CN104258885A - Preparation method of flaky hydroxyl copper phosphate nanometer material - Google Patents
Preparation method of flaky hydroxyl copper phosphate nanometer material Download PDFInfo
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- CN104258885A CN104258885A CN201410447849.3A CN201410447849A CN104258885A CN 104258885 A CN104258885 A CN 104258885A CN 201410447849 A CN201410447849 A CN 201410447849A CN 104258885 A CN104258885 A CN 104258885A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention belongs to the field of preparation of nanometer materials, and particularly relates to a preparation method of a flaky hydroxyl copper phosphate nanometer material. The preparation method takes inorganic copper salt and acid phosphate as raw materials; the flaky hydroxyl copper phosphate nanometer material can be prepared by a hydrothermal method at a certain temperature within a certain period of time under the regulation action of polypyrrolidone; and the thickness of the prepared flaky hydroxyl copper phosphate nanometer material is 20-50nm, and the diameter of the flaky hydroxyl copper phosphate nanometer material is within the range of tens of nanometers to hundreds of nanometers. The preparation method has the characteristics of being simple in synthesis method, convenient to operate, environment-friendly in raw materials, high in yield, easy to disperse and the like, thus being beneficial to realizing large-scale industrial production. The prepared flaky hydroxyl copper phosphate has excellent catalytic performance under the simulated sunlight, thus being applied to the field of industrial wastewater treatment.
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 (Cho I-S. Advanced Functional Materials, 2008 such as bar-shaped, flower-shaped, spherical and ellipsoid shape at present; 18 (15): 2154-2162.; Zhan Y, et al. Journal Of Hazardous Materials, 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 ~ 60 min;
2) add a certain amount of polyvinylpyrrolidone (K12 ~ 30) and continue adjust ph to 5 ~ 7 after stirring 10 ~ 30 min;
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 ~ 50 nm 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 ~ 2 M.
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 100 mg is inserted in photocatalytic system, add the methylene blue solution of 150 mL 10.0 mg/L under stirring, after being then placed in dark stirring and adsorbing half an hour, under xenon lamp (800 nm >=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 60 % in aqueous systems.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 ~ 50 nm 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) sodium hydrogen phosphate of the copper nitrate and 0.7098 g that weigh 1.87 g is dissolved in 30 ml water, adds 0.111g polyvinylpyrrolidone after stirring 30min, continues to stir 10min; Regulate pH to be 6 with the sodium hydroxide solution of 0.1 M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, react 6 h under 120 DEG C of conditions, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100 mg is inserted in photocatalytic system, the methylene blue solution of 150 mL 10.0 mg/L is added under stirring, then be placed in dark stirring and adsorbing to make catalyst reach adsorption equilibrium half an hour to adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, 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%, as shown in Figure 1 after 1h.
Embodiment 2:
(1) sodium hydrogen phosphate of the cupric sulfate pentahydrate and 0.7098 g that weigh 2.50 g is dissolved in 30 ml water, adds 0.222g polyvinylpyrrolidone after stirring 40 min, continues to stir 15min; Regulate pH to be 5 with the sodium hydroxide solution of 0.1 M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, react 8 h under 120 DEG C of conditions, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100 mg is inserted in photocatalytic system, the methylene blue solution of 150 mL 10.0 mg/L is added under stirring, then be placed in dark stirring and adsorbing to make catalyst reach adsorption equilibrium half an hour to adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, 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 60 % after 1h.
Embodiment 3:
(1) sodium hydrogen phosphate of the cupric sulfate pentahydrate and 0.7098 g that weigh 2.50 g is dissolved in 30 ml water, adds 0.555g polyvinylpyrrolidone after stirring 50 min, continues to stir 20min; Regulate pH to be 6 with the sodium hydroxide solution of 0.1 M 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 100 mg is inserted in photocatalytic system, the methylene blue solution of 150 mL 10.0 mg/L is added under stirring, then be placed in dark stirring and adsorbing to make catalyst reach adsorption equilibrium half an hour to adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, 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 58 % after 1h.
Embodiment 4:
(1) sodium hydrogen phosphate of the copper nitrate and 0.7098 g that weigh 1.87 g is dissolved in 30 ml water, adds 0.555g polyvinylpyrrolidone after stirring 60 min, continues to stir 30min; Regulate pH to be 7 with the sodium hydroxide solution of 0.1 M subsequently, loaded by mixed solution in stainless steel cauldron, move in air dry oven, react 12 h under 120 DEG C of conditions, after filtration, washing and drying obtain sheet hydroxyl cupric phosphate nano material.
(2) hydroxyl cupric phosphate taking 100 mg is inserted in photocatalytic system, the methylene blue solution of 150 mL 10.0 mg/L is added under stirring, then be placed in dark stirring and adsorbing to make catalyst reach adsorption equilibrium half an hour to adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, 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 55 % after 1h.
Claims (6)
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 ~ 60 min;
2) add a certain amount of polyvinylpyrrolidone (K12 ~ 30) and continue adjust ph to 5 ~ 7 after stirring 10 ~ 30 min;
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.
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 ~ 50 nm 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 and the concentration of acid phosphate in reaction system are 0.2 ~ 2 M.
4. the preparation method of sheet hydroxyl cupric phosphate nano material according to claim 1, is characterized in that: 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.
5. the preparation method of sheet hydroxyl cupric phosphate nano material according to claim 1, is characterized in that: described inorganic mantoquita can be the one in copper nitrate, copper chloride, copper sulphate.
6. the preparation method of sheet hydroxyl cupric phosphate nano material according to claim 1, is characterized in that: described acid phosphate can be the one in dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271156A (en) * | 2015-07-03 | 2016-01-27 | 合肥学院 | Preparation method of Cu2(OH)PO4 nanomaterial adopting hierarchical structure |
| 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 |
| CN106732693A (en) * | 2016-11-17 | 2017-05-31 | 复旦大学 | Flower-shaped, shape alkali formula phosphoric acid carbon/carbon-copper composite material and its preparation method and application of falling leaves 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 |
| CN110171811A (en) * | 2019-06-10 | 2019-08-27 | 河南大学 | A kind of preparation method of heat-staple cupric phosphate crystalline nanometric materials |
| CN114015068A (en) * | 2021-11-23 | 2022-02-08 | 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 |
| CN114956029A (en) * | 2022-05-25 | 2022-08-30 | 武汉材料保护研究所有限公司 | Copper phosphate nanosheet, preparation method and application |
| 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 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271156A (en) * | 2015-07-03 | 2016-01-27 | 合肥学院 | Preparation method of Cu2(OH)PO4 nanomaterial adopting hierarchical structure |
| 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 |
| CN106732693A (en) * | 2016-11-17 | 2017-05-31 | 复旦大学 | Flower-shaped, shape alkali formula phosphoric acid carbon/carbon-copper composite material and its preparation method and application of falling leaves based on copper sheet |
| 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 |
| CN110171811A (en) * | 2019-06-10 | 2019-08-27 | 河南大学 | A kind of preparation method of heat-staple cupric phosphate crystalline nanometric materials |
| CN114015068A (en) * | 2021-11-23 | 2022-02-08 | 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 |
| 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 |
| CN114956029A (en) * | 2022-05-25 | 2022-08-30 | 武汉材料保护研究所有限公司 | Copper phosphate nanosheet, preparation method and application |
| 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 |
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