CN103043702B - Method for grinding and preparing nano-cuprous oxide - Google Patents
Method for grinding and preparing nano-cuprous oxide Download PDFInfo
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- CN103043702B CN103043702B CN201210536157.7A CN201210536157A CN103043702B CN 103043702 B CN103043702 B CN 103043702B CN 201210536157 A CN201210536157 A CN 201210536157A CN 103043702 B CN103043702 B CN 103043702B
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- cuprous oxide
- mantoquita
- acid
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Abstract
The invention relates to a grinding and preparing nano-cuprous oxide, comprising the following steps: (1) uniformly stirring a copper salt, a reducing agent and dimethyl sulfoxide in a temperature range of 10-70 DEG C, and grinding for 0.2-0.6h; and (2) repeatedly washing the ground mixture with deionized water, ethanol and acetone for several times, to obtain stabilized nano-cuprous oxide. The beneficial effects of the method are that: (1) purer nan0-cuprous oxide particles can be prepared; (2) the copper salt amount in each reaction process is not limited without solubility, (3) the method has the advantages of simple technology, simple operation, mild reaction, short reaction time, high efficiency and large scale production; the product has good performances, the particle size particle size of the prepared nano-cuprous oxide is less than 20nm, and the nano-cuprous oxide has good secondary dispersibility in various oils; and the method is low in preparation cost and energy consumption, generates no harmful waste, and accords with the production requirement of green production, environmental protection and energy saving.
Description
Technical field
The present invention relates to Inorganic Chemicals production field, especially a kind of grinding production method of nano cuprous oxide.
Background technology
Red copper oxide (Cu
2o) be p-type semiconductor material, of many uses.Except can be used as catalyzer and use in organic synthesis, also can be used as boats and ships protective system and sterilant, be more applied to pottery and electron device aspect.Due to quantum size effect, grade cuprous oxide has special optics, electricity and PhotoelectrochemicalProperties Properties, potential application is had in solar cell, sensor, superconductor, hydrogen manufacturing and electrochromism etc., nano cuprous oxide also can process organic pollutant in the environment, and the method that therefore nano cuprous oxide is prepared in research just becomes one of current study hotspot.
Disclose a kind of preparation method of nano cuprous oxide in Chinese patent CN 1693204 A, step is as follows: 1) add mantoquita in deionized water, polyvinylpyrrolidone and sodium lauryl sulphate; 2) add hydrazine hydrate aqueous solution, regulate pH value, add paraffin or lubricating oil simultaneously, stir ageing; 3) centrifugation; 4) clean.Its shortcoming is: in system, contained formula is more, needs to add organic protective agent, and thus the purity of final nano cuprous oxide particle is not high.
Disclose a kind of preparation method of nano cuprous oxide in Chinese patent CN 102167388 A, step is as follows: 1) be dissolved in solvent by mantoquita and organic protective agent, is warming up to 20 – 70 DEG C gradually; 2) add in reaction system by reductive agent after temperature-stable, Keep agitation reaction afterwards, after 20-30 minute, cools gradually; 3) centrifugation; 4) clean.Its shortcoming is: the amount of the mantoquita added limits by its solubleness in used solvent.
Summary of the invention
The present invention will solve the shortcoming of above-mentioned prior art, provide that a kind of technique is simple, energy-conserving and environment-protective, nano cuprous oxide that gained nano cuprous oxide particle purity is higher grinding production method.
The present invention solves the technical scheme that its technical problem adopts: a kind of grinding production method of nano cuprous oxide comprises the following steps: 1) mantoquita, reductive agent and dimethyl sulfoxide (DMSO) are stirred at the temperature of 10-70 DEG C, and the 0.2-6h that mills;
2) mixture after milling is used deionized water, ethanol and acetone repetitive scrubbing several times successively, stable nano cuprous oxide can be obtained.
As preferably, reductive agent is one or more in formaldehyde, V-Brite B, hydroborate and hydrazine hydrate.
As preferably, the mol ratio of reductive agent and mantoquita is 1-10:1, and the ratio of dimethyl sulfoxide (DMSO) and mantoquita is 1-100ml:10g.
As preferably, mantoquita is copper sulfate, the title complex of cupric nitrate, cupric chloride, neutralized verdigris, copper and comprise one or several of organic copper of long-chain, and wherein the carbon chain lengths of organic copper is 8-16.
As preferably, the technique of milling of step 1) is mechanical disruption or mills by hand.
The grinding production method of another kind of nano cuprous oxide comprises the following steps: 1) mantoquita, reductive agent, acid and dimethyl sulfoxide (DMSO) are stirred at the temperature of 10-70 DEG C, and the 0.2-6h that mills;
2) mixture after milling is used deionized water, ethanol and acetone repetitive scrubbing several times successively, stable nano cuprous oxide can be obtained.
As preferably, reductive agent is one or several in hypophosphite, xitix, glucose, S-WAT, formic acid, trolamine, ethylene glycol, sorbyl alcohol, Xylitol and oxammonium hydrochloride.
As preferably, the mol ratio of reductive agent and mantoquita is 1-10:1, and the ratio of acid and mantoquita is 1-20ml:100g, and the ratio of dimethyl sulfoxide (DMSO) and mantoquita is 1-100ml:10g.
As preferably, mantoquita is copper sulfate, the title complex of cupric nitrate, cupric chloride, neutralized verdigris, copper and comprise one or several of organic copper of long-chain, and wherein the carbon chain lengths of organic copper is 8-16.
As preferably, acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, formic acid and oxalic acid; The technique of milling of step 1) can be mechanical disruption, also can be manual milling.
The effect that the present invention is useful is: one, only adopt mantoquita, reductive agent in preparation process, (reductive agent is one or more in formaldehyde, V-Brite B, hydroborate and hydrazine hydrate in acid, then without the need to acid adding) and dimethyl sulfoxide (DMSO) four kinds formula, wherein acid plays katalysis, temperature of reaction can be reduced, the generation of copper hydroxide can also be suppressed in addition, with the nano cuprous oxide particle that obtained purity is higher; Two, dimethyl sulfoxide (DMSO) (DMSO) is as protective material, and consumption is little, only needs moistening for the particle of reductive agent and mantoquita, and does not require that mantoquita is dissolved in DMSO, and the amount of mantoquita that therefore every secondary response can hold is not subject to the restriction of solubleness; Three, present invention process is simple, easy and simple to handle, reaction temperature and, the reaction times is short, and efficiency is high, is applicable to scale operation; Product performance are good, and the particle diameter of the nano cuprous oxide prepared is less than 20nm, in all kinds of finish, have good twice dispersing; The modern production requirement that preparation cost is low, and energy consumption is low, does not have bazardous waste to produce, meets " green production, environmental protection and energy saving ".
Embodiment
Embodiment 1: 20g cupric sulfate pentahydrate, 80g inferior sodium phosphate, 20ml dimethyl sulfoxide (DMSO) and 2ml sulfuric acid are joined in mortar, stir at the temperature of 10 DEG C, and hand lapping 50 minutes, then deionized water is used, ethanol and acetone repetitive scrubbing more than three times, namely purity is obtained high, the nano cuprous oxide that good stability, oil soluble are good.
Embodiment 2: 15g cupric chloride, 8g sodium borohydride and 20ml dimethyl sulfoxide (DMSO) are joined in mortar, stir at the temperature of 70 DEG C, and adopt mechanical mill 20min, then deionized water is used, ethanol and acetone repetitive scrubbing more than three times, namely purity is obtained high, the nano cuprous oxide that good stability, oil soluble are good.
Embodiment 3: 30g cupric sulfate pentahydrate, 100g xitix, 30ml dimethyl sulfoxide (DMSO) and 2ml formic acid are joined in mortar, stir at the temperature of 40 DEG C, and adopt mechanical mill 50min, then deionized water is used, ethanol and acetone repetitive scrubbing more than three times, namely purity is obtained high, the nano cuprous oxide that good stability, oil soluble are good.
Embodiment 4: 12g cupric nitrate, 25g S-WAT (seven water), 10ml dimethyl sulfoxide (DMSO) and 2ml nitric acid are joined in mortar, stir at the temperature of 50 DEG C, and adopt mechanical mill 30min, then deionized water is used, ethanol and acetone repetitive scrubbing more than three times, namely purity is obtained high, the nano cuprous oxide that good stability, oil soluble are good.
Embodiment 5: 16g cupric sulfate pentahydrate, 15g formic acid, 20ml dimethyl sulfoxide (DMSO) and 2ml formic acid are joined in mortar, stir at the temperature of 30 DEG C, and adopt mechanical mill 40min, then deionized water is used, ethanol and acetone repetitive scrubbing more than three times, namely purity is obtained high, the nano cuprous oxide that good stability, oil soluble are good.
Embodiment 6: 12g neutralized verdigris (water), 10g trolamine, 20ml dimethyl sulfoxide (DMSO) and 2ml acetic acid are joined in mortar, stir at the temperature of 35 DEG C, and grind 6 hours, then deionized water is used, ethanol and acetone repetitive scrubbing more than three times, namely purity is obtained high, the nano cuprous oxide that good stability, oil soluble are good.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.
Claims (8)
1. a grinding production method for nano cuprous oxide, is characterized in that:
1) mantoquita, reductive agent and dimethyl sulfoxide (DMSO) are stirred at the temperature of 10-70 DEG C, and the 0.2-6h that mills;
2) mixture after milling is used deionized water, ethanol and acetone repetitive scrubbing several times successively, stable nano cuprous oxide can be obtained;
The mol ratio of described reductive agent and mantoquita is 1-10:1, and the ratio of dimethyl sulfoxide (DMSO) and mantoquita is 1-100ml:10g.
2. the grinding production method of nano cuprous oxide according to claim 1, is characterized in that: described reductive agent is one or more in formaldehyde, V-Brite B, hydroborate and hydrazine hydrate.
3. the grinding production method of nano cuprous oxide according to claim 1 and 2, it is characterized in that: described mantoquita is copper sulfate, the title complex of cupric nitrate, cupric chloride, neutralized verdigris, copper and comprise one or several of organic copper of long-chain, and wherein the carbon chain lengths of organic copper is 8-16.
4. the grinding production method of nano cuprous oxide according to claim 1 and 2, is characterized in that: described step 1) technique of milling be mechanical disruption or manual mill.
5. a grinding production method for nano cuprous oxide, is characterized in that:
1) mantoquita, reductive agent, acid and dimethyl sulfoxide (DMSO) are stirred at the temperature of 10-70 DEG C, and the 0.2-6h that mills;
2) mixture after milling is used deionized water, ethanol and acetone repetitive scrubbing several times successively, stable nano cuprous oxide can be obtained;
The mol ratio of described reductive agent and mantoquita is 1-10:1, and the ratio of acid and mantoquita is 1-20ml:100g, and the ratio of dimethyl sulfoxide (DMSO) and mantoquita is 1-100ml:10g.
6. the grinding production method of nano cuprous oxide according to claim 5, is characterized in that: described reductive agent is one or several in hypophosphite, xitix, glucose, S-WAT, formic acid, trolamine, ethylene glycol, sorbyl alcohol, Xylitol and oxammonium hydrochloride.
7. the grinding production method of the nano cuprous oxide according to claim 5 or 6, it is characterized in that: described mantoquita is copper sulfate, the title complex of cupric nitrate, cupric chloride, neutralized verdigris, copper and comprise one or several of organic copper of long-chain, and wherein the carbon chain lengths of organic copper is 8-16.
8. the grinding production method of the nano cuprous oxide according to claim 5 or 6, is characterized in that: described acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, formic acid and oxalic acid; Step 1) technique of milling be mechanical disruption or manual mill.
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| CN103435090B (en) * | 2013-08-02 | 2015-06-10 | 浙江理工大学 | Grinding production method of nano cuprous chloride |
| CN105776310A (en) * | 2016-02-03 | 2016-07-20 | 常州市好利莱光电科技有限公司 | Method for preparing cuprous oxide |
| CN106115764B (en) * | 2016-06-23 | 2017-12-12 | 淮北师范大学 | The method that one pot of ball milling solid phase method prepares CuI nano-powders |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101778799A (en) * | 2007-07-25 | 2010-07-14 | Lg化学株式会社 | Spherical assembly particle composition of cuprous oxide and 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 |
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| CN102390861A (en) * | 2011-08-17 | 2012-03-28 | 金川集团有限公司 | Method for preparing cuprous oxide powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101778799A (en) * | 2007-07-25 | 2010-07-14 | Lg化学株式会社 | Spherical assembly particle composition of cuprous oxide and 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 |
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