CN106241854A - The method preparing nano cuprous oxide in glycerol and adipic acid positive dibutyl ester mixture system - Google Patents
The method preparing nano cuprous oxide in glycerol and adipic acid positive dibutyl ester mixture system Download PDFInfo
- Publication number
- CN106241854A CN106241854A CN201610800869.3A CN201610800869A CN106241854A CN 106241854 A CN106241854 A CN 106241854A CN 201610800869 A CN201610800869 A CN 201610800869A CN 106241854 A CN106241854 A CN 106241854A
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- China
- Prior art keywords
- glycerol
- adipic acid
- dibutyl ester
- cuprous oxide
- ester mixture
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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
Abstract
The invention discloses a kind of method preparing nano cuprous oxide in glycerol and adipic acid positive dibutyl ester mixture system, the method is with glycerol and adipic acid positive dibutyl ester mixed liquor for reaction system liquid, glycerol reducing agent, Tubercuprose. is copper source, the basic sodium sulfonate of cetyl trimethylammonium bromide, dodecane, polyvinyl pyrrolidone, sodium lauryl sulphate are dispersant, use solvent-thermal method successfully to prepare the nano cuprous oxide microcrystalline grain of cubic structure.Prepare that needed raw material is cheap and easy to get, technique is simple and convenient to operate, reproducible, get rid of without waste liquid, met requirement prepared by Product Green, these features produce and are all highly profitable carrying out industrial scale.Nano cuprous oxide material has a wide range of applications at photocatalyst material, industrial chemicals, photoelectron transition material, the negative material of lithium ion battery and the aspect such as ballast material, anti-biotic material, has wide market prospect and potential value.
Description
Technical field
The present invention relates to a kind of method preparing nano cuprous oxide.
Background technology
Red copper 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 coloring agent that glass industry produces, the catalyst of organic chemical industry's industry, the catalyst that Industry Waste Organic substance in water decomposes.By
In Red copper 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 in pond and ballast material etc..Therefore the Cu2O particle preparing specified particle diameter and pattern has broader city
Field prospect and potential value.
The technology of preparing of Red copper oxide common are electrolysis, solid phase method and liquid phase method (sodium sulfite reduction CuSO4 method,
Hydrazine hydrate reduction method, hydro-thermal method, microwave radiation method, high-energy ray irradiation method, method of glucose reduction) etc..Up to now, do not send out
Existing glycerol and the positive dibutyl ester of adipic acid are made hybrid reaction system liquid, are prepared the side of nano cuprous oxide powder body reducing Tubercuprose.
Method and patent documentation.It is simple that this preparation method compares technique with the preparation method reported, preparation process no waste discharge is required
Raw material sources are extensive and cheap, and product purity is high, and without adhesion, particle diameter is little, has good economic benefit and industrialization
Prospect.
Summary of the invention
It is an object of the invention to provide a kind of preparation nanometer in glycerol and adipic acid positive dibutyl ester mixture system
In the method for Red copper oxide crystal grain, particularly glycerol and adipic acid positive dibutyl ester mixed liquor reaction system, glycerol is reaction
The important component part of system liquid is again the simple chemical preparation process of technique of reducing agent.
The technical solution of the present invention is:
A kind of method preparing nano cuprous oxide in glycerol and adipic acid positive dibutyl ester mixture system, is characterized in that: bag
Include the following step:
(1) in a certain amount of glycerol and adipic acid positive dibutyl ester mixture system solution, add Tubercuprose., be simultaneously introduced point
Powder, stirs and makes suspension.
(2) quickly stir and heating blends under normal pressure, when temperature is increased to 350K, controls its temperature and slowly raise, often
Raise 5 DEG C of temperature controls to observe 30 minutes, finally make reaction temperature be strict controlled between 390-410K；
(3) keep the reaction temperature of step (2), control response time 80min-100min, stop heating, be cooled to room temperature,
To the suspension containing nano cuprous oxide；
(3) suspension that step (2) obtained adds filtration under diminished pressure after dehydrated alcohol or acetone dilution, then with dehydrated alcohol or third
Ketone cyclic washing；
(4) the nano cuprous oxide product vacuum after dehydrated alcohol or washing with acetone is dried, obtains red nano Red copper oxide
Product.
Waste liquid distillation after step (2) filtration is continuing with after processing.
In step (1), the mol ratio that volume ratio is 2:1, glycerol and Tubercuprose. of glycerol and the positive dibutyl ester of adipic acid is
20:1。
Dispersant is cetyl trimethylammonium bromide, the basic sodium sulfonate of dodecane, polyvinyl pyrrolidone or 12
Alkyl sodium sulfate.
The consumption of dispersant is the 1/4 1/6 of Tubercuprose. quality.
Step (4) vacuum drying temperature is 350K, time 480min.
The present invention is that single step reaction prepares nano cuprous oxide in glycerol and adipic acid positive dibutyl ester mixture system
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 the nano cuprous oxide prepared is brilliant
Grain size ratio is more uniform, and particle diameter is about 10nm 20nm.
Accompanying drawing explanation
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Fig. 1 is the XRD figure spectrum of the nano cuprous oxide crystal grain of embodiment 1 preparation.
Fig. 2 is the XRD figure spectrum of the nano cuprous oxide crystal grain of embodiment 2 preparation.
Fig. 3 is the XRD figure spectrum of the nano cuprous oxide crystal grain of embodiment 3 preparation.
Fig. 4 is the XRD figure spectrum of the nano cuprous oxide crystal grain of embodiment 4 preparation.
Detailed description of the invention
Embodiment 1
1) positive to 60mL glycerol and adipic acid dibutyl ester mixed liquor (volume ratio is 2::1) is put in there-necked flask, add first
Acid copper pressed powder 2.50g, is simultaneously introduced cetyl trimethylammonium bromide (CTMAB) 0.500g, makes to mix under being stirred continuously
Compound becomes suspension.
2) in quickly stirring, slowly raise the temperature of reactant mixture, when temperature is increased to 390K, control temperature not
Raise again, under temperature control 390K, continue stirring reaction 80min, naturally cool to room temperature, obtain hanging containing nano cuprous oxide
Turbid liquid.
3) by step 2) suspension that obtains adds filtration under diminished pressure after 60mL dehydrated alcohol or acetone dilution, then uses appropriate nothing
Water-ethanol or acetone cyclic washing 4 times
4) cuprous oxide powder cleaned up is put in vacuum drying oven, be vacuum dried 480min at a temperature of 350K, obtain
Red nano cuprous oxide powder end crystallite.
Fig. 1 is the XRD figure spectrum of the nano cuprous oxide powder body of the present embodiment 1 preparation, and compares with international standard card, determines
Prepared is pure Cu2O product, and diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Crystal face, for the Red copper oxide of cubic structure, does not has miscellaneous peak to occur in figure, illustrate that product nano Red copper oxide purity is higher, according to
Collection of illustrative plates calculates and SEM observes, and the granularity of Red copper oxide is 16nm.
Embodiment 2
1) positive to 60mL glycerol and adipic acid dibutyl ester mixed liquor (volume ratio is 2::1) is put in there-necked flask, add formic acid
Copper pressed powder 2.50g, is simultaneously introduced dodecylbenzene sodium sulfonate (SDBS) 0.500g, makes mixture become under being stirred continuously
Suspension.
2) in quickly stirring, slowly raise the temperature of reactant mixture, when temperature is increased to 400K, control temperature not
Raise again, under temperature control 400K, continue stirring reaction 90min, naturally cool to room temperature, obtain hanging containing nano cuprous oxide
Turbid liquid.
3) by step 2) suspension that obtains adds filtration under diminished pressure after 50mL dehydrated alcohol or acetone dilution, then uses appropriate nothing
Water-ethanol or acetone cyclic washing 3 times
4) cuprous oxide powder cleaned up is put in vacuum drying oven, be vacuum dried 480min at a temperature of 350K, obtain
Red nano cuprous oxide powder end crystal
Fig. 2 is the XRD figure spectrum of nano cuprous oxide powder body prepared by the present embodiment, and compares with international standard card, determines made
Standby is pure Cu2O product, and it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, for the Red copper oxide of cubic structure, does not has miscellaneous peak to occur in figure, illustrate that product nano Red copper oxide purity is higher, according to figure
Spectrum calculates and SEM observes, and the granularity of Red copper oxide is 18nm.
Embodiment 3
1) positive to 60mL glycerol and adipic acid dibutyl ester mixed liquor (volume ratio is 2::1) is put in there-necked flask, add formic acid
Copper pressed powder 2.50g, is simultaneously introduced polyvinylpyrrolidone (PVP) 0.400g, makes mixture become outstanding under being stirred continuously
Turbid liquid.
2) in quickly stirring, slowly raise the temperature of reactant mixture, when temperature is increased to 405K, control temperature not
Raise again, continue stirring reaction 95min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3) by step 2) suspension that obtains adds filtration under diminished pressure after 60mL dehydrated alcohol or acetone dilution, then uses appropriate nothing
Water-ethanol or acetone cyclic washing 4 times
4) cuprous oxide powder cleaned up is put in vacuum drying oven, be vacuum dried 480min at a temperature of 350K, obtain
Red nano cuprous oxide powder end crystal
Fig. 3 is the XRD figure spectrum of nano cuprous oxide powder body prepared by the present embodiment, and compares with international standard card, determines made
Standby is pure Cu2O product, and it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, for the Red copper oxide of cubic structure, does not has miscellaneous peak to occur in figure, illustrate that product nano Red copper oxide purity is higher, according to figure
Spectrum calculates and SEM observes, and the granularity of Red copper oxide is 12nm.
Embodiment 4
1) positive to 60mL glycerol and adipic acid dibutyl ester mixed liquor (volume ratio is 2::1) is put in there-necked flask, add formic acid
Copper pressed powder 2.50g, is simultaneously introduced sodium lauryl sulphate (SDS) 0.600g, makes mixture become outstanding under being stirred continuously
Turbid liquid.
2) in quickly stirring, slowly raise the temperature of reactant mixture, when temperature is increased to 410K, control temperature not
Raise again, continue stirring reaction 100min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3) by step 2) suspension that obtains adds filtration under diminished pressure after 50mL dehydrated alcohol or acetone dilution, then uses appropriate nothing
Water-ethanol or acetone cyclic washing 3 times
4) cuprous oxide powder cleaned up is put in vacuum drying oven, be vacuum dried 480min at a temperature of 350K, obtain
Red nano cuprous oxide powder end crystal
Fig. 4 is the XRD figure spectrum of nano cuprous oxide powder body prepared by the present embodiment, and compares with international standard card, determines made
Standby is pure Cu2O product, and it is brilliant that diffraction maximum from left to right corresponds respectively to (110), (111), (200), (220) and (311)
Face, for the Red copper oxide of cubic structure, does not has miscellaneous peak to occur in figure, illustrate that product nano Red copper oxide purity is higher, according to figure
Spectrum calculates and SEM observes, and the granularity of Red copper oxide is 20nm.
Claims (6)
1. the method preparing nano cuprous oxide in glycerol and adipic acid positive dibutyl ester mixture system, is characterized in that:
Comprise the following steps:
(1) in a certain amount of glycerol and adipic acid positive dibutyl ester mixture system solution, add Tubercuprose., be simultaneously introduced point
Powder, stirs and makes suspension；
(2) quickly stir and heating blends under normal pressure, when temperature is increased to 350K, controls its temperature and slowly raise, often raise 5
DEG C temperature control is observed 30 minutes, finally makes reaction temperature be strict controlled between 390-410K；
(3) keep the reaction temperature of step (2), control response time 80min-100min, stop heating, be cooled to room temperature,
To the suspension containing nano cuprous oxide；
(3) suspension that step (2) obtained adds filtration under diminished pressure after dehydrated alcohol or acetone dilution, then with dehydrated alcohol or third
Ketone cyclic washing；
(4) the nano cuprous oxide product vacuum after dehydrated alcohol or washing with acetone is dried, obtains red nano Red copper oxide
Product.
Nano cuprous oxide prepared by glycerol the most according to claim 1 and adipic acid positive dibutyl ester mixture system
Method, is characterized in that: the waste liquid distillation after step (2) filtration is continuing with after processing.
Nano oxidized Asia prepared by glycerol the most according to claim 1 and 2 and adipic acid positive dibutyl ester mixture system
The method of copper, is characterized in that: in step (1), the volume ratio of glycerol and the positive dibutyl ester of adipic acid is 2:1, glycerol and Tubercuprose.
Mol ratio be 20:1.
Nano oxidized Asia prepared by glycerol the most according to claim 1 and 2 and adipic acid positive dibutyl ester mixture system
The method of copper, is characterized in that: dispersant is cetyl trimethylammonium bromide, the basic sodium sulfonate of dodecane, polyvinylpyrrolidine
Alkanone or sodium lauryl sulphate.
Nano oxidized Asia prepared by glycerol the most according to claim 1 and 2 and adipic acid positive dibutyl ester mixture system
The method of copper, is characterized in that: the consumption of dispersant is the 1/4 1/6 of Tubercuprose. quality.
Nano oxidized Asia prepared by glycerol the most according to claim 1 and 2 and adipic acid positive dibutyl ester mixture system
The method of copper, is characterized in that: step (4) vacuum drying temperature is 350K, time 480min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN201710803494.0A Division 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 |
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| CN106241854A true CN106241854A (en) | 2016-12-21 |
| CN106241854B CN106241854B (en) | 2017-09-29 |
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| CN201710803494.0A Active 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 |
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Citations (5)
| 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 |
| WO2011052966A2 (en) * | 2009-10-26 | 2011-05-05 | Hanwha Chemical Corporation | Method for manufacturing conductive metal thin film using carboxylic acid |
| 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 (4)
| 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 |
| CN102557106B (en) * | 2012-01-12 | 2013-09-18 | 淮阴师范学院 | Preparation method of cuprous oxide hollow nanometer cubes |
| CN104030339B (en) * | 2013-04-03 | 2015-08-05 | 浙江理工大学 | A kind of preparation method of cubes cuprous nano material |
-
2016
- 2016-09-05 CN CN201610800869.3A patent/CN106241854B/en not_active Expired - Fee Related
- 2016-09-05 CN CN201710803494.0A patent/CN107601549B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011052966A2 (en) * | 2009-10-26 | 2011-05-05 | Hanwha Chemical Corporation | Method for manufacturing conductive metal thin film using carboxylic acid |
| 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 |
|---|
| MANOHAR A. BHOSALE等: "A simple approach for sonochemical synthesis of Cu2O nanoparticles with high catalytic properties", 《ADVANCED POWDER TECHNOLOGY》 * |
| 王鸿显等: "溶剂热法制备氧化亚铜纳米晶粒", 《电子元件与材料》 * |
| 王鸿显等: "甘油体系中纳米铜粉的制备研究", 《粉末冶金工业》 * |
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| Publication number | Publication date |
|---|---|
| CN107601549A (en) | 2018-01-19 |
| CN107601549B (en) | 2019-01-11 |
| CN106241854B (en) | 2017-09-29 |
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Granted publication date: 20170929 Termination date: 20180905 |