CN107601549B - The method of nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of simple process - Google Patents
The method of nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of simple process Download PDFInfo
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- CN107601549B CN107601549B CN201710803494.0A CN201710803494A CN107601549B CN 107601549 B CN107601549 B CN 107601549B CN 201710803494 A CN201710803494 A CN 201710803494A CN 107601549 B CN107601549 B CN 107601549B
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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 the methods that nano cuprous oxide is prepared in a kind of glycerine of simple process 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, polyvinylpyrrolidone, lauryl sodium sulfate are dispersing agent, and the nano cuprous oxide micromeritics of cubic structure has successfully been made using solvent-thermal method.Raw material is cheap and easy to get needed for preparing, simple process, it is easy to operate, reproducible, excluded without waste liquid, met the requirement of Product Green preparation, these features are all very useful to industrial scale production is carried out.Nano cuprous oxide material photocatalyst material, industrial chemicals, photoelectron transition material, the negative electrode material of lithium ion battery and ballast material, in terms of have a wide range of applications, have a vast market foreground and potential value.
Description
The application is application number: 201610800869.3 applyings date: " glycerine and adipic acid are just for 2016-09-05, title
The method of nano cuprous oxide is prepared in dibutyl ester mixture system " divisional application.
Technical field
The present invention relates to a kind of methods for preparing nano cuprous oxide.
Background technique
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 colorant of glass industry production, the catalyst of organic chemical industry's industry, the catalyst that Industry Waste Organic substance in water decomposes.By
In cuprous oxide forbidden bandwidth 2.2eV, it is a kind of important semiconductor material, can be used as photoelectron transition material, lithium-ion electric
The negative electrode material in pond and ballast material etc..Therefore the Cu2O particle for preparing specified particle diameter and pattern has broader city
Field prospect and potential value.
The technology of preparing of cuprous oxide common are electrolysis method, solid phase method and liquid phase method (sodium sulfite restore CuSO4 method,
Hydrazine hydrate reduction method, hydro-thermal method, microwave radiation method, high-energy ray irradiation method, method of glucose reduction) etc..So far, it does not send out
Existing glycerine and the positive dibutyl ester of adipic acid make hybrid reaction system liquid, to restore the side that copper formate prepares nano cuprous oxide powder body
Method and patent document.The preparation method compares simple process with reported preparation method, and preparation process no waste discharge is required
Raw material sources are extensive and cheap, and product purity is high, and no adhesion, partial size is small, have good economic benefit and industrialization
Prospect.
Summary of the invention
The purpose of the present invention is to provide one kind to prepare nanometer 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, especially glycerine and adipic acid
The important component of system liquid is the chemical preparation process of the simple process of reducing agent again.
The technical solution of the invention is as follows:
A kind of method that nano cuprous oxide is prepared in glycerine and the positive dibutyl ester mixture system of adipic acid, feature
It is: includes 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, adds simultaneously
Enter dispersing agent, stir and suspension is made.
(2) mixture is quickly stirred and heated under normal pressure, when temperature is increased to 350K, is controlled its temperature and is slowly increased, often
It increases 5 DEG C of temperature controls to observe 30 minutes, is finally strict controlled in reaction temperature between 390-410K；
(3) reaction temperature for keeping step (2), controls reaction time 80min-100min, stops heating, is cooled to room
Temperature obtains the suspension containing nano cuprous oxide；
(4) it is filtered under diminished pressure after dehydrated alcohol or acetone dilution being added in the suspension that step (2) obtains, then uses dehydrated alcohol
Or acetone washs repeatedly；
(5) the nano cuprous oxide product vacuum after dehydrated alcohol or acetone washing is dry, obtain red nano oxidation
Cuprous product.
It is continued to use after the filtered waste liquid distillation processing of step (2).
The volume ratio of glycerine and the positive dibutyl ester of adipic acid is 2:1 in step (1), and the molar ratio of glycerine and copper formate is
20:1。
Dispersing agent is cetyl trimethylammonium bromide, the basic sodium sulfonate of dodecane, polyvinylpyrrolidone or 12
Sodium alkyl sulfate.
The dosage of dispersing agent 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 does not need that reducing agent separately is added, preparation process is simple, and raw material is easy to get, and cost is relatively low, and nano cuprous oxide obtained is brilliant
Grain size is relatively uniform, and partial size is about 10nm -20nm.
Detailed description of the invention
Present invention will be further explained below with reference to the attached 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.
Specific embodiment
Embodiment 1
1) 60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2::1) of adipic acid are put into three-necked flask, are added
Enter copper formate solid powder 2.50g, while cetyl trimethylammonium bromide (CTMAB) 0.500g is added, under constant stirring
Mixture is set to become suspension.
2) temperature that reaction mixture is slowly increased in quick stirring, when temperature is increased to 390K, control temperature is not
It increases again, continues to be stirred to react 80min at temperature control 390K, naturally cool to room temperature, obtain outstanding containing nano cuprous oxide
Turbid.
3) it is filtered under diminished pressure after 60mL dehydrated alcohol or acetone dilution being added in suspension that step 2 obtains, then with appropriate nothing
Water-ethanol or acetone wash 4 times repeatedly
4) cuprous oxide powder cleaned up is put into vacuum oven, 480min is dried in vacuo at a temperature of 350K,
Obtain red nano cuprous oxide powder end crystallite.
Fig. 1 is the XRD spectrum of nano cuprous oxide powder body prepared by the present embodiment 1, and compared with international standard card, is determined
That prepared is pure Cu2O product, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311)
Crystal face is the cuprous oxide of cubic structure, do not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to
Map calculates and SEM observation, and the granularity of cuprous oxide is 16nm.
Embodiment 2
1) 60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2::1) of adipic acid are put into three-necked flask, are added
Copper formate solid powder 2.50g, while neopelex (SDBS) 0.500g is added, make mixture under constant stirring
As suspension.
2) temperature that reaction mixture is slowly increased in quick stirring, when temperature is increased to 400K, control temperature is not
It increases again, continues to be stirred to react 90min at temperature control 400K, naturally cool to room temperature, obtain outstanding containing nano cuprous oxide
Turbid.
3) it is filtered under diminished pressure after 50mL dehydrated alcohol or acetone dilution being added in suspension that step 2 obtains, then with appropriate nothing
Water-ethanol or acetone wash 3 times repeatedly
4) cuprous oxide powder cleaned up is put into vacuum oven, 480min is dried in vacuo at a temperature of 350K,
Obtain red nano cuprous oxide powder end crystal
Fig. 2 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, is determined
That prepared is pure Cu2O product, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311)
Crystal face is the cuprous oxide of cubic structure, do not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to
Map calculates and SEM observation, and the granularity of cuprous oxide is 18nm.
Embodiment 3
1) 60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2::1) of adipic acid are put into three-necked flask, are added
Copper formate solid powder 2.50g, while polyvinylpyrrolidone (PVP) 0.400g is added, make under constant stirring mixture at
For suspension.
2) temperature that reaction mixture is slowly increased in quick stirring, when temperature is increased to 405K, control temperature is not
It increases again, continues to be stirred to react 95min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3) it is filtered under diminished pressure after 60mL dehydrated alcohol or acetone dilution being added in suspension that step 2 obtains, then with appropriate nothing
Water-ethanol or acetone wash 4 times repeatedly
4) cuprous oxide powder cleaned up is put into vacuum oven, 480min is dried in vacuo at a temperature of 350K,
Obtain red nano cuprous oxide powder end crystal
Fig. 3 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, is determined
That prepared is pure Cu2O product, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311)
Crystal face is the cuprous oxide of cubic structure, do not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to
Map calculates and SEM observation, and the granularity of cuprous oxide is 12nm.
Embodiment 4
1) 60mL glycerine and the positive dibutyl ester mixed liquor (volume ratio 2::1) of adipic acid are put into three-necked flask, are added
Copper formate solid powder 2.50g, while lauryl sodium sulfate (SDS) 0.600g is added, make under constant stirring mixture at
For suspension.
2) temperature that reaction mixture is slowly increased in quick stirring, when temperature is increased to 410K, control temperature is not
It increases again, continues to be stirred to react 100min, naturally cool to room temperature, obtain the suspension containing nano cuprous oxide.
3) it is filtered under diminished pressure after 50mL dehydrated alcohol or acetone dilution being added in suspension that step 2 obtains, then with appropriate nothing
Water-ethanol or acetone wash 3 times repeatedly
4) cuprous oxide powder cleaned up is put into vacuum oven, 480min is dried in vacuo at a temperature of 350K,
Obtain red nano cuprous oxide powder end crystal
Fig. 4 is the XRD spectrum of nano cuprous oxide powder body manufactured in the present embodiment, and compared with international standard card, is determined
That prepared is pure Cu2O product, diffraction maximum from left to right correspond respectively to (110), (111), (200), (220) and (311)
Crystal face is the cuprous oxide of cubic structure, do not have miscellaneous peak appearance in figure, illustrate that product nano cuprous oxide purity is higher, according to
Map calculates and SEM observation, and the granularity of cuprous oxide is 20nm.
Claims (1)
1. the method that nano cuprous oxide is prepared in the positive dibutyl ester mixture system of the glycerine and adipic acid of a kind of simple process,
It is characterized in that: including the following steps:
1) 60mL glycerine and the positive dibutyl ester mixed liquor of adipic acid are put into three-necked flask, glycerine and positive two fourth of adipic acid
The volume ratio of ester is 2:1, copper formate solid powder 2.50g is added, while cetyl trimethylammonium bromide 0.500g is added,
Being stirred continuously down makes mixture become suspension；
2) temperature that reaction mixture is slowly increased in quick stirring, when temperature is increased to 390K, control temperature is no longer risen
Height continues to be stirred to react 80min at temperature control 390K, naturally cools to room temperature, obtains the suspension containing nano cuprous oxide；
3) be filtered under diminished pressure after 60mL dehydrated alcohol or acetone dilution being added in suspension that step 2 obtains, then with dehydrated alcohol or
Acetone washs 4 times repeatedly；
4) cuprous oxide powder cleaned up is put into vacuum oven, 480min is dried in vacuo at a temperature of 350K, obtained
Red nano cuprous oxide powder end crystallite；The granularity of cuprous oxide is 16nm.
Priority Applications (1)
| 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 |
Applications Claiming Priority (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 |
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| CN201610800869.3A Division 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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| CN107601549B true CN107601549B (en) | 2019-01-11 |
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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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| 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 |
| 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 |
| CN101805011B (en) * | 2010-04-06 | 2011-11-09 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN102557106B (en) * | 2012-01-12 | 2013-09-18 | 淮阴师范学院 | Preparation method of cuprous oxide hollow nanometer cubes |
| 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 |
| CN103172104B (en) * | 2013-04-03 | 2015-05-13 | 浙江理工大学 | Preparation method of nano cuprous oxide |
| CN105883894A (en) * | 2014-12-05 | 2016-08-24 | 天津工业大学 | Preparation method of cuprous oxide mesoporous nanospheres |
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| CN106241854A (en) | 2016-12-21 |
| CN106241854B (en) | 2017-09-29 |
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