CN102554263A - Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium - Google Patents
Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium Download PDFInfo
- Publication number
- CN102554263A CN102554263A CN2012100416573A CN201210041657A CN102554263A CN 102554263 A CN102554263 A CN 102554263A CN 2012100416573 A CN2012100416573 A CN 2012100416573A CN 201210041657 A CN201210041657 A CN 201210041657A CN 102554263 A CN102554263 A CN 102554263A
- Authority
- CN
- China
- Prior art keywords
- organic
- preparation
- solution
- dispersed
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title abstract 6
- 239000010949 copper Substances 0.000 claims abstract description 41
- 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 abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 150000002505 iron Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 208000035126 Facies Diseases 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002245 particle Substances 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000012074 organic phase Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 72
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 238000007865 diluting Methods 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- 229920013639 polyalphaolefin Polymers 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium, which comprises steps of adding a hydrazine hydrate water solution containing ammonia water into a copper salt water solution to react for 1-30min; adding a mixing water solution of ferrous salt and ferric salt to react for 10-60min; and finally adding a non-polar or weak-polar organic solvent dissolving with a dressing agent to react for 10-20min, standing for separation, taking the organic phase, and concentrating to obtain the Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium, wherein the molar ratio of the copper salt, the hydrazine hydrate, the ferrous salt and the dressing agent is 1:1-10:0.1-1:0.25-2, the molar ratio of the ammonia water to the hydrazine hydrate is 4.4-11:1, and the molar ratio of the ferric salt to the ferrous salt is 2:1. The method is simple in process, and low in cost, and has easily available and cheap raw materials; and the nanoparticles prepared by the method are small in particle diameter, good in dispersity and stability, and suitable for large-scale industrial production.
Description
Technical field
The invention belongs to new function nano material preparation technical field, be specifically related to a kind of organic dispersed Cu/Fe
3O
4The preparation method of magnetic composite nano particulate.
Background technology
The soft metal nano-particle of copper is characteristics such as specific area is big, quantum size effect, macro quanta tunnel effect because of having; And be widely used in catalysis, electronics, magnetics; Optics; Calorifics, coating, field such as lubricated for example are applied to effective catalyst, electrocondution slurry and lube oil additive etc.Research about preparation, performance and the application of nano-particle of copper in recent years receives much attention.Chinese patent 200610165009.3 discloses a kind of method that adopts high-gravity technology to prepare nano copper lubricating oil additive; It utilizes the alternate transmission invigoration effect of RPB and the characteristic that microcosmic mixes; Earlier mantoquita and reducing solution are reduced in supergravity reactor; And then distillate and dressing agent modified it in reaction kettle for reaction, last decompression distillation obtains the brownish red oily liquids of finishing, i.e. nano copper lubricating oil additive.It is fast that this method has reaction speed, the product good reproducibility, and product quality is high, the yield advantages of higher, but the instrument that is adopted is relatively harsher, and production equipment is required than higher.People such as high more honor adopt the method for complexing reduction in patent 96105280.5, prepare nano-particle of copper with active metal powder as reducing agent, and this method is difficult for cleaning because of reactive metal powder reducing agent after reaction is accomplished, and may have influence on the purity of copper nanoparticle.In addition, also have using plasma method, electric radiation method, mechanochemical reaction, thermal decomposition method or solvent-thermal method to wait and prepare nano-particle of copper.Wherein, plasma method equipment is simple, easy to operate, speed of production is fast, but energy consumption is big, and the high temperature bottom electrode is easy to melt and pollution products.Though radiation synthetic method preparation technology is simple, granularity is prone to control, productive rate is high, the product that is obtained is in the dispersoid state, collects very difficulty, is difficult for scale.Though mechanochemistry method technology is simple, can prepare refractory metal that other conventional methods are difficult to prepare, ceramic-metal composite etc., its shortcoming is that crystal is inhomogeneous, in mechanical milling process, is prone to introduce impurity.Thermal decomposition method is quicker, economical with respect to other method, but realizes institute's temperature that requires than higher, and that is that all right is ripe to the control technology of particle diameter and pattern, also differs greatly apart from commercial production.Solvent-thermal method working pressure device requires height to device materials, and condition is harsh relatively, is difficult for enlarging and produces.
In recent years, preparing the active method of nano-particle of copper is liquid phase reduction.Patent CN1188700A discloses a kind of sodium dithionite that adopts and in the mixed solvent of water and organic substance, has reduced the method for bivalent cupric ion.Patent CN1381328A discloses a kind of under higher temperature and pressure, prepares the method for nano-particle of copper with the hydrogen reduction mantoquita.Though existing these liquid-phase reduction methods can make tens metal particles to the hundreds of nanometer; But because the surface does not obtain sufficient modification; It is poor still can't to solve the nanoparticle of preparing property stable in the air, and the problem such as dispersed bad in organic media, is difficult to extensive use.
Summary of the invention
The object of the present invention is to provide a kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, the nanoparticle grain diameter that makes is little, dispersiveness and good stability.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, it comprises the steps: the hydrazine hydrate aqueous solution that contains ammoniacal liquor joined and reacts 1～30min in the copper salt solution; The mixed aqueous solution reaction 10～60min that adds divalent iron salt and trivalent iron salt again adds the nonpolar or weakly polar organic solvent reaction 10～120min that is dissolved with dressing agent at last, and standing separation is got organic facies, promptly gets after concentrating.Reaction temperature is controlled between 20-80 ℃ and is advisable.
The mol ratio of said mantoquita and hydrazine hydrate, divalent iron salt, dressing agent is 1:1-10:0.1-1:0. 25-2, and the mol ratio of ammoniacal liquor and hydrazine hydrate aqueous solution is 4.4-11:1, and the mol ratio of trivalent iron salt and divalent iron salt is 2:1.The mass fraction of ammoniacal liquor is advisable with 25-28%, and the hydrazine hydrate aqueous solution mass fraction is advisable with 50-85%, and the molar concentration of copper salt solution is advisable with 0.2-0.7mol/l.
Concrete, said mantoquita is preferably one or more in water-soluble mantoquitas such as copper sulphate, copper chloride, copper nitrate and copper acetate.
Said divalent iron salt is preferably one or more in ferrous sulfate, frerrous chloride, ferrous nitrate, the ferrous acetate; Said trivalent iron salt is preferably one or more in ferric sulfate, iron chloride, ferric nitrate, the ferric acetate.
Said dressing agent can be that carbochain is at C
6-C
40Between organic carboxyl acid and/or organic amine.Can be saturated, unsaturated, straight chain, side chain or contain one or more the mixture in the aromatic hydrocarbon group like organic carboxylic acid.The preferred carbochain of dressing agent is at C
10-C
20Between organic carboxyl acid and/or organic amine.
Said nonpolar or weakly polar organic solvent is that carbon number is not less than one or more the mixture in 5 alkane, cycloalkane, aromatic hydrocarbon and the chlorohydrocarbon.Organic solvent can also be the saturated alkane mixture in addition, like benzinum (mixture of pentane and hexane) etc.
The characteristic that the inventive method utilizes tri-iron tetroxide to be modified by coating material easily, the method through liquid-phase reduction prepares Cu/Fe
3O
4Composite nano particle has solved metallic nano-particle and has been difficult to the not difficult problem of sulfur-bearing, the modification of phosphorus dressing agent of quilt.This method mainly is divided into two big steps: 1) preparation copper colloidal sol: will contain disposable the joining in the copper salt solution of hydrazine hydrate aqueous solution of ammoniacal liquor, reaction obtains faint yellow transparent copper colloidal sol under magnetic agitation.2) divalence and the trivalent iron salt aqueous solution are joined in the copper colloidal sol, add the organic solvent that is dissolved with dressing agent after reaction a period of time, reaction coats nano-particle of copper after separation obtains oil-soluble tri-iron tetroxide thick, finishing.Prepared product has good dispersiveness in organic solvent; In air, has good oxidation stability.Good here dispersiveness refers to that product is dispersed in the said nonpolar or weakly polar organic solvent with 1% mass concentration, and no sedimentation takes place in 180 days.Good oxidation stability refers to that product is dispersed in the said nonpolar or weakly polar organic solvent with 1% mass concentration, no any change color in 180 days.
The method that the inventive method adopts the tri-iron tetroxide coating technology to combine with liquid-phase reduction; Solved the problem that the nano-particle of copper surface is not easy to modify in the liquid phase reduction; Gained nanoparticle grain diameter little (between the 2-15nm) and uniform particle diameter, dispersiveness and good stability.This method has that process equipment is simple, environmental protection, low in raw material cost are easy to get, cost is low, and characteristics such as the productive rate height of product can obtain particle diameter controllable compound nanoparticle through control reaction temperature condition (20-80 ℃), are fit to large-scale industrial production.Generally speaking, the particle diameter in lower temperature gained nanoparticle is especially little; And the nanoparticle particle diameter that under higher temperature, makes is bigger.As obtaining the composite nano particle particle diameter when the room temperature reaction is 2nm; The composite nano particle particle diameter that when 60 ℃ of reactions, obtains is 15nm.This method gained nanoparticle is scattered in the base oil, in air, can steady in a long-termly exist, and has the wide industrial application prospect.The gained composite nano particle has magnetic in addition, uses relatively easy recovery of back, and is environmentally friendly.
Description of drawings:
The Cu/Fe that the oleic acid that Fig. 1 makes for embodiment 1, oleyl amine are modified
3O
4The transmission electron microscope picture of nanoparticle;
The Cu/Fe that the oleic acid that Fig. 2 makes for embodiment 1, oleyl amine are modified
3O
4Nanoparticle is scattered in the optics picture among the PAO;
The Cu/Fe that the oleic acid that Fig. 3 makes for embodiment 1, oleyl amine are modified
3O
4The magnetic result of the test of nanoparticle;
The Cu/Fe that the oleic acid that Fig. 4 makes for embodiment 2, oleyl amine are modified
3O
4The transmission electron microscope picture of nanoparticle;
The Cu/Fe that the oleic acid that Fig. 5 makes for embodiment 2, oleyl amine are modified
3O
4Nanoparticle is scattered in the optics picture among the PAO.
The specific embodiment
In order to understand the present invention better, below the inventive method is done further to specify, but protection scope of the present invention is not limited thereto through preferred embodiment.
Embodiment 1
A kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, it comprises the steps:
1) gets the CuSO that 4ml concentration is 0.5mol/l
4The aqueous solution gets solution A with distilled water diluting to 50ml;
2) getting the ammoniacal liquor that the 6ml mass fraction is 25-28% (analyze pure, available from the Luoyang magnificent chemical reagent of sky Co., Ltd) and 0.8ml mass fraction is after 80% hydrazine hydrate aqueous solution mixes, and gets solution B with distilled water diluting to 50ml;
3) get 1ml concentration 1mol/l FeCl
3With 0.25ml concentration 2mol/l FeCl
2Mix the back and get solution C to 30ml with distilled water diluting; With 2mmol oleyl amine and 2mmol oleic acid be dissolved in the 100ml benzinum solution D;
4) solution A is changed in the three-neck flask of 500ml; Under normal temperature, stirring condition, solution B joined and react 2min (this moment solution be transparent faint yellow solution) in the solution A; Dropwise add solution C again, reaction 30min solution gradually becomes the rufous suspension, last property adding solution D reaction 1h; Reaction is transferred to standing demix in the separatory funnel with solution system after finishing; Solution divides two-layer (upper strata brownish black organic layer, the colourless water layer of lower floor), get the upper strata organic layer revolve steam brownish red viscous liquid product.
The even (see figure 1) of products obtained therefrom particle diameter, average grain diameter is about 2nm; It is dissolved in PAO (polyalphaolefin) (mass fraction is 1wt% in PAO), and the optical photograph that leaves standstill after 30 days is seen Fig. 2, can find out that by Fig. 2 it has good dispersiveness in base oil.In order to verify whether tri-iron tetroxide is coated on the nano-particle of copper and after coating whether have magnetic; Test as follows: its mother liquor is carried out attraction, and as shown in Figure 3, one side that material all attracted to magnet under the attraction of magnet is (among Fig. 3 as can be seen from Figure 3; The left side is a magnet); All the other are the solution of clear, illustrate that nano-particle of copper is all coated by tri-iron tetroxide, and have stronger magnetic after coating.
Embodiment 2
A kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, it comprises the steps:
1) gets the CuSO that 4ml concentration is 0.5mol/l
4The aqueous solution gets solution A with distilled water diluting to 50ml;
2) getting the 6ml mass fraction is that ammoniacal liquor and the 0.8ml mass fraction of 25-28% is after 80% hydrazine hydrate aqueous solution mixes, and gets solution B with distilled water diluting to 50ml;
3) get 1ml concentration 1mol/l FeCl
3With 0.25ml concentration 2mol/l FeCl
2Mix the back and get solution C to 30ml with distilled water diluting; With 2mmol oleyl amine and 2mmol oleic acid be dissolved in the 100ml benzinum solution D;
4) solution A is changed in the three-neck flask of 500ml; Under 60 ℃, stirring condition, solution B joined and react 2min (this moment, solution was transparent faint yellow solution) in the solution A; Dropwise add solution C again, reaction 30min solution gradually becomes the rufous suspension, last property adding solution D reaction 1h; Reaction is transferred to standing demix in the separatory funnel with solution system after finishing; Solution divides two-layer (upper strata brownish black organic layer, the colourless water layer of lower floor), get the upper strata organic layer revolve steam brownish black viscous liquid product.
The even (see figure 4) of products obtained therefrom particle diameter, average grain diameter is about 15nm; It is dissolved in PAO (polyalphaolefin) (mass fraction is 1wt% in PAO), and the optical photograph that leaves standstill after 30 days is seen Fig. 5, can find out that by Fig. 5 it has good dispersiveness in base oil.
Embodiment 3
A kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, it comprises the steps:
1) getting 4ml concentration is that the copper acetate aqueous solution of 0.25mol/l gets solution A with distilled water diluting to 50ml;
2) getting the 3ml mass fraction is that ammoniacal liquor and the 0.7ml mass fraction of 25-28% is after 50% hydrazine hydrate aqueous solution mixes, and gets solution B with distilled water diluting to 50ml;
3) get 0.5ml concentration 1mol/l Fe (NO
3)
3With 0.125ml concentration 2mol/l Fe (NO
3)
2Mix the back and get solution C to 30ml with distilled water diluting; With 1mmol n-octyl amine and 1mmol oleic acid be dissolved in the 100ml chloroform solution D;
4) solution A is changed in the three-neck flask of 500ml; Under 45 ℃, stirring condition, solution B joined and react 2min (this moment, solution was transparent pale yellow solution) in the solution A; Dropwise add solution C again, reaction 30min solution gradually becomes the reddish dark brown suspension, last property adding solution D reaction 1h; Reaction is transferred to standing demix in the separatory funnel with solution system after finishing; Solution divides two-layer (the colourless water layer in upper strata, the pale brown look organic layer of lower floor), take off a layer organic layer revolve steam pale brown look viscous liquid product.
Embodiment 4
A kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, it comprises the steps:
1) gets the CuCl that 6ml concentration is 0.5mol/l
2The aqueous solution gets solution A with distilled water diluting to 50ml;
2) getting the 6ml mass fraction is that ammoniacal liquor and the 1.6ml mass fraction of 25-28% is after 50% hydrazine hydrate aqueous solution mixes, and gets solution B with distilled water diluting to 50ml;
3) get 1ml concentration 1mol/l Fe (SO
4)
3With 0.25ml concentration 2mol/l Fe (SO
4)
2Mix the back and get solution C to 30ml with distilled water diluting; With 0.5mmol oleyl amine and 0.5mmol stearic acid be dissolved in the 100ml chloroform solution D;
4) solution A is changed in the three-neck flask of 500ml; Under 45 ℃ of stirring conditions, solution B joined and react 2min (this moment solution be transparent faint yellow solution) in the solution A; Dropwise add solution C again, reaction 30min solution gradually becomes brown suspension, last property adding solution D reaction 1h; Reaction is transferred to standing demix in the separatory funnel with solution system after finishing; Solution divides two-layer (the colourless water layer in upper strata, the brown organic layer of lower floor), take off a layer organic layer revolve steam brown viscous liquid product.
Embodiment 5
A kind of organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle, it comprises the steps:
1) gets the Cu (NO that 4ml concentration is 0.5mol/l
3)
2The aqueous solution gets solution A with distilled water diluting to 50ml;
2) getting the 6ml mass fraction is that ammoniacal liquor and the 1.2ml mass fraction of 25-28% is after 50% hydrazine hydrate aqueous solution mixes, and gets solution B with distilled water diluting to 50ml;
3) get 2ml concentration 1mol/l FeCl
3With 0.5ml concentration 2mol/l FeCl
2Mix the back and get solution C to 30ml with distilled water diluting; With 1mmol n-octyl amine and 1mmol tetradecylic acid be dissolved in the 100ml benzinum solution D;
4) solution A is changed in the three-neck flask of 500ml; Under normal temperature, stirring condition, solution B joined and react 2min (this moment solution be transparent faint yellow solution) in the solution A; Dropwise add solution C again, reaction 60min solution gradually becomes the dark-brown suspension, last property adding solution D reaction 1h; Reaction is transferred to standing demix in the separatory funnel with solution system after finishing; Solution divides two-layer (upper strata dark-brown organic layer, the colourless water layer of lower floor), get the upper strata organic layer revolve steam brown viscous liquid product.
Claims (7)
1. organic dispersed Cu/Fe
3O
4The preparation method of composite nano particle is characterized in that, comprises the steps: the hydrazine hydrate aqueous solution that contains ammoniacal liquor joined to react 1～30min in the copper salt solution; The mixed aqueous solution reaction 10～60min that adds divalent iron salt and trivalent iron salt again adds the nonpolar or weakly polar organic solvent reaction 10～120min that is dissolved with dressing agent at last, and standing separation is got organic facies, promptly gets after concentrating; The mol ratio of said mantoquita and hydrazine hydrate, divalent iron salt, dressing agent is 1:1-10:0.1-1:0. 25-2, and the mol ratio of ammoniacal liquor and hydrazine hydrate is 4.4-11:1, and the mol ratio of trivalent iron salt and divalent iron salt is 2:1.
2. organic according to claim 1 dispersed Cu/Fe
3O
4The preparation method of composite nano particle is characterized in that, said mantoquita is one or more in copper sulphate, copper chloride, copper nitrate and the copper acetate.
3. organic according to claim 1 dispersed Cu/Fe
3O
4The preparation method of composite nano particle is characterized in that, said divalent iron salt is one or more in ferrous sulfate, frerrous chloride, ferrous nitrate, the ferrous acetate; Said trivalent iron salt is one or more in ferric sulfate, iron chloride, ferric nitrate, the ferric acetate.
4. organic according to claim 1 dispersed Cu/Fe
3O
4The preparation method of composite nano particle is characterized in that, said dressing agent is that carbochain is at C
6-C
40Between organic carboxyl acid and/or organic amine.
5. like the said organic dispersed Cu/Fe of claim 4
3O
4The preparation method of composite nano particle is characterized in that, said dressing agent is that carbochain is at C
10-C
20Between organic carboxyl acid and/or organic amine.
6. organic according to claim 1 dispersed Cu/Fe
3O
4The preparation method of composite nano particle is characterized in that, said nonpolar or weakly polar organic solvent is that carbon number is not less than one or more the mixture in 5 alkane, cycloalkane, aromatic hydrocarbon and the chlorohydrocarbon.
7. organic according to claim 1 dispersed Cu/Fe
3O
4The preparation method of composite nano particle is characterized in that, reaction temperature is controlled between 20-80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210041657.3A CN102554263B (en) | 2012-02-23 | 2012-02-23 | Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210041657.3A CN102554263B (en) | 2012-02-23 | 2012-02-23 | Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102554263A true CN102554263A (en) | 2012-07-11 |
| CN102554263B CN102554263B (en) | 2014-01-08 |
Family
ID=46401627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210041657.3A Expired - Fee Related CN102554263B (en) | 2012-02-23 | 2012-02-23 | Preparation method for Cu/Fe3O4 composite nanoparticles having good dispersity in organic medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102554263B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437344A (en) * | 2014-10-13 | 2015-03-25 | 中南大学 | Copper doped composite magnetic nano-material and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0977212A2 (en) * | 1998-07-31 | 2000-02-02 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| CN101259531A (en) * | 2008-03-31 | 2008-09-10 | 河南大学 | Surface finish nano copper/copper alloy particles and preparation thereof |
| CN101345111A (en) * | 2008-05-20 | 2009-01-14 | 湖南工业大学 | Novel method of manufacturing Fe3O4/Pt magnetic complex nano particle |
| CN101372037A (en) * | 2007-08-23 | 2009-02-25 | 高愈尊 | Method for preparing nano copper powder |
| CN101391308A (en) * | 2008-10-10 | 2009-03-25 | 北京工业大学 | Preparation method of cuprum argentum composite powder |
-
2012
- 2012-02-23 CN CN201210041657.3A patent/CN102554263B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0977212A2 (en) * | 1998-07-31 | 2000-02-02 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| CN101372037A (en) * | 2007-08-23 | 2009-02-25 | 高愈尊 | Method for preparing nano copper powder |
| CN101259531A (en) * | 2008-03-31 | 2008-09-10 | 河南大学 | Surface finish nano copper/copper alloy particles and preparation thereof |
| CN101345111A (en) * | 2008-05-20 | 2009-01-14 | 湖南工业大学 | Novel method of manufacturing Fe3O4/Pt magnetic complex nano particle |
| CN101391308A (en) * | 2008-10-10 | 2009-03-25 | 北京工业大学 | Preparation method of cuprum argentum composite powder |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437344A (en) * | 2014-10-13 | 2015-03-25 | 中南大学 | Copper doped composite magnetic nano-material and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102554263B (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100579688C (en) | Surface finish nano copper/copper alloy particles and preparation thereof | |
| Chi et al. | Synthesis of Fe3O4@ SiO2–Ag magnetic nanocomposite based on small-sized and highly dispersed silver nanoparticles for catalytic reduction of 4-nitrophenol | |
| Zheng et al. | In situ loading of gold nanoparticles on Fe 3 O 4@ SiO 2 magnetic nanocomposites and their high catalytic activity | |
| Le et al. | Fibrous nano-silica containing immobilized Ni@ Au core–shell nanoparticles: a highly active and reusable catalyst for the reduction of 4-nitrophenol and 2-nitroaniline | |
| Ma et al. | Preparation of high-magnetization Fe3O4–NH2–Pd (0) catalyst for Heck reaction | |
| CN102554217B (en) | Water-soluble nano-copper and preparation method thereof | |
| CN102633307A (en) | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles | |
| Zhong et al. | APTES-functionalized Fe3O4 microspheres supported Cu atom-clusters with superior catalytic activity towards 4-nitrophenol reduction | |
| Wang et al. | Magnetic polymer nanocomposite-supported Pd: an efficient and reusable catalyst for the Heck and Suzuki reactions in water | |
| Islam et al. | Fluorescent silver nanoclusters (Ag NCs) in the metal–organic framework MIL-101 (Fe) for the catalytic hydrogenation of 4-nitroaniline | |
| CN108817414B (en) | Preparation method of gold nanoflower in ionic liquid aqueous solution | |
| CN101890506B (en) | Method for preparing nano-copper | |
| CN101007281A (en) | Novel preparation method of amorphous alloy catalyst | |
| CN102389949B (en) | A kind of preparation method of sea urchin-shaped nanometer copper particles | |
| CN103273083A (en) | Method for preparing gold nanoparticles | |
| CN102583576A (en) | Method for preparing paramagnetic Fe3O4 nanoparticles by using iron tailings | |
| Mirbagheri et al. | Magnetic ethyl-based organosilica supported Schiff-base/indium: A very efficient and highly durable nanocatalyst | |
| Banazadeh et al. | Novel synthesis and characterization of Fe3O4@ silica–palladium nanocatalyst: A highly active and reusable heterogeneous catalyst for Heck cross-coupling reactions | |
| CN103588178A (en) | Technology for synthesizing sulfur quantum dots through oil-water interface method | |
| CN108855217B (en) | Preparation method and application of copper-based metal organic framework nano sheet | |
| Li et al. | Ag/Au-decorated Fe3O4/SiO2 composite nanospheres for catalytic applications | |
| Ghazanfari et al. | Synthesis and characterization of Fe3O4@ Ag core-shell: structural, morphological, and magnetic properties | |
| Zhao et al. | Effective fenton catalyst from controllable framework doping of Fe in porous silica spheres | |
| CN108405879A (en) | A kind of preparation method of nano zero valence iron@meso pore silicon oxide materials | |
| CN102728847A (en) | Preparation method for gold-copper bimetal nanospheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 475001 Henan province city Minglun Street No. 85 Patentee after: Henan University Address before: 475004 Jinming Avenue, Kaifeng City, Henan Province Patentee before: Henan University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140108 |