CN102344649B - Method for preparing alpha-ferrite/poly(3,4-ethylenedioxythiophene)thiofuran composite nanorod - Google Patents
Method for preparing alpha-ferrite/poly(3,4-ethylenedioxythiophene)thiofuran composite nanorod Download PDFInfo
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- CN102344649B CN102344649B CN201010243102A CN201010243102A CN102344649B CN 102344649 B CN102344649 B CN 102344649B CN 201010243102 A CN201010243102 A CN 201010243102A CN 201010243102 A CN201010243102 A CN 201010243102A CN 102344649 B CN102344649 B CN 102344649B
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- dioxoethyl
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Abstract
The invention belongs to the material field of conductive polymer and inorganic magnetic material composite, and relates to a method for preparing polythiophene conductive polymer and inorganic magnetic material composite nanorod, particularly relates to a one step method for preparing alpha-ferrite/(alpha-FeO(OH))/poly(3,4-ethylenedioxythiophene)thiofuran(PEDOT) composite nanorod. According to the invention, under the room temperature condition, by applying the dual oxidants in a solution, the concentration of Fe<3+> and Fe<2+> in the solution can be simultaneously regulated, thereby the alpha-ferrite/(alpha-FeO(OH))/poly(3,4-ethylenedioxythiophene)thiofuran(PEDOT) composite nanorod with electrical function, magnetic function, and monocrystalline characteristic is obtained. The method of the present invention is mild, simple, controllable and easy to operate.
Description
Technical field
The invention belongs to conductive polymers and inorganic magnetic material compound field of materials; The preparation method who relates to polythiophene class conductive polymers and inorganic magnetic material compound nanometer rod; Be particularly related to the method that single stage method prepares α-ferrite (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.
Background technology
Conducting polymer composite material with electricity, magnetic function is owing to the potential application foreground in fields such as electromagnetic shielding, electrochromism, store energy and radar-wave absorbings enjoys people's attention.
In the preparation method of conductive polymers and inorganic magnetic material; Two kinds of methods are arranged usually, and a kind of is two-step approach, prepares magneticsubstance carries out conductive polymers again in comprising the dispersion system of magneticsubstance polyreaction earlier; Obtain the matrix material of conductive polymers and inorganic magnetic material; A kind of in addition method is exactly the matrix material that the employing single stage method prepares conductive polymers and inorganic magnetic material, (Macromol.Rapid Commun., 2007 such as Zhang; 28:585～690) adopt single stage method, through regulating Fe
3+And Fe
2+Concentration obtain comprising Y-Fe
2O
3Polyaniline fiber, (Journal ofPolumer Science:Part A:Polymer Chemistry, 2009) such as Wei-Dong zhang adopt single stage method to do at tosic acid under the situation of doping agent, have prepared the adulterated Fe of comprising of tosic acid
3O
4The polypyrrole nanotube, Xiao etc. (Composites Science and Technology 70 (2010) 909～915) utilize single stage method to prepare α-ferrite (α-FeO (OH)/polypyrrole (ppy) nano-complex under 0～5 ℃ of situation.PEDOT has high conductivity, low band gaps width, the particularly environmental stability and the stable conductivity property of excellence in conductive polymers family; Be the conductive polymers of tool application prospect, the technical scheme for preparing PEDOT and inorganic magnetic matrix material about single stage method is not all seen document and patent report.
Summary of the invention
The objective of the invention is to propose a kind of chemical single stage method and prepare α-ferrite (method of α-FeO (OH)/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.
α-ferrite of the present invention (preparation method of α-FeO (OH)/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod may further comprise the steps:
1) the persulfate oxidation agent is joined in the deionized water in the container, stirring and dissolving, obtaining volumetric molar concentration is 1 * 10
-4Mol/L～1 * 10
-2The persulfate solution of mol/L, making the persulfate solution total amount is 100ml, under agitation condition, adds 3 of 0.1～1ml, 4-dioxoethyl thiophene; Under agitation condition; Drip ferric salt solution 10～30ml of 0.8mol/L again; Stir (being generally 10～15 minutes), drip divalent iron salt solution 10～30ml of 0.8mol/L again, stir (being generally 10～15 minutes); In solution, feed rare gas element (like nitrogen), dropping 10ml mass concentration is 25% ammoniacal liquor; At room temperature continue stirring reaction (being generally about 2～8 hours), obtain containing α-ferrite (α-FeO (OH))/gather black emulsion of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod;
2) contain α-ferrite (α-FeO (OH))/gather (3 with what step 1) obtained; The 4-dioxoethyl) black emulsion spinning in the whizzer of 8000～10000rpm (being generally 8～10 minutes) of thiophene (PEDOT) composite Nano rod; Remove unreacted reactant, supernatant liquid is outwelled, it is to wash in 1: 1 water and the ethanol mixed solvent and carry out spinning by above-mentioned centrifugal condition that the black precipitate that obtains is dispersed in volume ratio again; The repeated centrifugation washing operation; Till supernatant liquid was colourless, the black precipitate that obtains at last was 80 ℃ of following vacuum-dryings 24 hours in temperature, obtains black powder; Above-mentioned black powder promptly is the α-ferrite described in the present invention (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.
Described α-ferrite (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod is the monocrystalline characteristic, and its diameter is between 5nm～50nm, and specific conductivity is 1 * 10
-3～1 * 10
-1Between the S/cm, saturation magnetization is 15～60emu/g.
Centrifuge speed during described spinning is 8000～10000rpm.
Described persulfate oxidation agent is ammonium persulphate, Potassium Persulphate, Sodium Persulfate or any mixture between them.
Described trivalent iron salt is iron nitrate, iron(ic)chloride or their mixture.
Described divalent iron salt is Iron nitrate, iron protochloride, ferrous sulfate or any mixture between them.
The present invention is at ambient temperature, through the application of two oxygenants (persulfate oxidation agent and trivalent iron salt oxygenant) in the solution, regulates and control Fe in the solution simultaneously
3+And Fe
2+Concentration, can obtain to have concurrently the α-ferrite with monocrystalline characteristic (α-FeO (OH)) of electricity, magnetic function/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.Method of the present invention is gentle, simple, easy row, controlled.
Description of drawings
Fig. 1. the α-ferrite (α-FeO (OH)) of the embodiment of the invention 1 preparation/the gather SEM photo of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.
Fig. 2. the α-ferrite (α-FeO (OH)) of the embodiment of the invention 2 preparation/the gather high resolution TEM photo of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.
Embodiment
Embodiment 1
1) the ammonium persulphate oxygenant is joined in the deionized water in the container, stirring and dissolving, obtaining volumetric molar concentration is 1.0 * 10
-4The ammonium persulfate solution of mol/L, making the ammonium persulfate solution total amount is 100ml, under agitation condition, adds 3 of 0.1ml, 4-dioxoethyl thiophene stirred 10 minutes; And under agitation condition, drip the liquor ferri trichloridi 10ml of 0.8mol/L again, stirred about 10 minutes; Drip the ferrous sulfate aqueous solution 30ml of 0.8mol/L again; Stirred about 10 minutes, and in solution, fed nitrogen, dropping 10ml mass concentration is 25% ammoniacal liquor; At room temperature continue stirring reaction 4 hours, obtain containing α-ferrite (α-FeO (OH))/gather black emulsion of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod;
2) contain α-ferrite/gather (3 with what step 1) obtained; The 4-dioxoethyl) the black emulsion of thiophene composite Nano rod spinning 8～10 minutes in 8000～10000rpm whizzer; Remove unreacted reactant, supernatant liquid is outwelled, it is to wash in 1: 1 water and the ethanol mixed solvent and carry out spinning by above-mentioned centrifugal condition that the black precipitate that obtains is dispersed in volume ratio again; The repeated centrifugation washing operation; Till supernatant liquid was colourless, the black precipitate that obtains at last was 80 ℃ of following vacuum-dryings 24 hours in temperature, obtains black powder; Above-mentioned black powder promptly is the α-ferrite described in the present invention (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.This composite Nano rod is the monocrystalline characteristic, and its diameter is about 10nm, and specific conductivity is 5.0 * 10
-3S/cm, saturation magnetization 56emu/g.
Embodiment 2
1) the Potassium Persulphate oxygenant is joined in the deionized water in the container, stirring and dissolving, obtaining volumetric molar concentration is 5.0 * 10
-3The potassium persulfate solution of mol/L, making the potassium persulfate solution total amount is 100ml, under agitation condition, adds 3 of 0.5ml, 4-dioxoethyl thiophene stirred 10 minutes; And under agitation condition, drip the iron nitrate solution 20ml of 0.8mol/L again, and stirred about 15 minutes, drip the ferrous chloride aqueous solution 20ml of 0.8mol/L again, stirred about 10 minutes, in solution, feed nitrogen, dropping 10ml mass concentration is 25% ammoniacal liquor; At room temperature continue stirring reaction 2 hours, obtain containing α-ferrite (α-FeO (OH))/gather black emulsion of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod;
2) contain α-ferrite/gather (3 with what step 1) obtained; The 4-dioxoethyl) the black emulsion of thiophene composite Nano rod is according to embodiment 1 step 2) technical scheme implement; Obtain α-ferrite (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.This composite Nano rod is the monocrystalline characteristic, and its diameter is about 30nm, and specific conductivity is 3.2 * 10
-2S/cm, saturation magnetization is 36emu/g.
Embodiment 3
1) the Sodium Persulfate oxygenant is joined in the deionized water in the container, stirring and dissolving, obtaining volumetric molar concentration is 1.0 * 10
-2The Sodium Persulfate solution of mol/L, making Sodium Persulfate solution total amount is 100ml, under agitation condition, adds 3 of 1.0ml, 4-dioxoethyl thiophene stirred 10 minutes; And under agitation condition, drip the iron nitrate solution 30ml of 0.8mol/L again, and stirred about 15 minutes, drip the ferrous nitrate aqueous solution 10ml of 0.8mol/L again, stirred about 15 minutes, in solution, feed nitrogen, dropping 10ml mass concentration is 25% ammoniacal liquor; At room temperature continue stirring reaction 8 hours, obtain containing α-ferrite (α-FeO (OH))/gather black emulsion of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod;
2) contain α-ferrite/gather (3 with what step 1) obtained; The 4-dioxoethyl) the black emulsion of thiophene composite Nano rod is according to embodiment 1 step 2) technical scheme implement; Obtain α-ferrite (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.This composite Nano rod is the monocrystalline characteristic, and its diameter is about 43nm, and specific conductivity is 9.8 * 10
-2S/cm, saturation magnetization is 23emu/g.
Embodiment 4
1) Sodium Persulfate, ammonium persulphate and Potassium Persulphate oxygenant are joined in the deionized water in the container, stirring and dissolving, the volumetric molar concentration that obtains Sodium Persulfate is 2.0 * 10
-3The volumetric molar concentration of mol/L, ammonium persulphate is 5.0 * 10
-3The volumetric molar concentration of mol/L, Potassium Persulphate is 5.0 * 10
-4The persulphate mixing solutions of mol/L, making persulphate mixing solutions total amount is 100ml, under agitation condition, adds 3 of 0.6ml, 4-dioxoethyl thiophene stirred 10 minutes; And under agitation condition; Drip iron nitrate solution and each 10ml of ferric chloride Solution(38 that concentration all is 0.8mol/L more respectively; Stirred about 15 minutes, and dripped each 10ml of the aqueous solution of Iron nitrate, iron protochloride and ferrous sulfate that concentration all is 0.8mol/L more respectively, stirred about 15 minutes; In solution, feed nitrogen, dropping 10ml mass concentration is 25% ammoniacal liquor; At room temperature continue stirring reaction 6 hours, obtain containing α-ferrite (α-FeO (OH))/gather black emulsion of (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod;
2) contain α-ferrite/gather (3 with what step 1) obtained; The 4-dioxoethyl) the black emulsion of thiophene composite Nano rod is according to embodiment 1 step 2) technical scheme implement; Obtain α-ferrite (α-FeO (OH))/gather (3, the 4-dioxoethyl) thiophene (PEDOT) composite Nano rod.This composite Nano rod is the monocrystalline characteristic, and its diameter is about 30nm, and specific conductivity is 4.2 * 10
-2S/cm, saturation magnetization is 50emu/g.
Comparative example
Embodiment is identical with embodiment 1, just in system, removes the persulfate oxidation agent, can not get the form of nanometer rod.
Claims (8)
1. a α-ferrite/gather the preparation method of (3, the 4-dioxoethyl) thiophene composite Nano rod is characterized in that described method may further comprise the steps:
1) the persulfate oxidation agent is joined in the deionized water in the container, stirring and dissolving, obtaining volumetric molar concentration is 1 * 10
-4Mol/L～1 * 10
-2The persulfate solution of mol/L; Making the persulfate solution total amount is 100ml, under agitation condition, adds 3 of 0.1～1ml; Divalent iron salt solution 10～30ml of 4-dioxoethyl thiophene, the ferric salt solution 10～30ml that drips 0.8mol/L and dropping 0.8mol/L; Stir, in solution, feed rare gas element, dropping 10ml mass concentration is 25% ammoniacal liquor; At room temperature continue stirring reaction, obtain containing α-ferrite/gather black emulsion of (3, the 4-dioxoethyl) thiophene composite Nano rod;
2) unreacted reactant is removed in the black emulsion spinning in whizzer that contains α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod that step 1) is obtained; Supernatant liquid is outwelled; It is washing and spinning in 1: 1 water and the ethanol mixed solvent that the black precipitate that obtains is dispersed in volume ratio again, and the repeated centrifugation washing operation is till supernatant liquid is colourless; The black precipitate that obtains at last is 80 ℃ of following vacuum-dryings in temperature, obtains black powder; Be described α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod;
Described trivalent iron salt is iron nitrate, iron(ic)chloride or their mixture;
Described divalent iron salt is Iron nitrate, iron protochloride, ferrous sulfate or any mixture between them.
2. method according to claim 1 is characterized in that: described α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod is the monocrystalline characteristic.
3. method according to claim 1 and 2 is characterized in that: the diameter of described α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod is between 5nm～50nm.
4. method according to claim 3 is characterized in that: the specific conductivity of described α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod is 1 * 10
-3～1 * 10
-1Between the S/cm, saturation magnetization is 15～60emu/g.
5. method according to claim 1 and 2 is characterized in that: the specific conductivity of described α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod is 1 * 10
-3～1 * 10
-1Between the S/cm.
6. method according to claim 5 is characterized in that: the saturation magnetization of described α-ferrite/gather (3, the 4-dioxoethyl) thiophene composite Nano rod is 15～60emu/g.
7. method according to claim 1 is characterized in that: the centrifuge speed during described spinning is 8000～10000rpm.
8. method according to claim 1 is characterized in that: described persulfate oxidation agent is ammonium persulphate, Potassium Persulphate, Sodium Persulfate or any mixture between them.
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|---|---|---|---|---|
| CN101186745A (en) * | 2007-11-09 | 2008-05-28 | 华南理工大学 | Method for preparing polythiophene-metal oxide nano composite material |
| CN101585907A (en) * | 2008-05-21 | 2009-11-25 | 中国科学院理化技术研究所 | The preparation method of conductive polymer poly (3,4 dioxoethyl) thiophene tiny balloon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186745A (en) * | 2007-11-09 | 2008-05-28 | 华南理工大学 | Method for preparing polythiophene-metal oxide nano composite material |
| CN101585907A (en) * | 2008-05-21 | 2009-11-25 | 中国科学院理化技术研究所 | The preparation method of conductive polymer poly (3,4 dioxoethyl) thiophene tiny balloon |
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