalum oxide gel powder into a corundum crucible, placing the corundum crucible into a muffle furnace, heating to 600 ℃ at the temperature rising speed of 10 ℃/min, and preserving heat for 4h to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
1g of white Ta2O5Powder, 1g NaBH4Mixing, grinding, placing in a tube furnace, annealing under protective atmosphere with argon and/or nitrogen at 450 deg.C for 0.5h, taking out when the temperature in the furnace is reduced to room temperature, washing with deionized water and methanol for 3 times to remove excessive unreacted NaBH4To obtain black Ta2O5。
Example 2
Black Ta2O5The preparation method comprises the following steps:
s1 preparation of TaCl5Sol precursor
10g of TaCl5Dissolving in a glass beaker filled with 30mL of absolute ethanol, slowly adding 2mL of acetylacetone stabilizer, and magnetically stirring for 6h to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven at the temperature of 60 ℃, taking out the massive solid at the bottom of the beaker after the ethanol solvent is completely volatilized, transferring the massive solid into a ball milling tank, and performing ball milling for 48 hours to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Placing tantalum oxide gel powder into a corundum crucible, placing the corundum crucible into a muffle furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
1g of white Ta2O5Powder, 2g NaBH4Mixing, grinding, placing in a tube furnace, annealing under protective atmosphere with argon and/or nitrogen at 400 deg.C for 1h, taking out when the temperature in the furnace is reduced to room temperature, washing with deionized water and methanol for 3 times to remove excessive unreacted NaBH4To obtain black Ta2O5。
Example 3
Black Ta2O5The preparation method comprises the following steps:
s1 preparation of TaCl5Sol precursor
6g of TaCl5Dissolving in a glass beaker filled with 30mL of absolute ethanol, slowly adding 4mL of acetylacetone stabilizer, and magnetically stirring for 5h to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven at the temperature of 70 ℃, taking out the massive solid at the bottom of the beaker after the ethanol solvent is completely volatilized, transferring the massive solid into a ball milling tank, and performing ball milling for 36 hours to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Placing tantalum oxide gel powder into a corundum crucible, placing the corundum crucible into a muffle furnace, heating to 700 ℃ at the temperature rising speed of 8 ℃/min, and preserving heat for 3h to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
1g of white Ta2O5Powder, 1.5g NaBH4Mixing, grinding, placing in a tube furnace, annealing under protective atmosphere with argon and/or nitrogen at 450 deg.C for 0.8 hr, taking out when the temperature in the furnace is reduced to room temperature, washing with deionized water and methanol for 3 times to remove excessive unreacted NaBH4To obtain black Ta2O5。
Example 4
Black Ta2O5The preparation method comprises the following steps:
s1 preparation of TaCl5Sol precursor
5g of TaCl5Dissolving in a glass beaker filled with 30mL of absolute ethanol, slowly adding 3mL of acetylacetone stabilizer, and magnetically stirring for 5h to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven at the temperature of 60 ℃, taking out the massive solid at the bottom of the beaker after the ethanol solvent is completely volatilized, transferring the massive solid into a ball milling tank, and performing ball milling for 24 hours to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Placing the tantalum oxide gel powder into a corundum crucible, placing the corundum crucible into a muffle furnace, heating to 600 ℃ at the temperature rising speed of 5 ℃/min, and preserving heat for 4h to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
1g of white Ta2O5Powder, 1g NaBH4Uniformly mixing and grinding, placing in a tube furnace, annealing under protective atmosphere, wherein the protective gas is argon, the annealing temperature is 400 ℃, the annealing time is 1h, taking out after the temperature in the furnace is reduced to room temperature, respectively washing 3 times by using deionized water and methanol to remove redundant unreacted NaBH4Drying at 60 ℃ in an oven to obtain black Ta2O5。
Example 5
Black Ta2O5The preparation method comprises the following steps:
s1 preparation of TaCl5Sol precursor
5g of TaCl5Dissolving in a glass beaker filled with 30mL of absolute ethanol, slowly adding 5mL of acetylacetone stabilizer, and magnetically stirring for 6h to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven at the temperature of 60 ℃, taking out the massive solid at the bottom of the beaker after the ethanol solvent is completely volatilized, transferring the massive solid into a ball milling tank, and performing ball milling for 24 hours to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Placing tantalum oxide gel powder into a corundum crucible, placing the corundum crucible into a muffle furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3h to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
1g of white Ta2O5Powder, 2g NaBH4Mixing, grinding, placing in a tube furnace, annealing under protective atmosphere with argon gas at 400 deg.C for 0.5 hr, cooling to room temperature, taking out, washing with deionized water and methanol for 3 times to remove excessive unreacted NaBH4Drying at 60 ℃ in an oven to obtain black Ta2O5。
Referring to FIGS. 1-5, FIG. 1 is white Ta prepared in example 52O5And black Ta2O5A photograph of the sample of (1); FIG. 2 is the black Ta prepared in example 52O5A TEM photograph of; FIG. 3 is the black Ta prepared in example 52O5The absorption spectrum of the powder; FIG. 4 is the black Ta prepared in example 52O5Electron paramagnetic resonance spectroscopy of (1); FIG. 5 is the black Ta prepared in example 52O5The methylene blue dye in the water body is catalytically degraded under the irradiation of visible light. The invention has simple preparation process, uniform product particle size, no use of toxic and harmful raw materials, and suitability for large-scale industrial production. Under visible light irradiation, black Ta2O5Photo-generated electrons with strong reducibility and holes with strong oxidizing property are generated on the surface, and the removal rate of methylene blue pollutants with the concentration of 10ppm in the water body within 2 hours reaches 98.5 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. Black Ta2O5The preparation method is characterized by comprising the following steps:
s1 preparation of TaCl5Sol precursor
Adding TaCl5Dissolving in absolute ethyl alcohol, adding acetylacetone stabilizer, and stirring to obtain TaCl5Sol precursor;
s2 preparation of tantalum oxide gel powder
Adding TaCl5Aging the sol precursor in an oven, taking out the massive solid at the bottom, and ball-milling to obtain tantalum oxide gel powder;
s3, white Ta prepared2O5Powder of
Delivering the tantalum oxide gel powder into a muffle furnace, heating to 600-800 ℃, and preserving heat to obtain white Ta2O5Powder;
s4 preparation of Black Ta2O5Powder of
White Ta2O5Powder, NaBH4Uniformly mixing and grinding, placing in a tube furnace, annealing at a temperature of more than or equal to 400 ℃ in a protective atmosphere, and cooling to obtain black Ta2O5。
2. The black Ta of claim 12O5Characterized in that, in S1, TaCl5And the weight volume ratio g of the absolute ethyl alcohol is as follows: ml is 3-10: 30.
3. the black Ta of claim 12O5Characterized in that, in S1, TaCl5And the weight volume ratio g of acetylacetone is as follows: ml is 3-10: 2-5。
4. The black Ta of claim 12O5The preparation method is characterized in that in S2, the temperature of the oven is more than or equal to 60 ℃.
5. The black Ta of claim 12O5The preparation method is characterized in that in S2, the ball milling treatment time is not less than 24 h.
6. The black Ta of claim 12O5The method of (1) is characterized in that in S3, the temperature rise rate of the muffle furnace is controlled to be 5-10 ℃/min.
7. The black Ta of claim 12O5Characterized in that, in S4, NaBH is added4With white Ta2O5The mass ratio of the powder is more than or equal to 1: 1.
8. the black Ta of claim 12O5The preparation method is characterized in that in S4, annealing treatment is carried out under protective atmosphere, and the protective atmosphere is argon and/or nitrogen; preferably, the annealing time is 0.5-1 h.
9. Black Ta2O5Characterized by using black Ta according to any one of claims 1 to 82O5The preparation method is as follows.
10. A black Ta as claimed in claim 92O5The application in photocatalytic reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533163A (en) * | 2020-05-20 | 2020-08-14 | 中国科学技术大学 | Black lithium titanate material for lithium ion battery cathode and preparation method and application thereof |
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2019
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Non-Patent Citations (3)
| Title |
|---|
| CHENG XU ET AL.: ""Laser-induced damage of Ta2O5films obtained from TaCl5precursorand annealed at different temperatures"", 《APPLIED SURFACE SCIENCE》 * |
| GUILIAN ZHU ET AL.: ""Gray Ta2O5 Nanowires with Greatly Enhanced Photocatalytic Performance"", 《ACS APPL. MATER. INTERFACES》 * |
| ZHENG-WEI ZHOU ET AL.: ""Elaborate synthesis of black tin oxide–black titanium oxide core–shell nanotubes for ultrastable and fast lithium storage"", 《CHEM. COMMUN.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533163A (en) * | 2020-05-20 | 2020-08-14 | 中国科学技术大学 | Black lithium titanate material for lithium ion battery cathode and preparation method and application thereof |
| CN111533163B (en) * | 2020-05-20 | 2022-04-19 | 中国科学技术大学 | Black lithium titanate material for lithium ion battery cathode and preparation method and application thereof |
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Application publication date: 20200512 |