CN103112883B - Method for preparing superfine cuprous oxide powder - Google Patents
Method for preparing superfine cuprous oxide powder Download PDFInfo
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- CN103112883B CN103112883B CN201310072729.5A CN201310072729A CN103112883B CN 103112883 B CN103112883 B CN 103112883B CN 201310072729 A CN201310072729 A CN 201310072729A CN 103112883 B CN103112883 B CN 103112883B
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- cuprous oxide
- oxide powder
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Abstract
The invention relates to a method for preparing superfine cuprous oxide powder. The method comprises the following steps of: (1) adding a reducing agent to dimethyl sulfoxide organic liquid containing cupric ions, and carrying out reaction for 0.5-8 hours at the temperature of 15-90 DEG C; and (2) centrifuging, washing and drying obtained turbid liquid, thereby obtaining the cuprous oxide powder. The method has the beneficial effects that prepared cuprous oxide particles have the particle diameter being smaller than 20nm and have good secondary dispersity in various oil agents; the preparation cost is low, the energy source consumption is low, no hazardous wastes are produced, and thus, the requirements of modern production on green production, environment-friendliness and energy saving are met; and the process is simple, the operation is simple and convenient, the reactions are mild, the reaction time is short, and the efficiency is high, and therefore the method is applicable to large-scale production.
Description
Technical field
The present invention relates to Inorganic Chemicals production field, especially a kind of method adopting reduction method to prepare ultrafine cuprous oxide powder.
Background technology
Red copper oxide (Cu
2o) be a kind of p-type semiconductor material, energy gap is about 2.2eV, compares TiO
23.2eV much lower, there is typical optical solitons, in magnetic memory apparatus etc., have potential application prospect.Cuprous oxide powder, as Inorganic Chemicals, has purposes widely in pigment, boats and ships, antiseptic-germicide, coating, electronic product.In addition, be also widely used in the negative material etc. of superconductor, solar cell, catalyzer, lithium ion battery.Meanwhile, Red copper oxide also has potential application prospect in photocatalysis degradation organic contaminant, in environmental pollution improvement, therefore receive the strong interest of environmental research person.
At present, the method for industrial production Red copper oxide mainly contains: sintering process, electrolytic process, using sulfur dioxide reduction method, liquid phase reduction etc.Sintering process first carries out solid-solid reaction by after cupric oxide and copper powder mixing at about 1000 DEG C, and produce Red copper oxide, this method labor condition is poor, and energy consumption is large, and Red copper oxide purity is low, and the quality of product depends on the quality of oxidation of precursor copper more.Electrolytic process makes anode with metallic copper, electrolysis in the solution of copper ions, and the product cut size of this method gained is bigger than normal, and power consumption is high, production efficiency is low, production environment is poor.Using sulfur dioxide reduction method is using pyrophosphate salt as catalyzer, and sulfurous gas, as reductive agent, prepares Red copper oxide, and this method reagent consumption is large, and production cost is high, high to equipment sealing requirements, operating environment is poor.Liquid phase reduction is widely used because of equipment used less investment and the pattern of product and size tunable.The people such as Xu reduce Cu (CH in aqueous with xitix
3cOO)
2obtain the Cu of porous
2o nanometer ball [Xuet al.Nanotechnology.4 (2009): 045605]; The people such as Cui take glucose as reductive agent, under CTAB protection, at Cu
2+under the condition that concentration is lower, reduction has obtained the cuprous oxide powder [Cui ZLMaterials Science and Engineering B.162 (2009): 82-86] of recessed octahedral build.The turbid solution that aqueous ascorbic acid and cupric oxide pressed powder are formed is transferred in the stainless steel water heating kettle of inner liner polytetrafluoroethylene by Yue Linhai, hydrothermal treatment consists 3-6 hour at 60-100 DEG C, obtain cuprous oxide powder [Yue Linhai etc., number of patent application: 201110007688.2].Number of patent application be 201110235648.3 Chinese invention patent application disclose a kind of method preparing cuprous oxide powder, using sulphite as reductive agent, join in the solution containing bivalent cupric ion, carry out reaction and prepare cuprous oxide powder.These methods above-mentioned or need to add other organic additive, or reaction conditions is harsher, and obtained Red copper oxide particle all comparatively large (being greater than 20nm).
Summary of the invention
The present invention will solve the shortcoming of above-mentioned prior art, provides that a kind of technique is simple, energy consumption and the low method preparing ultrafine cuprous oxide powder of cost, is less than the cuprous oxide powder of 20nm with obtained particle diameter.
The present invention solves the technical scheme that its technical problem adopts: a kind of method preparing ultrafine cuprous oxide powder, comprises the following steps:
1) reductive agent is added to containing in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, under temperature is 15 DEG C of-90 DEG C of conditions, reaction 0.5-8h;
2) by centrifugal for gained turbid solution, washing, drying, cuprous oxide powder is 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 bivalent cupric ion is 1-10: 1.
As preferably, be 1-50g/L containing bivalent cupric ion concentration in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, wherein solvent is the dimethyl sulphoxide solution that absolute dimethyl sulfoxide or mass percent are greater than 50%, solute is cupric nitrate, the title complex of cupric chloride, neutralized verdigris, copper sulfate, copper and comprise one or several of organic copper of long-chain, and wherein organic copper carbon chain lengths is 8-16.
Another kind prepares the method for ultrafine cuprous oxide powder, comprises the following steps:
1) add reductive agent to containing in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, and regulate the pH value of reaction system to be 1.5-6.5, temperature is 15 DEG C-90 DEG C, reaction 0.5-8h;
2) by centrifugal for gained turbid solution, washing, drying, cuprous oxide powder is 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 bivalent cupric ion is 1-10: 1.
As preferably, be 1-50g/L containing bivalent cupric ion concentration in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, wherein solvent is the dimethyl sulphoxide solution that absolute dimethyl sulfoxide or mass percent are greater than 50%, solute is cupric nitrate, the title complex of cupric chloride, neutralized verdigris, copper sulfate, copper and comprise one or several of organic copper of long-chain, and wherein organic copper carbon chain lengths is 8-16.
As preferably, in preparation process, carry out adjust ph by one or more adding in sulfuric acid, hydrochloric acid, acetic acid, nitric acid, phosphoric acid, formic acid or oxalic acid.
The invention has the beneficial effects as follows: one, the present invention adopts dimethyl sulfoxide (DMSO) to make solvent, utilize the effect between dimethyl sulfoxide (DMSO) and cupric ion, limit the growth of Red copper oxide particle, prepared by Red copper oxide grain diameter be out less than 20nm, in all kinds of finish, there is good twice dispersing.Two, preparation cost is low, and energy consumption is low, produces, meet the modern production requirement of " green production, environmental protection and energy saving " without bazardous waste.Three, technique is simple, easy and simple to handle, reaction temperature and, the reaction times is short, and efficiency is high, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1 is that the transmission electron microscope (TEM) that the present invention obtains cuprous oxide powder observes photo.
Fig. 2 is that the XRD (X-ray) that the present invention obtains cuprous oxide powder tests collection of illustrative plates.
Embodiment
The present invention utilizes dimethyl sulfoxide solvent itself to make template; additionally do not add other organic protective agent; reductive agent is joined in the dimethyl sulfoxide (DMSO) organic solution containing bivalent cupric ion, hierarchy of control pH value and temperature, after reaction certain hour, prepare ultrafine cuprous oxide powder.
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment 1:
Get 12g cupric sulfate pentahydrate and 30g inferior sodium phosphate joins in 2L dimethyl sulphoxide solution, and this solution is heated to 50 DEG C; Use sulfuric acid regulation solution pH=1.5, react 2 hours; By centrifugal for gained turbid solution, washing, drying, obtain cuprous oxide powder.
Make transmission electron microscope (TEM) to gained cuprous oxide powder to observe, as shown in Figure 1, its particle diameter known is less than 20nm, and X ray test collection of illustrative plates as shown in Figure 2.
Embodiment 2:
126g neutralized verdigris and 120g sodium borohydride join in dimethyl sulphoxide solution 10L, solution are heated to 30 DEG C, reaction 1h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
Embodiment 3:
Get 12g cupric nitrate and 25g S-WAT (seven water) joins in 1L dimethyl sulphoxide solution, and this solution is heated to 40 DEG C, and maintain pH value of solution=2.5 with sulfuric acid, reaction 1h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
Embodiment 4:
Get 16g copper sulfate and 35g inferior sodium phosphate (water) joins in the mixed solvent of 950ml dimethyl sulfoxide (DMSO) and 50ml water, and this solution is heated to 50 DEG C, and maintain pH value of solution=3.5 with sulfuric acid, reaction 3h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
Embodiment 5:
Get 16g cupric chloride (two water) and 35g xitix joins in 1L dimethyl sulfoxide solvent, and this solution is heated to 60 DEG C, and maintain pH value of solution=4.5 with acetic acid, reaction 4h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
Embodiment 6:
Get 16g cupric sulfate pentahydrate and 15g formic acid joins in the mixed solvent of 800ml dimethyl sulfoxide (DMSO) and 200ml DMF, and maintain pH value of solution=4.5 with acetic acid, this solution is heated to 70 DEG C, reaction 4h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
Embodiment 7:
Get 13g cupric sulfate pentahydrate and 15g hydrazine hydrate joins in 1L dimethyl sulfoxide solvent, this solution is heated to 30 DEG C, reaction 2h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
Embodiment 8:
Get 16g cupric sulfate pentahydrate and 15g oxammonium hydrochloride joins in 1L dimethyl sulfoxide solvent, and maintain pH value of solution=6.5 with oxalic acid, this solution is heated to 90 DEG C, reaction 8h; By centrifugal for gained turbid solution, washing, drying, obtain the cuprous oxide powder that particle diameter is less than 20nm.
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 (6)
1. prepare a method for ultrafine cuprous oxide powder, it is characterized in that:
1) reductive agent is added to containing in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, under temperature is 15 DEG C of-90 DEG C of conditions, reaction 0.5-8 h; Described reductive agent is one or more in formaldehyde, V-Brite B, hydroborate and hydrazine hydrate;
2) by centrifugal for gained turbid solution, washing, drying, cuprous oxide powder is obtained;
Wherein said is 1-50 g/L containing bivalent cupric ion concentration in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, wherein solvent is the dimethyl sulphoxide solution that absolute dimethyl sulfoxide or mass percent are greater than 50%, solute is cupric nitrate, the title complex of cupric chloride, neutralized verdigris, copper sulfate, copper and comprise one or several of organic copper of long-chain, and wherein organic copper carbon chain lengths is 8-16.
2. the method preparing ultrafine cuprous oxide powder according to claim 1, is characterized in that: the mol ratio of described reductive agent and bivalent cupric ion is 1-10:1.
3. prepare a method for ultrafine cuprous oxide powder, it is characterized in that:
1) add reductive agent to containing in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, and regulate the pH value of reaction system to be 1.5-6.5, temperature is 15 DEG C-90 DEG C, reaction 0.5-8 h;
2) by centrifugal for gained turbid solution, washing, drying, cuprous oxide powder is obtained;
Wherein said is 1-50 g/L containing bivalent cupric ion concentration in the dimethyl sulfoxide (DMSO) organic solution of bivalent cupric ion, wherein solvent is the dimethyl sulphoxide solution that absolute dimethyl sulfoxide or mass percent are greater than 50%, solute is cupric nitrate, the title complex of cupric chloride, neutralized verdigris, copper sulfate, copper and comprise one or several of organic copper of long-chain, and wherein organic copper carbon chain lengths is 8-16.
4. the method preparing ultrafine cuprous oxide powder according to claim 3, 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.
5. the method preparing ultrafine cuprous oxide powder according to claim 3 or 4, is characterized in that: the mol ratio of described reductive agent and bivalent cupric ion is 1-10:1.
6. the method preparing ultrafine cuprous oxide powder according to claim 3 or 4, is characterized in that: carry out adjust ph by one or more adding in sulfuric acid, hydrochloric acid, acetic acid, nitric acid, phosphoric acid, formic acid or oxalic acid in preparation process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103274444B (en) * | 2013-06-05 | 2014-09-24 | 沈阳化工大学 | Preparation method for ultrafine cuprous oxide |
| CN103435091A (en) * | 2013-08-02 | 2013-12-11 | 浙江理工大学 | Method for preparing superfine cuprous chloride |
| CN104445359B (en) * | 2014-11-17 | 2015-12-09 | 河南大学 | A kind of method preparing cuprous nano structure on phosphor bronze surface |
| CN104591257B (en) * | 2015-01-12 | 2016-01-06 | 广东光华科技股份有限公司 | The preparation method of the micro-nano cuprous oxide powder of a kind of cubes |
| CN105400955A (en) * | 2015-11-19 | 2016-03-16 | 湖南力泓新材料科技股份有限公司 | Method for removing copper ions in zinc sulfate solution |
| CN106191452B (en) * | 2016-09-28 | 2018-10-30 | 江苏理工学院 | A method of preparing cuprous oxide using copper scrap tungsten alloy as raw materials recovery |
| CN109248685A (en) * | 2018-10-10 | 2019-01-22 | 吉林农业大学 | It is a kind of to prepare octahedral figure Cu2The method of O nano material |
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| JP2006096655A (en) * | 2004-09-06 | 2006-04-13 | Fuji Photo Film Co Ltd | Method for producing cuprous oxide particle and cuprous oxide particle |
| 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 |
| CN101784352A (en) * | 2007-07-26 | 2010-07-21 | Lg化学株式会社 | Preparation method of copper particle composition |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006096655A (en) * | 2004-09-06 | 2006-04-13 | Fuji Photo Film Co Ltd | Method for producing cuprous oxide particle and cuprous oxide particle |
| 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 |
| CN101784352A (en) * | 2007-07-26 | 2010-07-21 | Lg化学株式会社 | Preparation method of copper particle composition |
| 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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Effective date of registration: 20190924 Address after: 244000 Fengxin Group 7, Charencun, Tongling Development Zone, Tongling City, Anhui Province Patentee after: Tongling Mdt InfoTech Ltd Address before: 310018, No. 118, 2 street, Xiasha Higher Education Park, Hangzhou, Zhejiang Patentee before: Zhejiang University of Technology |
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