CN106241854B - The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid - Google Patents
The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid Download PDFInfo
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- CN106241854B CN106241854B CN201610800869.3A CN201610800869A CN106241854B CN 106241854 B CN106241854 B CN 106241854B CN 201610800869 A CN201610800869 A CN 201610800869A CN 106241854 B CN106241854 B CN 106241854B
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- cuprous oxide
- glycerine
- adipic acid
- dibutyl ester
- nano cuprous
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid, this method is using glycerine and the positive dibutyl ester mixed liquor of adipic acid as reaction system liquid, glycerine reducing agent, copper formate is copper source, the basic sodium sulfonate of cetyl trimethylammonium bromide, dodecane, PVP, lauryl sodium sulfate are dispersant, and the nano cuprous oxide micromeritics of cubic structure has successfully been made using solvent-thermal method.Prepare needed for raw material is cheap and easy to get, technique is simple and convenient to operate, it is reproducible, without waste liquid exclude, met Product Green preparation requirement, these features to carry out industrial scale production be all highly profitable.Nano cuprous oxide material has a wide range of applications in terms of photocatalyst material, industrial chemicals, photoelectron transition material, the negative material of lithium ion battery and ballast material, anti-biotic material, with wide market prospects and potential value.
Description
Technical field
The present invention relates to a kind of method for preparing nano cuprous oxide.
Background technology
Cuprous oxide is a kind of widely used materials of electronic components and industrial chemicals, can be used as the sterilization of agricultural production
Agent, the colouring agent of glass industry production, the catalyst of organic chemical industry's industry, the catalyst that Industry Waste Organic substance in water is decomposed.By
In cuprous oxide energy gap 2.2eV, it is a kind of important semi-conducting material, can be used as photoelectron transition material, lithium-ion electric
The negative material and ballast material in pond etc..Therefore the Cu of specified particle diameter and pattern is prepared2O particles have broader market
Prospect and potential value.
The technology of preparing of cuprous oxide common are electrolysis, solid phase method and liquid phase method, and (sodium sulfite reduces CuSO4Method,
Hydrazine hydrate reduction method, hydro-thermal method, microwave radiation method, high-energy ray irradiation method, method of glucose reduction) etc..So far, do not send out
Existing glycerine and the positive dibutyl ester of adipic acid make hybrid reaction system liquid, to reduce the side that copper formate prepares nano cuprous oxide powder body
Method and patent document.The preparation method compares technique with the preparation method reported simply, and preparation process no waste discharge is required
Raw material sources are extensive and cheap, and product purity is high, and no adhesion, particle diameter is small, with good economic benefit and industrialization
Prospect.
The content of the invention
It is an object of the invention to provide one kind nanometer is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid
Glycerine is both reaction in the positive dibutyl ester mixed liquor reaction system of the method for cuprous oxide crystal grain, particularly glycerine and adipic acid
The important component of system liquid is the simple chemical preparation process of technique of reducing agent again.
The present invention technical solution be：
A kind of method that nano cuprous oxide is prepared in positive dibutyl ester mixture system of glycerine and adipic acid, its feature
It is：Comprise the following steps：
(1) in a certain amount of glycerine and the positive dibutyl ester mixture system solution of adipic acid, copper formate is added, while plus
Enter dispersant, stir and suspension is made.
(2) quickly stir under normal pressure and heat mixture, when temperature is increased to 350K, control its temperature slowly to raise, often
5 DEG C of temperature controls of rise are observed 30 minutes, finally reaction temperature is strict controlled between 390-410K；
(3) reaction temperature of step (2) is kept, reaction time 80min-100min is controlled, stops heating, is cooled to room
Temperature, obtains the suspension containing nano cuprous oxide；
(4) suspension for obtaining step (2) is filtered under diminished pressure after adding absolute ethyl alcohol or acetone dilution, then uses absolute ethyl alcohol
Or acetone cyclic washing；
(5) the nano cuprous oxide product vacuum after absolute ethyl alcohol or acetone washing is dried, obtains red nano oxidation
Cuprous product.
It is continuing with after waste liquid distillation processing after step (2) filtering.
The volume ratio of glycerine and the positive dibutyl ester of adipic acid is 2 in step (1):1, the mol ratio of glycerine and copper formate is
20:1。
Dispersant is cetyl trimethylammonium bromide, the basic sodium sulfonate of dodecane, PVP or 12
Sodium alkyl sulfate.
The consumption of dispersant is 1/4-the 1/6 of formic acid copper mass.
Step (5) vacuum drying temperature is 350K, time 480min.
The present invention is that nano cuprous oxide is made in single step reaction in glycerine and the positive dibutyl ester mixture system of adipic acid
Product, it is not necessary to separately add reducing agent, preparation technology is simple, and raw material is easy to get, and cost is relatively low, and obtained nano cuprous oxide is brilliant
Grain size is than more uniform, and particle diameter is about 10nm -20nm.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 1.
Fig. 2 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 2.
Fig. 3 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 3.
Fig. 4 is the XRD spectrum of nano cuprous oxide crystal grain prepared by embodiment 4.
Embodiment
Embodiment 1
1) 60mL glycerine and the positive dibutyl ester mixed liquor of adipic acid, (volume ratio is 2::1) it is put into three-necked flask, plus
Enter copper formate solid powder 2.50g, while cetyl trimethylammonium bromide (CTMAB) 0.500g is added, in the case where being stirred continuously
Mixture is set to turn into suspension.
2) the slow temperature for raising reactant mixture in quick stirring, when temperature is increased to 390K, control temperature is not
Raise again, continue stirring reaction 80min under temperature control 390K, naturally cool to room temperature, obtain outstanding containing nano cuprous oxide
Turbid liquid.
3) by step 2) obtained suspension is filtered under diminished pressure after adding 60mL absolute ethyl alcohols or acetone dilution, then use appropriate nothing
Water-ethanol or acetone cyclic washing 4 times.
4) cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K,
Obtain the last crystallite of nano cuprous oxide powder of red.
Fig. 1 is the XRD spectrum of nano cuprous oxide powder body prepared by the present embodiment 1, and is compared with international standard card, it is determined that
That prepared is pure Cu2O products, it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, is not have miscellaneous peak appearance in the cuprous oxide of cubic structure, figure, illustrates that product nano cuprous oxide purity is higher, according to figure
Spectrum is calculated and SEM observations, and the granularity of cuprous oxide is 16nm.
Embodiment 2
1) 60mL glycerine and the positive dibutyl ester mixed liquor of adipic acid, (volume ratio is 2::1) it is put into three-necked flask, adds
Copper formate solid powder 2.50g, while adding neopelex (SDBS) 0.500g, makes mixture in the case where being stirred continuously
As suspension.
2) the slow temperature for raising reactant mixture in quick stirring, when temperature is increased to 400K, control temperature is not
Raise again, continue stirring reaction 90min under temperature control 400K, naturally cool to room temperature, obtain outstanding containing nano cuprous oxide
Turbid liquid.
3) by step 2) obtained suspension is filtered under diminished pressure after adding 50mL absolute ethyl alcohols or acetone dilution, then use appropriate nothing
Water-ethanol or acetone cyclic washing 3 times.
4) cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K,
Obtain the last crystal of nano cuprous oxide powder of red.
Fig. 2 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, it is determined that
That prepared is pure Cu2O products, it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, is not have miscellaneous peak appearance in the cuprous oxide of cubic structure, figure, illustrates that product nano cuprous oxide purity is higher, according to figure
Spectrum is calculated and SEM observations, and the granularity of cuprous oxide is 18nm.
Embodiment 3
1) 60mL glycerine and the positive dibutyl ester mixed liquor of adipic acid, (volume ratio is 2::1) it is put into three-necked flask, adds
Copper formate solid powder 2.50g, at the same add polyvinylpyrrolidone (PVP) 0.400g, make in the case where being stirred continuously mixture into
For suspension.
2) the slow temperature for raising reactant mixture in quick stirring, when temperature is increased to 405K, control temperature is not
Raise again, continue stirring reaction 95min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3) by step 2) obtained suspension is filtered under diminished pressure after adding 60mL absolute ethyl alcohols or acetone dilution, then use appropriate nothing
Water-ethanol or acetone cyclic washing 4 times.
4) cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K,
Obtain the last crystal of nano cuprous oxide powder of red.
Fig. 3 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, it is determined that
That prepared is pure Cu2O products, it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, is not have miscellaneous peak appearance in the cuprous oxide of cubic structure, figure, illustrates that product nano cuprous oxide purity is higher, according to figure
Spectrum is calculated and SEM observations, and the granularity of cuprous oxide is 12nm.
Embodiment 4
1) 60mL glycerine and the positive dibutyl ester mixed liquor of adipic acid, (volume ratio is 2::1) it is put into three-necked flask, adds
Copper formate solid powder 2.50g, at the same add lauryl sodium sulfate (SDS) 0.600g, make in the case where being stirred continuously mixture into
For suspension.
2) the slow temperature for raising reactant mixture in quick stirring, when temperature is increased to 410K, control temperature is not
Raise again, continue stirring reaction 100min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3) by step 2) obtained suspension is filtered under diminished pressure after adding 50mL absolute ethyl alcohols or acetone dilution, then use appropriate nothing
Water-ethanol or acetone cyclic washing 3 times.
4) cuprous oxide powder cleaned up is put into vacuum drying chamber, 480min is dried in vacuo at a temperature of 350K,
Obtain the last crystal of nano cuprous oxide powder of red.
Fig. 4 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, it is determined that
That prepared is pure Cu2O products, it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, is not have miscellaneous peak appearance in the cuprous oxide of cubic structure, figure, illustrates that product nano cuprous oxide purity is higher, according to figure
Spectrum is calculated and SEM observations, and the granularity of cuprous oxide is 20nm.
Claims (4)
1. the method for nano cuprous oxide is prepared in a kind of glycerine and the positive dibutyl ester mixture system of adipic acid, it is characterized in that：
Comprise the following steps：
(1) in a certain amount of glycerine and the positive dibutyl ester mixture system solution of adipic acid, copper formate is added, is divided while adding
Powder, stirs and suspension is made；The volume ratio of glycerine and the positive dibutyl ester of adipic acid is 2:1, glycerine and copper formate rub
Your ratio is 20:1；
(2) quickly stir under normal pressure and heat mixture, when temperature is increased to 350K, controls its temperature slowly to raise, often raise 5
DEG C temperature control is observed 30 minutes, finally reaction temperature is strict controlled between 390-410K；
(3) reaction temperature of step (2) is kept, reaction time 80min-100min is controlled, stops heating, is cooled to room temperature, obtains
To the suspension containing nano cuprous oxide；
(4) step (2) is obtained suspension is filtered under diminished pressure after adding absolute ethyl alcohol or acetone dilution, then with absolute ethyl alcohol or acetone
Cyclic washing；
(5) the nano cuprous oxide product vacuum after absolute ethyl alcohol or acetone are washed is dried, and obtains the production of red nano cuprous oxide
Thing.
2. prepare nano cuprous oxide in glycerine according to claim 1 and the positive dibutyl ester mixture system of adipic acid
Method, it is characterized in that：Dispersant is cetyl trimethylammonium bromide, PVP or lauryl sodium sulfate.
3. prepare nano oxidized Asia in glycerine according to claim 1 or 2 and the positive dibutyl ester mixture system of adipic acid
The method of copper, it is characterized in that：The consumption of dispersant is 1/4-the 1/6 of formic acid copper mass.
4. prepare nano oxidized Asia in glycerine according to claim 1 or 2 and the positive dibutyl ester mixture system of adipic acid
The method of copper, it is characterized in that：Step (5) vacuum drying temperature is 350K, time 480min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710803494.0A CN107601549B (en) | 2016-09-05 | 2016-09-05 | The method of nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of simple process |
| CN201610800869.3A CN106241854B (en) | 2016-09-05 | 2016-09-05 | The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid |
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| CN201610800869.3A CN106241854B (en) | 2016-09-05 | 2016-09-05 | The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid |
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| CN201610800869.3A Expired - Fee Related CN106241854B (en) | 2016-09-05 | 2016-09-05 | The method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805011A (en) * | 2010-04-06 | 2010-08-18 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN102167388A (en) * | 2010-02-26 | 2011-08-31 | 上海亿金纳米科技有限公司 | Novel and large-scale preparation method of nano-cuprous oxide |
| CN102849778A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Octahedron cuprous oxide crystal and preparation method thereof |
| CN105883894A (en) * | 2014-12-05 | 2016-08-24 | 天津工业大学 | Preparation method of cuprous oxide mesoporous nanospheres |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4719848B2 (en) * | 2005-02-24 | 2011-07-06 | 独立行政法人科学技術振興機構 | Transition metal oxide nanotubes |
| CN101157851B (en) * | 2007-08-28 | 2010-05-19 | 华中师范大学 | Preparation method of quantum dot self-assembling nano structural material |
| KR101651932B1 (en) * | 2009-10-26 | 2016-08-30 | 한화케미칼 주식회사 | Method for manufacturing of conductive metal thin film using carboxylic acid |
| CN102557106B (en) * | 2012-01-12 | 2013-09-18 | 淮阴师范学院 | Preparation method of cuprous oxide hollow nanometer cubes |
| CN104030340B (en) * | 2013-04-03 | 2015-11-11 | 浙江理工大学 | A kind of preparation method of hollow ball cuprous nano material |
-
2016
- 2016-09-05 CN CN201710803494.0A patent/CN107601549B/en active Active
- 2016-09-05 CN CN201610800869.3A patent/CN106241854B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167388A (en) * | 2010-02-26 | 2011-08-31 | 上海亿金纳米科技有限公司 | Novel and large-scale preparation method of nano-cuprous oxide |
| CN101805011A (en) * | 2010-04-06 | 2010-08-18 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN102849778A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Octahedron cuprous oxide crystal and preparation method thereof |
| CN105883894A (en) * | 2014-12-05 | 2016-08-24 | 天津工业大学 | Preparation method of cuprous oxide mesoporous nanospheres |
Non-Patent Citations (3)
| Title |
|---|
| A simple approach for sonochemical synthesis of Cu2O nanoparticles with high catalytic properties;Manohar A. Bhosale等;《Advanced Powder Technology》;20161230;第27卷;第238-244页 * |
| 溶剂热法制备氧化亚铜纳米晶粒;王鸿显等;《电子元件与材料》;20120831;第31卷(第8期);第16-24页 * |
| 甘油体系中纳米铜粉的制备研究;王鸿显等;《粉末冶金工业》;20100430;第20卷(第2期);第12-16页 * |
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| CN106241854A (en) | 2016-12-21 |
| CN107601549B (en) | 2019-01-11 |
| CN107601549A (en) | 2018-01-19 |
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