CN101224420A - Uses of light degradation catalyst tungstic oxide nano-powder - Google Patents
Uses of light degradation catalyst tungstic oxide nano-powder Download PDFInfo
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- CN101224420A CN101224420A CNA2008100195292A CN200810019529A CN101224420A CN 101224420 A CN101224420 A CN 101224420A CN A2008100195292 A CNA2008100195292 A CN A2008100195292A CN 200810019529 A CN200810019529 A CN 200810019529A CN 101224420 A CN101224420 A CN 101224420A
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- tungstic oxide
- oxide nano
- methylene blue
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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 usage of a photolysis catalyst tungstic oxide nano powder is that the powder is applied as a photocatalyst in the degradation of an azo color methylene blue. The tungstic oxide nano powder is prepared by a low temperature hydrothermal method and a chemical precipitation method. When the catalyst is put in a methylene blue solution and kept for 3 hours under sunshine, then the discoloring ratio D is higher than or equal to 90%, and the discoloring ratio can be more than or equal to 97%, more particularly, in a flow system. Compared with a quadrature phase tungstic oxide nano powder, the catalytic activity of an m-zro2 tungstic oxide nano powder is higher. The removal rate of Chemical Oxygen consumption CODcr is measured as 91.7% when the methylene blue solution is degraded by a photolysis catalyst. The result of an ion-chromatographic analysis indicates the methylene blue is degraded into ions such as Cl<->, SO4<2->, NO<3->, etc. by tungstic oxide. The catalyst is characterized by high catalytic activity, stable performance, and repeatable usage, having enormous use value and wide potential application in actual production and living.
Description
One, technical field
The present invention relates to a kind of nano material and uses thereof, exactly is that tungstic oxide nano-powder is as the application of catalyst in light degradation azo dyes methine orchid.
Two, background technology
In recent years, the control of environmental pollution has become the human major issue of being badly in need of solution with improvement.Characteristics such as waste water from dyestuff has complicated component, colourity height, discharge capacity is big, toxicity is big are the difficult problems in the environmental pollution improvement always.Semi-conducting material becomes a kind of new technology with waste water control of broad prospect of application as photochemical catalyst catalytic degradation waste water from dyestuff.Under the irradiation of specific wavelength light source, the semiconductor light-catalyst generation electron-hole pair that is stimulated further generates strong oxidizer hydroxyl radical free radical (OH), and hydroxyl radical free radical (OH) has very strong oxidisability can be oxidized to CO with organic pollution
2, H
2Non-toxic products such as O.This technology is one of active research field the most in the world in recent years.[1] such as Saquib M. has studied the photocatalytic degradation of titanium dioxide to this dyestuff of triphenylmenthane, but titanium dioxide because the narrow ultraviolet light that can only absorb of band gap, so photocatalytic activity is lower.[2] such as Jang Jum Suk have reported ZnO and ZnS nanometer sheet photocatalytic degradation of dye acid red, only at ZnS that obtains below 500 ℃ and the ZnO that obtains more than 550 ℃ higher photocatalytic activity are arranged, to having relatively high expectations of experiment condition.XingJingcheng etc. [3] utilize synthetic Nb
2O
5, SrNb
2O
6Nanometer powder and both compound photocatalytic degradation methyl orange, result show effectively degraded methyl orange of compound.[4] such as Huang Lei have synthesized the Cu of different-shape
2O, the nanometer that obtains is box-like, nanotube-shaped, the spherical Cu of nanometer
2The multiple organic dyestuff of O photocatalytic degradation is found nanotube-shaped Cu
2O photocatalytic activity height is so require relatively harsher to the pattern of product.
Three, summary of the invention
The present invention is intended to dye wastewater treatment using, and with catalyst photocatalytic degradation azo dyes methine orchid, technical problem to be solved is to select the high catalyst of catalytic activity.
The applicant is through a large amount of tungstic acid (WO that experimental studies have found that
3) nano-powder can high efficiency photocatalysis degraded methine orchid.The WO that the present invention is alleged
3The purposes of nano-powder is exactly nanometer WO
3In the processing of degrade azo dyestuff methine orchid as the application of Photodegradation catalyst.
WO
3Nano-powder prepares with hydrothermal reaction at low temperature and chemical precipitation method, and XRD analysis is the result show, the WO of hydrothermal reaction at low temperature preparation
3Powder is the quadrature phase, the WO of chemical precipitation method preparation
3Powder is the monocline phase.The SEM photo shows WO
3Powder is uniform nanometer sheet.
WO with certain mass
3Nano-powder drops in the blue solution of certain density methine, and behind the illumination certain hour, the methine orchid is just by photocatalytic degradation.Estimate the degree and the effect of photocatalytic degradation in the present invention with following three aspects.
1, dye decolored rate (D)
D=[(A
0-A)/A
0] * 100%, A in the formula
0Be the absorbance of former dye solution, A is the absorbance of the dye solution measured under maximum absorption wavelength behind the photocatalytic degradation.
Experiment shows that the crystalline phase of the quality of catalyst, light source, light application time, catalyst and the temperature of system are all influential to D.Under the room temperature, be advisable 0.0080g monocline phase WO in 3 hours with sunshine illumination
3The photocatalytic activity of nano-powder is higher than 0.0080g quadrature phase WO
3Nano-powder.With distilled water and absolute ethyl alcohol cyclic washing, drying, its catalytic activity does not subtract catalyst, stability is high, can reclaim repeated use after reclaiming.
2, chemical oxygen consumption (COC) (CODcr)
Chemical oxygen consumption (COC) (CODcr) is to weigh the important indicator of content of organics in the aqueous solution.Measuring the blue solution of methine by the CODcr value before and after the photocatalytic degradation.Get the blue solution 5mL of methine, add 5mL potassium bichromate standard liquid (0.025mol/L) and 15mL concentrated sulfuric acid solution, behind the ultrasonic 30min, cool to room temperature is an indicator with the ferroin, uses the iron ammonium sulfate standard solution titration.After measured, the CODcr clearance of methine orchid is 91.7%.This explanation, the blue solution of methine is through WO
3Behind the nano-powder photocatalytic degradation, organic content obviously reduces in the solution.
3, the content of inorganic ions in the blue solution of the methine crossed of catalytic degradation
In order to judge WO
3To methine orchid photocatalytic degradation whether, the blue solution of methine that catalytic degradation is crossed carries out ion chromatography, records the pH=4.8 of the blue solution of methine this moment, is acid, and the ion concentration in the solution is as follows:
| Cl - | 5.39166mg/L |
| SO 4 2- | 6.49399mg/L |
| NO 3 - | 2.07008mg/L |
Azo dyes methine orchid has following stable chemical constitution:
The chromatography of ions result shows WO
3Nano-powder has catalytic activity, is Cl with methine blue streak catalytic degradation
-, SO
4 2-, NO
3 -Deng inorganic ions, reached the purpose of catalytic degradation.
Compare this Photodegradation catalyst WO with the conventional semiconductor photochemical catalyst
3The nano powder preparation method is simple, with low cost, stability is high, catalytic activity is high, photocatalytic degradation to the methine orchid is more thorough, and the band-gap energy of tungstic acid is 2.5ev, can be excited by the light radiation of wavelength＜500nm, can make full use of sunshine, be a kind of outstanding semiconductor light-catalyst.
Four, description of drawings
Fig. 1 is the XRD diffraction pattern of the tungstic acid of hydrothermal reaction at low temperature preparation, and all diffraction maximums are all pointed out, with the standard quadrature mutually tungstic acid card (71-0131) match.
Fig. 2 is the SEM photo of the tungstic acid of hydrothermal reaction at low temperature preparation.Sample is a nanometer sheet, and outward appearance is even, the about 200nm of the length of side, and thickness is about tens nanometers.
Fig. 3 is the XRD diffraction pattern of the tungstic acid of chemical precipitation method preparation, shows the structure of monocline phase tungstic acid, and card (72-0677) is identical mutually with the standard monocline, and all diffraction maximums are all pointed out.
Fig. 4 is the SEM photo of the tungstic acid of chemical precipitation method preparation.Sample is a nano-sheet, and the length of side is about 400nm, and thickness is about tens nanometers.
Fig. 5 is the WO of monocline phase
3Sample is reused five times after reclaim the XRD diffraction pattern of surveying, and the result shows, WO
3Sample still is the monocline phase, and its thing is mutually constant.A is monocline phase WO among the figure
3The XRD diffraction pattern of sample, b is for using the WO that reclaims for five times
3The XRD diffraction pattern of sample.
Five, the specific embodiment
(1) WO
3The preparation of nano-powder
1, hydrothermal reaction at low temperature prepares WO
3Nano-powder
Take by weighing the 3.0000g sodium tungstate, 0.0010g CTAB is dissolved in the 30mL distilled water, stirs, and getting above-mentioned solution 3mL, dropwise to splash into 5mL concentration be 3molL
-1HCl in, stir 0.5h, the yellow solution that obtains is moved into to be had in the teflon-lined stainless steel cauldron, places 24h for 100 ℃ in baking oven, it is centrifugal to take out the back, obtains yellow mercury oxide, will precipitate and use distilled water, acetone cyclic washing 3～4 times.80 ℃ of drying 6～7h in baking oven put into 300 ℃ of calcination 3h of Muffle furnace then.
The XRD diffraction pattern and the SEM photo of synthetic product are seen Fig. 1, Fig. 2.
2, chemical precipitation method prepares WO
3Nano-powder
Take by weighing the 3.0000g sodium tungstate, 0.0010g CTAB is dissolved in the 30mL distilled water, stirs, and getting above-mentioned solution 3mL, dropwise to splash into 5mL concentration be 3molL
-1HCl in, stir 2h and make it to react completely, the yellow sol that obtains is centrifugal, obtain yellow mercury oxide, with distilled water, acetone cyclic washing 3～4 times.80 ℃ of drying 6～7h in baking oven put into 300 ℃ of calcination 3h of Muffle furnace then.
The XRD diffraction pattern and the SEM photo of synthetic product are seen Fig. 3, Fig. 4.
(2) WO
3The test of nano-powder photocatalytic degradation methine orchid
1, the quality of catalyst is to the influence of percent of decolourization
The WO that in the blue dye solution of 5mL 10mg/L methine, adds the monocline phase of different quality respectively
3Sample, under sunshine the irradiation 3h after, sample analysis (table 1).Along with the increase of catalyst quality, percent of decolourization increases gradually, and when catalyst consumption was 0.0080g, percent of decolourization was maximum.And catalyst consumption is when continuing to be increased to 0.0100g, and percent of decolourization descends on the contrary.
The quality of table 1 catalyst is to the influence of dye decolored rate
| The quality of catalyst | Percent of decolourization D |
| 0.0020g 0.0040g 0.0060g 0.0080g 0.0100g | 90.93％ 92.87％ 94.31％ 97.15％ 93.76％ |
2, light source is to the influence of percent of decolourization
The WO that in the blue dye solution of 5mL10mg/L methine, adds 0.0080g monocline phase
3Sample, respectively under sunshine and the ultraviolet light irradiation 3h after, sample analysis.The result shows, at the solar light irradiation monoclinic phase WO that places an order
3Sample is 95.36% to the percent of decolourization of methine orchid, and the percent of decolourization to the methine orchid under UV-irradiation is 76.78%.Compare with uviol lamp, better with sunshine as light source.
3, light application time is to the influence of percent of decolourization
The WO that in the blue dye solution of 5mL10mg/L methine, adds 0.0080g monocline phase
3Sample, as light source, the absorbance every 0.5h surveys the blue dye solution of each methyl the results are shown in Table 2 with sunshine.Along with the increase percent of decolourization of light application time increases gradually, 3h rear decoloring rate changes not quite substantially.
Table 2 light application time is to the influence of dye decolored rate
| Time | Percent of decolourization D |
| 0.5h 1h 1.5h 2h 3h 4h | 90.73％ 93.75％ 94.47％ 95.88％ 96.06％ 96.10％ |
4, temperature is to the influence of percent of decolourization
The WO that in the blue dye solution of 5mL10mg/L methine, adds 0.0080g monocline phase
3Sample, to system heating, respectively under different temperature, solar light irradiation 1h, sample analysis.As shown in Table 3, along with the rising of temperature, the percent of decolourization of dye solution increases gradually.
Table 3 temperature is to the influence of percent of decolourization
| Temperature | Percent of |
| 20 |
61.71％ 65.54％ 86.07％ 91.58％ |
5, WO in the current system
3Nano-powder is to the photocatalytic activity of methine orchid
For handling the actual conditions of industry and sanitary sewage in the simulation productive life, this experiment adds the WO of 0.0080g monocline phase in the blue dye solution of 5mL10mg/L methine
3Sample, and make whole system be in flow regime, under sunshine, shine, at regular intervals, sample analysis the results are shown in Table 4.Increase percent of decolourization with light application time increases, and 2.5h can reach the highest percent of decolourization 97.44%.Be 96.06% to compare through the percent of decolourization of 3h solution in the above-mentioned non-current system of mentioning, the decolorization rate of current system is fast, and decolorizing effect is better.This shows WO
3Nano-powder is a kind of good photochemical catalyst, has huge using value in the productive life of reality.
WO in table 4 current system
3Photocatalytic activity
| Time | Percent of decolourization D |
| 0.5h 1h 1.5h 2h 2.5h | 81.42％ 86.05％ 91.94％ 93.67％ 97.44％ |
6, the WO of jljl phase not
3Percent of decolourization to the methine orchid
The quadrature phase WO that in the blue dye solution of 5mL10mg/L methine, adds the 0.0080g Hydrothermal Preparation respectively
3The monocline of sample and the preparation of the 0.0080g precipitation method is WO mutually
3Sample, under sunshine the irradiation 3h after, sample analysis.The WO of monocline phase
3Sample is 97.41% to the percent of decolourization of dyestuff, the WO of quadrature phase
3Sample is 91.40% to the percent of decolourization of dyestuff, the WO of monocline phase
3The catalytic activity of sample is higher.
7, the stability of catalyst
WO with the monocline phase
3Sample recycles repeatedly, and it is constant substantially to record its catalytic activity, and percent of decolourization all remains on more than 90% each time, WO
3Sample recycles XRD diffraction pattern such as Fig. 5 of surveying, used repeatedly monocline phase WO five times after reclaiming
3The sample thing is mutually constant, thus explanation WO
3As the photochemical catalyst stable performance, reusable.
Claims (1)
1. the purposes of a light degradation catalyst tungstic oxide nano-powder is characterized in that: tungstic oxide nano-powder in the processing of degrade azo dyestuff methine orchid as the application of photochemical catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068981A (en) * | 2010-12-31 | 2011-05-25 | 同济大学 | Hydrothermal preparation method and product of film nano material with photocatalysis property |
| CN104803435A (en) * | 2014-01-23 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Sewage treatment purification agent, preparation method and applications thereof |
| CN105461008A (en) * | 2016-01-25 | 2016-04-06 | 河南科技学院 | Method for degrading rhodamine B by adopting octahedral-structure WO3 photocatalyst |
| CN106622383A (en) * | 2016-09-27 | 2017-05-10 | 天津师范大学 | Prussian blue/tungsten trioxide composite photocatalyst and preparation method and application thereof |
| CN106868527A (en) * | 2017-01-18 | 2017-06-20 | 湖南大学 | A kind of tungsten oxide raw powder's production technology |
| CN107151038A (en) * | 2017-05-31 | 2017-09-12 | 山东理工大学 | A kind of method for alkaline solution Methylene Blue of being degraded under sunshine |
| CN110904677A (en) * | 2019-11-14 | 2020-03-24 | 南通大学 | Cotton fabric for photocatalytic degradation of azo dye and preparation method thereof |
| CN114163057A (en) * | 2021-12-23 | 2022-03-11 | 南京信息工程大学 | Method for catalytically degrading organic matters in waste water containing nitrosyl sulfuric acid dye by using tungsten oxide |
-
2008
- 2008-01-22 CN CNA2008100195292A patent/CN101224420A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068981B (en) * | 2010-12-31 | 2013-03-13 | 同济大学 | Hydrothermal preparation method and product of film nano material with photocatalysis property |
| CN102068981A (en) * | 2010-12-31 | 2011-05-25 | 同济大学 | Hydrothermal preparation method and product of film nano material with photocatalysis property |
| CN104803435A (en) * | 2014-01-23 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Sewage treatment purification agent, preparation method and applications thereof |
| CN105461008A (en) * | 2016-01-25 | 2016-04-06 | 河南科技学院 | Method for degrading rhodamine B by adopting octahedral-structure WO3 photocatalyst |
| CN105461008B (en) * | 2016-01-25 | 2017-11-03 | 河南科技学院 | One kind is using octahedral structure WO3Photochemical catalyst is used for the method for rhodamine B degradation |
| CN106622383B (en) * | 2016-09-27 | 2019-06-11 | 天津师范大学 | Prussian blue/tungstic acid composite photo-catalyst of one kind and the preparation method and application thereof |
| CN106622383A (en) * | 2016-09-27 | 2017-05-10 | 天津师范大学 | Prussian blue/tungsten trioxide composite photocatalyst and preparation method and application thereof |
| CN106868527A (en) * | 2017-01-18 | 2017-06-20 | 湖南大学 | A kind of tungsten oxide raw powder's production technology |
| CN107151038A (en) * | 2017-05-31 | 2017-09-12 | 山东理工大学 | A kind of method for alkaline solution Methylene Blue of being degraded under sunshine |
| CN110904677A (en) * | 2019-11-14 | 2020-03-24 | 南通大学 | Cotton fabric for photocatalytic degradation of azo dye and preparation method thereof |
| CN110904677B (en) * | 2019-11-14 | 2022-04-22 | 南通大学 | Cotton fabric for photocatalytic degradation of azo dye and preparation method thereof |
| CN114163057A (en) * | 2021-12-23 | 2022-03-11 | 南京信息工程大学 | Method for catalytically degrading organic matters in waste water containing nitrosyl sulfuric acid dye by using tungsten oxide |
| CN114163057B (en) * | 2021-12-23 | 2023-04-18 | 南京信息工程大学 | Method for catalytically degrading organic matters in waste water containing nitrosyl sulfuric acid dye by using tungsten oxide |
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Open date: 20080723 |