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
- dimethyl sulfoxide
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- copper
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 28
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 20
- 230000002829 reductive effect Effects 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical group [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000002920 hazardous waste Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- YNIRKEZIDLCCMC-UHFFFAOYSA-K trisodium;phosphate;hydrate Chemical compound [OH-].[Na+].[Na+].[Na+].OP([O-])([O-])=O YNIRKEZIDLCCMC-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Catalysts (AREA)
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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CN201310072729.5A CN103112883B (en) | 2012-12-10 | 2013-03-07 | Method for preparing superfine cuprous oxide powder |
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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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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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