CN104258885B - A kind of preparation method of sheet hydroxyl cupric phosphate nano material - Google Patents
A kind of preparation method of sheet hydroxyl cupric phosphate nano material Download PDFInfo
- Publication number
- CN104258885B CN104258885B CN201410447849.3A CN201410447849A CN104258885B CN 104258885 B CN104258885 B CN 104258885B CN 201410447849 A CN201410447849 A CN 201410447849A CN 104258885 B CN104258885 B CN 104258885B
- Authority
- CN
- China
- Prior art keywords
- phosphate
- preparation
- hydroxyl cupric
- nano material
- cupric phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to the preparation field of nano material, be specifically related to a kind of preparation method of sheet hydroxyl cupric phosphate nano material.This preparation method with inorganic mantoquita and acid phosphate for raw material, under the regulating and controlling effect of polypyrrole alkane ketone, by hydro-thermal method in uniform temperature and time, sheet hydroxyl cupric phosphate nano material can be prepared, its thickness is 20 ~ 50nm, and diameter is between tens nanometers to hundreds of nanometer.The features such as this preparation method has that synthetic method is simple, easy to operate, raw material environmental protection, productive rate are high, easy dispersion, are beneficial to and realize large-scale industrial production.Prepared sheet hydroxyl cupric phosphate has excellent catalytic performance under simulated solar irradiation, can be applicable to the water treatment field of industrial wastewater.
Description
Technical field
The present invention relates to a kind of preparation method of nano material, be specifically related to a kind of preparation method of sheet hydroxyl cupric phosphate nano material.
Technical background
Current, day by day serious problem of environmental pollution has obtained the great attention of people, and wherein water pollution problems is urgently prevented especially and administered.But along with water pollutant qualitative diversity and complexity, traditional method for treating water can not meet the requirement of people.Photocatalysis relies on the advantages such as self is simple to operate, low energy consumption, reaction condition gentleness, non-secondary pollution, has become the new technology of wastewater treatment, has had vast potential for future development.Nano-photocatalyst has larger specific area and carrier mobility faster, demonstrates more excellent catalytic performance.Hydroxyl cupric phosphate is a kind of novel photocatalyst, under ultraviolet-visible even region of ultra-red, all have good catalytic activity, is a kind of novel active photochemical catalyst with applications well prospect.The hydroxyl cupric phosphate of open report has (ChoI-S.AdvancedFunctionalMaterials, 2008 such as bar-shaped, flower-shaped, spherical and ellipsoid shape at present; 18 (15): 2154-2162.; ZhanY, etal.JournalOfHazardousMaterials, 2010; 180 (1-3): 481-485. and Chinese patent CN201310531313.5).But, up to now, yet there are no the preparation method of sheet hydroxyl cupric phosphate nano material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of sheet hydroxyl cupric phosphate nano material; Synthesized sheet hydroxyl cupric phosphate nano material by wet chemical method, this hydroxyl cupric phosphate nanometer sheet has excellent photocatalytically degradating organic dye performance under simulated solar irradiation.
The present invention with inorganic mantoquita, acid phosphate for raw material polyvinylpyrrolidone regulation and control under prepared flake nano hydroxyl cupric phosphate.
A preparation method for flake nano hydroxyl cupric phosphate, is characterized in that step is as follows:
1) take inorganic mantoquita that stoichiometric proportion is 2 ︰ 1, acid phosphate in container, add the water of certain volume and stir 30 ~ 60min;
2) add a certain amount of polyvinylpyrrolidone (K12 ~ 30) and continue adjust ph to 5 ~ 7 after stirring 10 ~ 30min;
3) above-mentioned suspension is transferred to 100 ~ 140 DEG C of reaction 6-12h in reactor;
4) cool, filter, dry hydroxyl cupric phosphate after washing; In the form of sheets, thickness is 20 ~ 50nm to the hydroxyl cupric phosphate of preparation, and diameter is between tens nanometers to hundreds of nanometer.
Further, described inorganic mantoquita and the concentration of acid phosphate in reaction system are 0.2 ~ 2M.
Further, in described reaction system, polyvinylpyrrolidone (calculating according to its construction unit molecular weight 111g/mol) is 1 ~ 5 ︰ 1 with the chemical dosage ratio of copper ion.
Further, described inorganic mantoquita can be the one in copper nitrate, copper chloride, copper sulphate etc.
Further, described acid phosphate can be the one in dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate etc.
Sheet hydroxyl cupric phosphate nano material of the present invention has excellent photocatalytically degradating organic dye performance, can be used for the water treatment field of industrial wastewater.
The catalytic performance test method adopted is as follows:
The flake nano hydroxyl cupric phosphate taking 100mg is inserted in photocatalytic system, add the methylene blue solution of 150mL10.0mg/L under stirring, after being then placed in dark stirring and adsorbing half an hour, under xenon lamp (800nm >=λ >=320nm), carry out light-catalyzed reaction.
When not adding electron capture agent, flake nano hydroxyl cupric phosphate degradable in 1 hour removes the methylene blue of in aqueous systems 60%.The above results shows, prepared sheet hydroxyl cupric phosphate nano material has excellent photocatalysis performance under simulated solar irradiation, is a kind of potential Industrial Wastewater Treatment material.
Advantage of the present invention is as follows:
Adopt the sheet hydroxyl cupric phosphate nano material of wet chemical method fabricated in situ, this preparation method have that synthetic method is simple, easy to operate, the feature such as raw material environmental protection, productive rate are high, easy dispersion, be beneficial to and realize large-scale industrial production.
In the form of sheets, thickness is 20 ~ 50nm to the hydroxyl cupric phosphate of synthesis, and diameter is about tens nanometers to hundreds of nanometer.Its nanometer sheet structure effectively can increase specific area, the raising carrier mobility of material, and the photocatalysis performance of reinforcing material is a kind of potential catalysis material that can be applicable to contaminant degradation in industrial wastewater.
Accompanying drawing explanation
Fig. 1 is the SEM figure of sheet hydroxyl cupric phosphate nano material in the present invention.
Fig. 2 is the XRD figure of sheet hydroxyl cupric phosphate nano material in the present invention.
Fig. 3 be under room temperature in embodiment 1 sample catalytic degradation performance map.
Detailed description of the invention
As shown in Figure 1 and Figure 2, the schematic diagram of sheet hydroxyl cupric phosphate nano material for being prepared by method of the present invention; Preparation method of the present invention is illustrated below in conjunction with example.
Embodiment 1:
(1) the weighing copper nitrate of 1.87g and the sodium hydrogen phosphate of 0.7098g are dissolved in 30ml water, add 0.111g polyvinylpyrrolidone after stirring 30min, continue to stir 10min; Regulate pH to be 6 with the sodium hydroxide solution of 0.1M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 6h, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100mg is inserted in photocatalytic system, the methylene blue solution of 150mL10.0mg/L is added under stirring, then being placed in dark stirring and adsorbing makes catalyst reach adsorption equilibrium employing 300W xenon lamp half an hour, at ultraviolet-visible light (under (800nm >=λ >=320nm), be about 10cm place from catalyst to shine, sample every 30min, through 5000rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid the absorbance remaining methylene blue at 664nm place, thus obtain the degradation rate of a time period methylene blue.Fig. 3 is the photocatalysis methylene blue degradation curve of sample in embodiment 1, as seen under the condition of not adding hydrogen peroxide, degrades the methylene blue of 62% after 1h.
Embodiment 2:
(1) the weighing cupric sulfate pentahydrate of 2.50g and the sodium hydrogen phosphate of 0.7098g are dissolved in 30ml water, add 0.222g polyvinylpyrrolidone after stirring 40min, continue to stir 15min; Regulate pH to be 5 with the sodium hydroxide solution of 0.1M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 8h, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100mg is inserted in photocatalytic system, the methylene blue solution of 150mL10.0mg/L is added under stirring, then being placed in dark stirring and adsorbing makes catalyst reach adsorption equilibrium employing 300W xenon lamp half an hour, at ultraviolet-visible light (under (800nm >=λ >=320nm), be about 10cm place from catalyst to shine, sample every 30min, through 5000rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid the absorbance remaining methylene blue at 664nm place, thus obtain the degradation rate of a time period methylene blue.Under the condition of not adding hydrogen peroxide, after 1h, degrade the methylene blue of 60%.
Embodiment 3:
(1) the weighing cupric sulfate pentahydrate of 2.50g and the sodium hydrogen phosphate of 0.7098g are dissolved in 30ml water, add 0.555g polyvinylpyrrolidone after stirring 50min, continue to stir 20min; Regulate pH to be 6 with the sodium hydroxide solution of 0.1M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 10h, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100mg is inserted in photocatalytic system, the methylene blue solution of 150mL10.0mg/L is added under stirring, then being placed in dark stirring and adsorbing makes catalyst reach adsorption equilibrium employing 300W xenon lamp half an hour, at ultraviolet-visible light (under (800nm >=λ >=320nm), be about 10cm place from catalyst to shine, sample every 30min, through 5000rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid the absorbance remaining methylene blue at 664nm place, thus obtain the degradation rate of a time period methylene blue.Under the condition of not adding hydrogen peroxide, after 1h, degrade the methylene blue of 58%.
Embodiment 4:
(1) the weighing copper nitrate of 1.87g and the sodium hydrogen phosphate of 0.7098g are dissolved in 30ml water, add 0.555g polyvinylpyrrolidone after stirring 60min, continue to stir 30min; Regulate pH to be 7 with the sodium hydroxide solution of 0.1M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 12h, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100mg is inserted in photocatalytic system, the methylene blue solution of 150mL10.0mg/L is added under stirring, then being placed in dark stirring and adsorbing makes catalyst reach adsorption equilibrium employing 300W xenon lamp half an hour, at ultraviolet-visible light (under (800nm >=λ >=320nm), be about 10cm place from catalyst to shine, sample every 30min, through 5000rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid the absorbance remaining methylene blue at 664nm place, thus obtain the degradation rate of a time period methylene blue.Under the condition of not adding hydrogen peroxide, after 1h, degrade the methylene blue of 55%.
Claims (4)
1. a preparation method for sheet hydroxyl cupric phosphate nano material, is characterized in that: it comprises the steps:
1) take inorganic mantoquita that stoichiometric proportion is 2 ︰ 1, acid phosphate in container, add the water of certain volume and stir 30 ~ 60min;
2) add a certain amount of polyvinylpyrrolidone K12 ~ 30 and continue adjust ph to 5 ~ 7 after stirring 10 ~ 30min;
3) above-mentioned suspension is transferred to reactor, at 100 ~ 140 DEG C of reaction 6-12h;
4) cool, filter, dry hydroxyl cupric phosphate after washing;
Described inorganic mantoquita and the concentration of acid phosphate in reaction system are 0.2 ~ 2M; Calculate according to its construction unit molecular weight 111g/mol, in described reaction system, the stoichiometric proportion of polyvinylpyrrolidone and copper ion is 1 ~ 5 ︰ 1; When not adding electron capture agent, flake nano hydroxyl cupric phosphate degraded in 1 hour remove in aqueous systems 60% methylene blue.
2. the preparation method of a kind of sheet hydroxyl cupric phosphate nano material according to claim 1, is characterized in that: in the form of sheets, thickness is 20 ~ 50nm to prepared hydroxyl cupric phosphate, and diameter is between tens nanometers to hundreds of nanometer.
3. the preparation method of sheet hydroxyl cupric phosphate nano material according to claim 1, is characterized in that: described inorganic mantoquita is the one in copper nitrate, copper chloride, copper sulphate.
4. the preparation method of sheet hydroxyl cupric phosphate nano material according to claim 1, is characterized in that: described acid phosphate is the one in dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447849.3A CN104258885B (en) | 2014-09-04 | 2014-09-04 | A kind of preparation method of sheet hydroxyl cupric phosphate nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447849.3A CN104258885B (en) | 2014-09-04 | 2014-09-04 | A kind of preparation method of sheet hydroxyl cupric phosphate nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104258885A CN104258885A (en) | 2015-01-07 |
| CN104258885B true CN104258885B (en) | 2016-04-20 |
Family
ID=52150533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410447849.3A Expired - Fee Related CN104258885B (en) | 2014-09-04 | 2014-09-04 | A kind of preparation method of sheet hydroxyl cupric phosphate nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104258885B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271156B (en) * | 2015-07-03 | 2017-11-21 | 合肥学院 | A kind of hierarchy Cu2(OH)PO4The preparation method of nano material |
| CN106076376A (en) * | 2016-05-31 | 2016-11-09 | 南京信息工程大学 | A kind of preparation method of butterfly-like copper hydroxyphosphate catalyst |
| CN106732693B (en) * | 2016-11-17 | 2019-10-15 | 复旦大学 | Flower-shaped, fallen leaves shape alkali formula cupric phosphate composite material and preparation method and application based on copper sheet |
| CN107572650A (en) * | 2017-09-04 | 2018-01-12 | 东华理工大学 | A kind of method using hydroxyl cupric phosphate photocatalysis treatment uranium-containing waste water |
| CN110171811B (en) * | 2019-06-10 | 2020-10-20 | 河南大学 | Preparation method of thermostable copper phosphate crystal nano material |
| CN114015068B (en) * | 2021-11-23 | 2023-02-10 | 中国医学科学院生物医学工程研究所 | Flower-shaped MOF material based on coordination of baicalein and copper ions and preparation method and application thereof |
| CN114956028A (en) * | 2022-05-25 | 2022-08-30 | 武汉材料保护研究所有限公司 | Copper phosphate with porous structure and preparation method thereof |
| CN114956029B (en) * | 2022-05-25 | 2024-01-23 | 中国机械总院集团武汉材料保护研究所有限公司 | Copper phosphate nano-sheet, preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103101897A (en) * | 2012-09-24 | 2013-05-15 | 渤海大学 | Method for preparing copper hydroxide phosphate micro-crystals with different shapes |
| CN103551201B (en) * | 2013-11-01 | 2016-03-30 | 长沙理工大学 | A kind of preparation method of copper hydroxyphosphate catalyst |
-
2014
- 2014-09-04 CN CN201410447849.3A patent/CN104258885B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104258885A (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104258885B (en) | A kind of preparation method of sheet hydroxyl cupric phosphate nano material | |
| Du et al. | Enhanced catalytic peroxymonosulfate activation for sulfonamide antibiotics degradation over the supported CoSx-CuSx derived from ZIF-L (Co) immobilized on copper foam | |
| CN105749893B (en) | A kind of preparation method of the modified active carbon fiber silk of area load nano titanium oxide | |
| Xiao et al. | Ordered mesoporous CeO2/ZnO composite with photodegradation concomitant photocatalytic hydrogen production performance | |
| Zhang et al. | Fly ash cenospheres supported visible-light-driven BiVO4 photocatalyst: synthesis, characterization and photocatalytic application | |
| CN106732524B (en) | Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof | |
| Hu et al. | Fabrication of graphitic carbon nitride functionalized P–CoFe2O4 for the removal of tetracycline under visible light: Optimization, degradation pathways and mechanism evaluation | |
| Li et al. | Activation of peroxymonosulfate by a waste red mud-supported Co3O4 quantum dots under visible light for the degradation of levofloxacin | |
| CN106955708A (en) | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water | |
| Jiang et al. | Hydrothermal deposition of CoFe2O4 nanoparticles on activated carbon fibers promotes atrazine removal via physical adsorption and photo-Fenton degradation | |
| Chen et al. | Salt-assisted synthesis of hollow Bi2WO6 microspheres with superior photocatalytic activity for NO removal | |
| CN109847786A (en) | A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H | |
| Wu et al. | Enhanced degradation of chloramphenicol through peroxymonosulfate and visible light over Z-scheme Photocatalysts: Synergetic performance and mechanism insights | |
| Zheng et al. | Nonthermal plasma-vulcanized flower-like ZnS/Zn-Al composites from Zn-Al layered double hydroxides for the adsorption-photo-reduction of Cr (VI) | |
| CN103252244A (en) | Preparation method and application method of visible-light response type bismuth oxychloride photocatalyst | |
| CN106268869A (en) | A kind of preparation method and application of carbon quantum dot/flower-shaped indium sulfide calcium composite photo-catalyst | |
| CN106975503B (en) | A kind of preparation method of the modified phosphotungstic acid/titanium dioxide composite film catalyst of silver | |
| CN104707641A (en) | Metal-nitrogen co-doped titanium dioxide hollow sphere catalyst and preparation method thereof | |
| Chen et al. | Synthesis of micro-nano Ag3PO4/ZnFe2O4 with different organic additives and its enhanced photocatalytic activity under visible light irradiation | |
| CN108079993B (en) | Preparation method of ferrous oxide/cuprous oxide nano composite material | |
| Xiao et al. | Graphitic carbon nitride for photocatalytic degradation of sulfamethazine in aqueous solution under simulated sunlight irradiation | |
| Zhang et al. | Dual sites design of CoFe/Mg MMO catalyst for effectively suppressing dimethylamine re-emission: Degradation products and DFT calculation | |
| CN103342402A (en) | Method for degrading methylene blue by using nitrogen-doped oxygen vacancy type TiO2 catalyst | |
| Fan et al. | Mechanism study on NO removal over the CQDs@ MIL-100 (Fe) composite photocatalyst | |
| CN114956194A (en) | Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160420 Termination date: 20170904 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |