CN103011287A - Preparation for pyro-vanadic acid zinc hollow microsphere and application thereof - Google Patents
Preparation for pyro-vanadic acid zinc hollow microsphere and application thereof Download PDFInfo
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- CN103011287A CN103011287A CN2012105120674A CN201210512067A CN103011287A CN 103011287 A CN103011287 A CN 103011287A CN 2012105120674 A CN2012105120674 A CN 2012105120674A CN 201210512067 A CN201210512067 A CN 201210512067A CN 103011287 A CN103011287 A CN 103011287A
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- hollow microsphere
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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
Abstract
A preparation method for pyro-vanadic acid zinc hollow microsphere comprises the following specific steps of respectively weighting zinc oxide, vanadium oxide, ethylenediamine tetraacetic acid and polyethylene glycol according to weight ratio of (4-6.6):(10-12.6):(1.2-1.6):1; adding the raw material into distilled water of the same weight of 40-50 parts of zinc oxide, stirring at room temperature, thus obtaining mixed liquor after ultrasound; putting the mixed liquor into a self-generated pressure hydrothermal reaction kettle, carrying out constant temperature hydrothermal reaction for 10-15 hours at 160-170 DEG C, then naturally cooling down to room temperature, finally filtering, washing, and drying substrate at the bottom of the kettle so as to obtain breen pyro-vanadic acid zinc hollow microsphere powder for sewage treatment. The preparation method has no secondary pollution and has low raw material cost, the defect of the TiO2 taken as traditional photocatalyst in practical application of sewage purification is effectively overcome by the pyro-vanadic acid zinc hollow microsphere as the photocatalyst, the whole process of the method is simple, the manufacture cost is lower, the method has high feasibility, and is applicable to industrialized mass production of photocatalyst.
Description
Technical field
The invention belongs to engineering materials, technical field of nano material, the particularly preparation method of pyrovanadic acid zinc hollow microsphere and application thereof.
Background technology
The tradition nano-TiO
2Photocatalyst has higher charge recombination rate and wide forbidden band (3.2eV) and causes its visible light efficiency of conversion lower and limited its practical application.At present to nano-TiO
2The research of the Visible-light Irradiation of photocatalyst mainly concentrates on the aspects such as doping (metal ion and nonmetal), dye photoactivation, semi-conductor be compound, when having obtained challenging preliminary study progress, also exist some problems: really can strengthen it in expansion degree and the absorption intensity of visible-range such as mixing, but TiO after mixing
2The thermally-stabilised poor problem of ubiquity, and its photocatalytic activity is subject to the restriction of the many factors such as kind, concentration, preparation method and post-treating method of dopant ion; Catalyzer by method preparations such as dye photoactivation, semi-conductor are compound mostly exists composition, pattern poor controllability, material bodies phase or surface and exists and variously cause the compound defective of photo-generated carrier, also " bleaching " phenomenon can occur because material is unstable in the photocatalysis to degrade organic matter process.In a word, at present both at home and abroad to TiO
2Carried out a large amount of study on the modification, although help to expand its light abstraction width, improve photochemical catalysis quantum yield and photocatalysis performance, but the photocatalytic activity after the modification is still not high enough, is improving the Journal of Sex Research progress that do not make a breakthrough yet aspect the efficient of directly utilizing sunlight.
The activity of conductor photocatalysis depends on its physico-chemical property, easily the compound of light induced electron-hole occurs and lower its photocatalytic activity in crystal grid defective, so degree of crystallinity is one of principal element that affects the light-catalyzed reaction activity.Obviously, no matter be that simple semiconductor is mixed or compound etc. all existed the easy Complex Problem in light induced electron-hole, do not cause its photocatalytic activity high and restrict its practical application.Therefore research and develop that single-phase, visible light-responded strong novel narrow band gap photocatalyst becomes environmental science and material science needs the preferential research topic that solves.
Nanometer pyrovanadic acid zinc is the relatively more popular a kind of functional inorganic materials of Recent study, the defectives such as the pattern that this compound has been reported has nano belt, nanometer rod, nano flower etc., and these inorganic nano materials are applied to that water treatment field exists that specific surface area is large not, powder and the aqueous solution are not easily separated.The development specific surface area is large, powder can effectively solve this application bottleneck with the segregative pyrovanadic acid zinc of water body hollow microsphere.
Pyrovanadic acid zinc hollow microsphere has no the pertinent literature report.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method and application of pyrovanadic acid zinc hollow microsphere, effectively solve present TiO
2As the defective of traditional photocatalyst in sewage purification practical application existence.
For achieving the above object, solution of the present invention is:
A kind of preparation method of pyrovanadic acid zinc hollow microsphere, its concrete preparation process is:
Step 1, take by weighing zinc oxide, vanadium oxide, ethylenediamine tetraacetic acid (EDTA) and the polyoxyethylene glycol that weight ratio is 4 6.6:10 12.6:1.2-1.6:1 respectively;
Step 2, above-listed raw material is successively joined in the distilled water of 40 50 parts of zinc oxide weight stirring at room, the mixed solution that obtains after ultrasonic again;
Step 3, mixed solution is packed in the autogenous pressure hydrothermal reaction kettle, reacted 10 15 hours at 160-170 degree centigrade of lower incubation water heating, naturally cool to again room temperature;
Step 4, finally by filter, washing, oven dry bottoms namely get breen pyrovanadic acid zinc hollow microsphere powder.
In the described step 2 stirring at room 30-50 minute, the mixed solution that obtains after ultrasonic 30 minutes again.
Described pyrovanadic acid zinc hollow microsphere can be applicable to sewage treatment area, particularly has significant performance aspect photocatalysis degradation organic contaminant.
After adopting such scheme, the present invention has following effect:
1, because the raw materials such as zinc oxide of the present invention, vanadium oxide and ethylenediamine tetraacetic acid (EDTA) is cheapness, nontoxic reagent, therefore preparation technology of the present invention green, non-secondary pollution, raw materials cost are low.
2, the photocatalyst pyrovanadic acid zinc hollow microsphere of the present invention's development can effectively solve present TiO
2As the defective of traditional photocatalyst in sewage purification practical application existence, as improving the visible absorption utilization ratio, suppressing the light induced electron-hole of semi-conductor inside to compound and then raising photochemical catalysis quantum yield; Specific surface area is large, is conducive to absorption and photocatalyst for degrading organic pollutant; Coagulation very easily in water body is convenient to recovery and reproducible utilization behind the catalyzer.
3, photocatalyst pyrovanadic acid zinc hollow microsphere of the present invention can excite that lower energy is efficient at visible light (such as sunlight), organic pollutant, particularly hardly degraded organic substance such as phenol organic matter in the degree of depth degradation of sewage.
4, the whole flow operations of the inventive method is simple, and production cost is lower, and feasibility is larger, is easy to realize the industrialized mass production photocatalyst.
Embodiment
The present invention has disclosed a kind of preparation method of pyrovanadic acid zinc hollow microsphere, and it is that warm hydrothermal method is synthetic in adopting, and concrete preparation process is as follows:
Step 1, take by weighing zinc oxide, vanadium oxide, ethylenediamine tetraacetic acid (EDTA) and the polyoxyethylene glycol that weight ratio is 4 6.6:10 12.6:1.2-1.6:1 respectively;
Step 2, above-listed raw material is successively joined in the distilled water of 40 50 parts of zinc oxide weight, stirring at room 30-50 minute, the mixed solution that obtains after ultrasonic 30 minutes again;
Step 3, mixed solution is packed in 100 milliliters of autogenous pressure hydrothermal reaction kettles of inner bag volume, reacted 10 15 hours at 160-170 degree centigrade of lower incubation water heating, naturally cool to again room temperature;
Step 4, finally by filter, washing, oven dry bottoms namely get breen pyrovanadic acid zinc hollow microsphere powder.
Because the raw materials such as zinc oxide of the present invention, vanadium oxide and ethylenediamine tetraacetic acid (EDTA) are cheapness, nontoxic reagent, therefore preparation technology of the present invention green, non-secondary pollution, raw materials cost are low.
Utilize the pyrovanadic acid zinc hollow microsphere of the inventive method preparation to be applied to sewage disposal, be specially: sewage disposal is adopted and is contained organic pollutant (methylene blue and p-NP) laboratory simulation sewage, with photocatalyst its photocatalytic degradation of research, mineralising effect under daylight (the outdoor illumination of ZhangZhou 2-4 in afternoon in August point) irradiation of patent development of the present invention.
The photocatalyst pyrovanadic acid zinc hollow microsphere of the present invention's development can effectively solve present TiO
2As the defective of traditional photocatalyst in sewage purification practical application existence, as improving the visible absorption utilization ratio, suppressing the light induced electron-hole of semi-conductor inside to compound and then raising photochemical catalysis quantum yield.This photocatalyst pyrovanadic acid zinc hollow microsphere can excite that lower energy is efficient at visible light (such as sunlight), organic pollutant, the particularly photocatalyst such as hardly degraded organic substance such as phenol organic matter in the degree of depth degradation of sewage.
Adopt the synthetic photocatalyst of the inventive method to compare with similar photocatalyst, have obvious advantage:
(1) the microballoon specific surface area is large, can reach 120 m
2/ g; Microsphere diameter is about 1.2 μ m, and inner hollow diameter is between 30-50nm;
(2) strong to visible absorption, at 400 800 nm obvious absorption is arranged;
(3) sedimentation is rapid in water body, can see obvious sedimentation demixing phenomenon in 5 minutes;
(4) the photocatalytic degradation effect is remarkable, with laboratory visible light source simulated solar rayed, 1.5g.L
-1The catalyzer usage quantity to 20 mg.L
-1The Photocatalytic Activity for Degradation experimental result of methylene blue solution show, it faded in 3 hours fully, the clearance of total organic carbon (TOC) can reach 65%; At degraded 10mg.l
-1In the p-NP experiment, basic mineralising was complete in 5 hours.
Also have, the whole flow operations of the present invention is simple, and production cost is lower, and feasibility is larger, is easy to realize the industrialized mass production photocatalyst.In this preparation process, adopt single stage method to realize that the self-assembly in hydro-thermal atmosphere of different metal ion prepares pyrovanadic acid zinc hollow microsphere synthesis strategy, efficiently solve at present mostly photocatalyst multistep experiment flow, need high temperature, the high drawback of apparatus for preparation requirement.
Claims (3)
1. the preparation method of a pyrovanadic acid zinc hollow microsphere, its concrete preparation process is:
Step 1, take by weighing zinc oxide, vanadium oxide, ethylenediamine tetraacetic acid (EDTA) and the polyoxyethylene glycol that weight ratio is 4 6.6:10 12.6:1.2-1.6:1 respectively;
Step 2, above-listed raw material is successively added in the distilled water of 40 50 parts of zinc oxide weight ratios stirring at room, the mixed solution that obtains after ultrasonic again;
Step 3, mixed solution is packed in the autogenous pressure hydrothermal reaction kettle, reacted 10 15 hours at 160 170 degrees centigrade of lower incubation water heatings, naturally cool to again room temperature;
Step 4, finally by filter, washing, oven dry bottoms namely get breen pyrovanadic acid zinc hollow microsphere powder.
2. the preparation method of pyrovanadic acid zinc hollow microsphere as claimed in claim 1, it is characterized in that: stirring at room is 30 50 minutes in the described step 2, the mixed solution that obtains after ultrasonic 30 minutes again.
3. the pyrovanadic acid zinc hollow microsphere that obtains of the preparation method of pyrovanadic acid zinc hollow microsphere as claimed in claim 1 or 2 is applied to sewage disposal.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103730642A (en) * | 2014-01-24 | 2014-04-16 | 厦门大学 | Negative electrode material of lithium ion battery and preparation method thereof |
| CN105253915A (en) * | 2015-11-02 | 2016-01-20 | 渤海大学 | Preparation method of Zn2(OH)3VO3 micro-sphere |
| CN106082331A (en) * | 2016-05-23 | 2016-11-09 | 贵州民族大学 | A kind of Zn3(OH)2v2o72H2the preparation method of O nanometer sheet |
| CN106954637A (en) * | 2017-03-17 | 2017-07-18 | 闽南师范大学 | A kind of deodorizing fungus-proof removes stacte of formaldehyde and preparation method thereof |
Citations (3)
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| US20100254875A1 (en) * | 2004-06-21 | 2010-10-07 | Kalaga Murali Krishna | Monodisperse nanoparticles and method of making |
| CN102140691A (en) * | 2011-02-12 | 2011-08-03 | 河北联合大学 | Method for synthesizing vanadium acid zinc micro/nanowire material by adopting hydrothermal method |
| CN102786090A (en) * | 2012-09-05 | 2012-11-21 | 河北联合大学 | Method for synthesizing vanadic acid zinc overlength nanowire material by microwave radiation |
-
2012
- 2012-12-04 CN CN2012105120674A patent/CN103011287A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100254875A1 (en) * | 2004-06-21 | 2010-10-07 | Kalaga Murali Krishna | Monodisperse nanoparticles and method of making |
| CN102140691A (en) * | 2011-02-12 | 2011-08-03 | 河北联合大学 | Method for synthesizing vanadium acid zinc micro/nanowire material by adopting hydrothermal method |
| CN102786090A (en) * | 2012-09-05 | 2012-11-21 | 河北联合大学 | Method for synthesizing vanadic acid zinc overlength nanowire material by microwave radiation |
Non-Patent Citations (1)
| Title |
|---|
| 贺淳晓: ""含钒三元氧化物纳米晶体的制备、表征及应用"", 《万方学位论文全文数据库》, 31 July 2012 (2012-07-31), pages 44 - 53 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103730642A (en) * | 2014-01-24 | 2014-04-16 | 厦门大学 | Negative electrode material of lithium ion battery and preparation method thereof |
| CN105253915A (en) * | 2015-11-02 | 2016-01-20 | 渤海大学 | Preparation method of Zn2(OH)3VO3 micro-sphere |
| CN105253915B (en) * | 2015-11-02 | 2017-03-22 | 渤海大学 | Preparation method of Zn2(OH)3VO3 micro-sphere |
| CN106082331A (en) * | 2016-05-23 | 2016-11-09 | 贵州民族大学 | A kind of Zn3(OH)2v2o72H2the preparation method of O nanometer sheet |
| CN106954637A (en) * | 2017-03-17 | 2017-07-18 | 闽南师范大学 | A kind of deodorizing fungus-proof removes stacte of formaldehyde and preparation method thereof |
| CN106954637B (en) * | 2017-03-17 | 2019-06-18 | 闽南师范大学 | A kind of deodorizing fungus-proof removes stacte of formaldehyde and preparation method thereof |
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Application publication date: 20130403 |