CN101716503A - Visible light catalyst BiNbO4, preparation method thereof and application thereof - Google Patents
Visible light catalyst BiNbO4, preparation method thereof and application thereof Download PDFInfo
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- CN101716503A CN101716503A CN200910234581A CN200910234581A CN101716503A CN 101716503 A CN101716503 A CN 101716503A CN 200910234581 A CN200910234581 A CN 200910234581A CN 200910234581 A CN200910234581 A CN 200910234581A CN 101716503 A CN101716503 A CN 101716503A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000010955 niobium Substances 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001621 bismuth Chemical class 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 abstract 1
- 239000010919 dye waste Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a visible light catalyst BiNbO4, a preparation method thereof and application thereof. The method for preparing the catalyst comprises the following steps: mixing niobium precursor and soluble bismuth salt to form transparent solution after stirring; stirring the mixture at the temperature of between 60 and 80 DEG C, and adjusting pH value to be between 7 and 8; baking the adjusted solution in an oven at the temperature of between 80 and 250 DEG C for 3 to 10 hours to obtain yellowish-brown precursor powder; and annealing the precursor powder at the temperature of between 550 and 1,050 DEG C for 1 to 24 hours to obtain BiNbO4 powder. The BiNbO4 powder in various crystal forms capable of catalytically decomposing organic dyes under visible light is discovered for the first time; the method for synthesizing the catalyst is simple; and the synthesized BiNbO4 powder has high catalytic activity, can completely degrade methyl violet under the visible light for 1.5 hours, can be used for treating industrial waste water, degrading dye waste water and the like, and has wide application range.
Description
Technical field
The present invention relates to a kind of novel B iNbO
4The synthetic method of visible light catalyst and this kind catalyst and application.Catalyst of the present invention is applicable to the light decomposing, purifying processing of the organic pollution in the sky G﹠W, belongs to the photocatalysis technology field.
Background technology
Semiconductor oxide catalyst has important and wide application prospect in the environmental improvement field, can degrade from environment and also effectively remove toxic chemical pollutant, particularly aspect the processing of industrial wastewater.At present, the photochemical catalyst that photocatalysis field adopted mostly is conductor oxidate, as ZnO, TiO
2, SrTiO
3, Fe
2O
3Or the like.Conductor oxidate is because its preparation is simple, stable in properties, advantage such as cheap and obtain people's extensive concern.But in these conductor oxidates, major part only just has excellent catalytic under ultraviolet light, and catalytic is very weak or do not have under visible light.And at occurring in nature, the main concentration of energy of sunshine is at visible light wave range, and greatly about 50%, and ultraviolet light only is about 7%, and how making full use of this natural green sustainable energy is the problem that people are concerned about.At environmental area,, promote the degraded of pollutant to eliminate if can will help energy savings by the sunshine industrial wastewater of degrading.BiNbO
4Material is as a kind of novel catalysis material, and its photocatalysis property is not still studied fully.And its excellent visible light catalytic, for the processing of industrial wastewater, the particularly degraded of dyeing crystal violet (MV) has good prospects for application.
Chinese invention patent " the stable water miscible niobium and the preparation method and the application of tantalum precursor " (publication number CN1699186, open day on November 23rd, 2005) in, a kind of preparation method of niobium and tantalum precursor of dissolubility is disclosed, this method utilizes cheapness, stable oxide to be raw material, by a kind of simple and feasible synthesis path, obtain the precursor of stable water miscible niobium.This method is used Nb
2O
5Be raw material, mixed grinding is even in molar ratio with itself and potassium hydroxide or NaOH, and first calcination is dissolved in deionized water again, after the filtration, makes solution be highly acid (pH＜2), and the niobium in the solution is precipitated out fully with the niobic acid form; Stir in the lemon aqueous acid that the adding of niobic acid precipitation is an amount of, finally obtain the water miscible niobium precursor aqueous solution.
The niobium precursor solution that relates among the present invention is prepared from according to this method just.The present invention has found BiNbO
4The visible light catalytic effect, preparation method's simple economy is effective, the catalytic height has favorable industrial application prospect.
Summary of the invention
Technical problem to be solved by this invention provides the strong novel B iNbO of a kind of catalytic activity
4Visible light catalyst, this catalyst have the effect of catalytic decomposition organic dyestuff crystal violet under visible light source or sunshine.This Preparation of catalysts technology is simple, but suitability for industrialized production.
Visible light catalyst BiNbO of the present invention
4, be to be prepared from by following method:
1) niobium precursor and soluble bismuth salt mixed in 1: 1.05 in molar ratio, after stirring under the 40-60 ℃ of condition, form clear solution;
2) solution that mixes stirs under 60～80 ℃ of conditions, adds conditioning agent regulator solution pH value to 7～8, and the solution after the adjusting is colourless transparent liquid;
3) above-mentioned colourless transparent solution was dried by the fire in 80～250 ℃ baking oven 3～10 hours, obtain yellowish-brown precursor powder;
4) precursor powder is carried out 550～1050 ℃ of annealing 1～24h hour, obtain BiNbO
4Powder.
Above-mentioned steps 1) soluble bismuth salt is five water bismuth nitrates.
Above-mentioned steps 2) be to be pH value conditioning agent with ammoniacal liquor or ethylenediamine.
In addition, the present invention also provides this visible light catalyst BiNbO
4The preparation method, and the application of catalytic decomposition organic matter dyestuff under visible light source or sunshine.
Photocatalysis of the present invention experiment is to carry out respectively indoor and outdoor, with LA-410UV (300W) visible light source or sunshine as light source.During light-catalyzed reaction, carry out under magnetic agitation, the catalyst use amount is 0.5～10g/L, and within a certain period of time, degraded crystal violet dyestuff detects the variation of solution concentration with the transmitance of spectrophotometric determination solution, thereby calculates organic degradation rate.
The present invention has found the BiNbO of various crystal formations first
4Powder can be at catalytic decomposition organic matter dyestuff under the visible light.And the synthetic method of this catalyst is simple, and synthetic BiNbO
4Powder has high catalytic activity, crystal violet can be degraded fully in 1.5 hours under visible light, and decomposition reaction as light source, can be saved a large amount of energy in order to sunshine, and it can be used for the improvement of trade effluent, the degraded of waste water from dyestuff etc., and range of application is wider.
Description of drawings
Fig. 1 is BiNbO
4The X-ray diffractogram of powder
Fig. 2 is BiNbO
4The SEM pattern photo of powder, wherein 700 ℃ of annealing of Fig. 2 (a) are 3 hours; 1000 ℃ of annealing of Fig. 2 (b) 3 hours; 1050 ℃ of annealing of Fig. 2 (c) 3 hours.
Fig. 3 is the BiNbO for preparing under the different annealing temperature
4To the visible light degradation curve of crystal violet, catalytic amount is 1g/L, sampling interval 0.5h.
The specific embodiment
Embodiment 1:
Get 7.45g niobium precursor (134.2 μ mol/g) in the 50ml beaker, with 0.51g five water bismuth nitrate (Bi (NO
3)
35H
2O) be dissolved in wherein, the solution that mixes stirs under 60 ℃ of conditions, adds ammoniacal liquor and regulates pH value to 7～8, and solution is colourless transparent liquid.Solution prepares the back and dried by the fire 4 hours in 180 ℃ of baking ovens earlier, obtains yellowish-brown precursor powder.In 700 ℃ of Muffle furnaces, carry out calcining in 3 hours then, obtain white BiNbO
4Powder, the specific area of product is about 10.44m
2/ g.Fig. 1 is BiNbO
4The X-ray diffractogram of powder.3 hours BiNbO of 700 ℃ of annealing of Fig. 2 (a)
4The SEM pattern photo of powder; 1000 ℃ of annealing of Fig. 2 (b) 3 hours; 1050 ℃ of annealing of Fig. 2 (c) 3 hours.
With the crystal violet solution of this white powder (1g/L) degraded 10mg/L,, reacted 1.5 hours under the visible light after 10 minutes in ultrasonic dispersion in the ultra sonic bath under the room temperature, degradation rate has reached 100%.
Embodiment 2:
After 3 hours, end product is a white powder to other conditions with 1,1000 ℃ of annealing of embodiment.With the crystal violet solution of the powder that obtains (1g/L) degraded 10mg/L, ultrasonic dispersion is 10 minutes under the room temperature, and visible light reacted 2.5 hours down, and degradation rate has reached 100%, and the product specific area is about 11.47m
2/ g; Fig. 2 (b) is 3 hours BiNbO of 1000 ℃ of annealing
4The SEM pattern photo of powder.
Embodiment 3:
After 3 hours, end product is a white powder to other conditions with one, 1050 ℃ of annealing of embodiment.With the crystal violet solution of the powder that obtains (1g/L) degraded 10mg/L, ultrasonic dispersion is 10 minutes under the room temperature, and visible light reacted 2.5 hours down, and degradation rate has reached 100%, and the product specific area is about 7.86m
2/ g.Fig. 2 (c) is 3 hours BiNbO of 1050 ℃ of annealing
4The SEM pattern photo of powder.
Fig. 3 is the BiNbO for preparing under the different annealing temperature
4To the visible light degradation curve of crystal violet, catalytic amount is 1g/L, sampling interval 0.5h.
Claims (7)
1. visible light catalyst BiNbO
4, it is characterized in that being prepared from by following method:
1) niobium precursor and soluble bismuth salt mixed in 1: 1.05 in molar ratio, after stirring under the 40-60 ℃ of condition, form clear solution;
2) solution that mixes stirs under 60～80 ℃ of conditions, adds conditioning agent regulator solution pH value to 7～8, and the solution after the adjusting is colourless transparent liquid;
3) above-mentioned colourless transparent solution was dried by the fire in 80～250 ℃ baking oven 3～10 hours, obtain yellowish-brown precursor powder;
4) precursor powder is carried out 550～1050 ℃ of annealing 1～24h hour, obtain BiNbO
4Powder.
2. visible light catalyst BiNbO according to claim 1
4, it is characterized in that the described soluble bismuth salt of step 1) is five water bismuth nitrates.
3. visible light catalyst BiNbO according to claim 1
4, it is characterized in that step 2) and be to be pH value conditioning agent with ammoniacal liquor.
4. visible light catalyst BiNbO
4The preparation method, it is characterized in that may further comprise the steps:
1) niobium precursor and soluble bismuth salt mixed in 1: 1.05 in molar ratio, after stirring under the 40-60 ℃ of condition, form clear solution;
2) solution that mixes stirs under 60～80 ℃ of conditions, adds conditioning agent regulator solution pH value to 7～8, and the solution after the adjusting is colourless transparent liquid;
3) above-mentioned colourless transparent solution was dried by the fire in 80～250 ℃ baking oven 3～10 hours, obtain yellowish-brown precursor powder;
4) precursor powder is carried out 550～1050 ℃ of annealing 1～24h hour, obtain BiNbO
4Powder.
5. visible light catalyst BiNbO according to claim 4
4, it is characterized in that the described soluble bismuth salt of step 1) is five water bismuth nitrates.
6. visible light catalyst BiNbO according to claim 4
4, it is characterized in that step 2) and be to be pH value conditioning agent with ammoniacal liquor.
7. the described visible light catalyst BiNbO of claim 1
4The application of catalytic decomposition organic dyestuff crystal violet under visible light source or sunshine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102345814A CN101716503B (en) | 2009-11-23 | 2009-11-23 | Visible light catalyst BiNbO4, preparation method thereof and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102345814A CN101716503B (en) | 2009-11-23 | 2009-11-23 | Visible light catalyst BiNbO4, preparation method thereof and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101716503A true CN101716503A (en) | 2010-06-02 |
| CN101716503B CN101716503B (en) | 2011-11-09 |
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ID=42431197
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102284305A (en) * | 2011-06-24 | 2011-12-21 | 西安理工大学 | Method for preparing nano bismuth niobate resin-loaded photocatalyst |
| CN102294271A (en) * | 2011-06-24 | 2011-12-28 | 西安理工大学 | Preparation method of synthetic resin loaded nanometer bismuth niobate photocatalyst |
| CN103360070A (en) * | 2012-03-31 | 2013-10-23 | 深圳光启创新技术有限公司 | Ceramic substrate based metamaterial and preparation method |
| CN105597729A (en) * | 2016-01-11 | 2016-05-25 | 苏州格瑞惠农膜材料科技有限公司 | Preparing method of niobate photocatalyst Bi3Nb17O47 and application of niobate photocatalyst Bi3Nb17O47 |
| CN105771957A (en) * | 2016-03-22 | 2016-07-20 | 中国科学院地球环境研究所 | Bismuth niobate porous microspheres with photocatalytic activity and ultrasonic atomizing preparation method thereof |
| CN106349756A (en) * | 2016-08-27 | 2017-01-25 | 湖南汉瑞新材料科技有限公司 | Yellow inorganic pigment taking bismuth and vanadium as basic adulterants as well as preparation method and application thereof |
| CN109865512A (en) * | 2019-03-05 | 2019-06-11 | 西安理工大学 | A method of preparing α-bismuth niobate photocatalyst |
-
2009
- 2009-11-23 CN CN2009102345814A patent/CN101716503B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102284305A (en) * | 2011-06-24 | 2011-12-21 | 西安理工大学 | Method for preparing nano bismuth niobate resin-loaded photocatalyst |
| CN102294271A (en) * | 2011-06-24 | 2011-12-28 | 西安理工大学 | Preparation method of synthetic resin loaded nanometer bismuth niobate photocatalyst |
| CN102294271B (en) * | 2011-06-24 | 2012-11-28 | 西安理工大学 | Preparation method of synthetic resin loaded nanometer bismuth niobate photocatalyst |
| CN103360070A (en) * | 2012-03-31 | 2013-10-23 | 深圳光启创新技术有限公司 | Ceramic substrate based metamaterial and preparation method |
| CN103360070B (en) * | 2012-03-31 | 2015-11-18 | 深圳光启创新技术有限公司 | A kind of based on ceramic substrate metamaterial and preparation method |
| CN105597729A (en) * | 2016-01-11 | 2016-05-25 | 苏州格瑞惠农膜材料科技有限公司 | Preparing method of niobate photocatalyst Bi3Nb17O47 and application of niobate photocatalyst Bi3Nb17O47 |
| CN105771957A (en) * | 2016-03-22 | 2016-07-20 | 中国科学院地球环境研究所 | Bismuth niobate porous microspheres with photocatalytic activity and ultrasonic atomizing preparation method thereof |
| CN106349756A (en) * | 2016-08-27 | 2017-01-25 | 湖南汉瑞新材料科技有限公司 | Yellow inorganic pigment taking bismuth and vanadium as basic adulterants as well as preparation method and application thereof |
| CN109865512A (en) * | 2019-03-05 | 2019-06-11 | 西安理工大学 | A method of preparing α-bismuth niobate photocatalyst |
| CN109865512B (en) * | 2019-03-05 | 2022-02-01 | 西安理工大学 | Method for preparing alpha-bismuth niobate photocatalyst |
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|---|---|
| CN101716503B (en) | 2011-11-09 |
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