CN102240816B - Method for preparing nano nickel by taking nano spherical polyelectrolyte brush as reactor and application of nano nickel - Google Patents
Method for preparing nano nickel by taking nano spherical polyelectrolyte brush as reactor and application of nano nickel Download PDFInfo
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- CN102240816B CN102240816B CN 201110163416 CN201110163416A CN102240816B CN 102240816 B CN102240816 B CN 102240816B CN 201110163416 CN201110163416 CN 201110163416 CN 201110163416 A CN201110163416 A CN 201110163416A CN 102240816 B CN102240816 B CN 102240816B
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Abstract
The invention discloses a method for preparing nano nickel by taking a nano spherical polyelectrolyte brush as a microreactor and an application of the nano nickel. The method comprises the following steps of: preparing polymer microspheres with the particle size of 80-140nm by adopting emulsion polymerization initiated by an oxidation-reduction system; adding a photoinitiator in the terminal stage of the emulsion polymerization, coating the photoinitiator on the surfaces of the polymer microspheres to form a photoinitiator layer, then utilizing an ultraviolet lamp to initiate polyelectrolyte monomers to be polymerized so as to obtain a spherical electrolyte brush with the particle size of 10-400nm; then adding sodium hydroxide to dissociate carboxyl on an electrolyte chain; treating the dissociated spherical polyelectrolyte brush by use of a nickel chloride aqueous solution, thus nickel ions exchange sodium ions and enters into the polyelectrolyte brush; and adding sodium borohydride to reduce the nickel ions into nano nickel in situ, thus finally obtaining controllable nano nickel which are uniformly distributed inside the nano spherical polyelectrolyte brush and have the particle size of 1-14nm. The nano nickel loaded on the spherical polyelectrolyte brush is an ideal efficient nano catalyst.
Description
Technical field
The present invention relates to preparation method and the application thereof of nano nickel, the emulsion polymerisation and the light emulsion polymerisation process that specifically first utilize oxidation-reduction system to cause prepare spherical polyelectrolyte brush, prepare the nano nickel compound particle take spherical polyelectrolyte brush as nano-reactor by the in-situ reducing bivalent nickel ion again, and the nano-complex particle that obtains is used as effective catalyst.
Background technology
When linear polymer chain one end with electric charge is fixed on spherical substrate surface and dense arrangement, due to volume excluding effect and electrostatic repulsion, their free end will be done one's utmost ground and outwards be stretched, and forms a kind of structure as brush, i.e. so-called spherical polyelectrolyte brush.The special structure of spherical polyelectrolyte brush has been strengthened the Donnan effect of polyelectrolyte chain enrichment counter ion greatly, thereby can adsorb and concentrated counter ion, and this phenomenon is particularly remarkable under low ion concentration.Therefore, we can utilize nanometer spherical polyelectrolyte brush to come original position to prepare nano nickel as nano-reactor.
The first inventor of the application in 1999 has realized that first the light emulsion polymerisation prepares nanometer spherical polyelectrolyte brush, soon light trigger is connected on the core surface and trigger monomer in-situ polymerization formation spherical polyelectrolyte brush under UV-irradiation, and adopt this method to synthesize size and brush at the spherical polyacrylic acid brush of 100～200 nanometers and polyvinylbenzenesulfonic acid sodium that (Macromolecules 1999,32,6043).The applicant had prepared the spherical polyelectrolyte brush of magnetic Nano (publication number CN101544730) by the method that coats previously prepared magnetic nanoparticle in core in 2008.
Nano nickel should have high catalytic activity in theory owing to having great specific area, has broad application prospects in chemical catalysis field.The major obstacle that affects at present its application is the size of nano nickel and distributes wayward and easy the reunion.The present invention has found a kind of suitable method can control well the nano nickel of preparation favorable dispersibility and improve its stability.
Summary of the invention
The object of the invention is to solve the problem that exists in above-mentioned preparation nano nickel process, namely control the preparation nano nickel take nanometer spherical polyelectrolyte brush as nano-reactor.Main contents of the present invention are as follows:
Prepare the method for nano nickel take nanometer spherical polyelectrolyte brush as reactor, comprise the steps:
(1) add deionized water, surfactant and peroxide oxidant in reactor, fully after dissolving, add polymer monomer, take out inflated with nitrogen 3～5 times, the rotating speed of stirring is controlled at 200～500 rev/mins; After temperature is raised to 30～40 ℃, the first reducing agent is dissolved in deionized water, be added dropwise to fast described reactor, polymerisation finished after 2～6 hours, obtained nanometer polymer micro emulsion ball; Wherein, polymer monomer: surfactant: peroxide oxidant: the mass ratio of the first reducing agent is 1:0.02～0.05:0.05～0.08:0.01～0.03;
(2) in step (1) the reaction later stage, lentamente light trigger is added drop-wise in reaction system, the addition of described light trigger is equivalent to 1～10% of described polymer monomer quality; Be added dropwise to complete afterreaction 2～4 hours, and namely obtained the micro polymer milk-globule that light trigger coats; Be that the bag filter of 14000 g/mols is dialysed to emulsion with molecular cut off, until the emulsion ionic strength no longer changes;
(3) the micro polymer milk-globule that the described light trigger that obtains in the step that will dialyse (2) coats mixes with water-soluble monomer and adds in Photoreactor, described water-soluble monomer addition be described light trigger coating micro polymer milk-globule solid content 25～100%; Take out inflated with nitrogen 3～5 times, reacted under ultraviolet lighting 2～5 hours, can obtain having the nanometer spherical polyelectrolyte brush of nucleocapsid structure;
(4) add inorganic base in the emulsion of the nanometer spherical polyelectrolyte brush that has nucleocapsid structure described in step (3), stirring reaction 7～24 hours, the inside that makes alkali metal ion in described inorganic base enter the nanometer spherical polyelectrolyte brush of described nucleocapsid structure forms the nanometer spherical polyelectrolyte brush that polyelectrolyte chain dissociates; The addition of described inorganic base be in described nanometer spherical polyelectrolyte brush with nucleocapsid structure the carboxyl mole 50～100%, the solid content of the nanometer spherical polyelectrolyte brush that described polyelectrolyte chain dissociates is 0.8～1.3%;
(5) nanometer spherical polyelectrolyte brush that polyelectrolyte chain described in step (4) is dissociated is placed in ultrafiltration apparatus, adopt the aqueous solution of divalent nickel salt to carry out ultrafiltration as mobile phase, make the nickel ion of described divalent nickel salt and described alkali metal ion carry out the inside that ion-exchange enters the nanometer spherical polyelectrolyte brush that described polyelectrolyte chain dissociates, form the nanometer spherical polyelectrolyte brush that absorption has nickel ion; Then, then carry out the ultrafiltration washing with deionized water, remove free nickel ion; Wherein, the concentration of the divalent nickel salt aqueous solution is 0.0001～0.002 mol/L, and consumption is 1～6 liter, and the consumption of deionized water is 1～3 liter;
(6) absorption that step (5) is obtained has the emulsion of the nanometer spherical polyelectrolyte brush of nickel ion to add in there-necked flask, takes out inflated with nitrogen 3～5 times; Second reductant solution that will be dissolved in deionized water slowly joins in there-necked flask, rate of addition is 3～7 seconds/, temperature is controlled to be 0～60 ℃, and stir speed (S.S.) is to react under 200～500 rev/mins 1～3 hour, the final nano nickel that obtains to load on nanometer spherical polyelectrolyte brush; Mole addition of described the second reducing agent is 2～5 times of nickel ion molar content, and it is 0.1～0.5% that described absorption has the mass fraction of nanometer spherical polyelectrolyte brush in reaction system of nickel ion;
Described the first reducing agent is frerrous chloride or sodium hydrogensulfite;
Described the second reducing agent is sodium borohydride or hydrazine hydrate.
Described surfactant is dodecyl sodium sulfate or neopelex; Described peroxide oxidant is hydrogen peroxide or potassium peroxydisulfate.
Described inorganic base is NaOH or potassium hydroxide.
Described divalent nickel salt is Nickel dichloride hexahydrate or four hydration nickel acetates.
Described water-soluble monomer is acrylic or methacrylic acid, and described polymer monomer is styrene or methyl methacrylate.
Described light trigger is HMEM, and structural formula is as follows:
The chemical equation of preparation light trigger is as follows:
The step of preparation light trigger is: at first, 2-hydroxyl-4 '-hydroxyl-oxethyl-2-aminomethyl phenyl ethyl ketone (HMP) is dissolved in acetone and pours reaction flask into, the pyridine that adds new purifying in this flask, then methacrylic chloride (MC) is added drop-wise in reaction flask, stirs and react end in 10～20 hours; Reacting liquid filtering, the clear liquid chromatography obtains light trigger HMEM; The mass ratio of raw material is HMP: pyridine: MC=1:0.1～0.5:0.1～0.5.
The particle diameter of described nano nickel is 1～14 nanometer, and the standard deviation of particle size is less than 1.
Load on the application of nano nickel in catalytic reaction on nanometer spherical polyelectrolyte brush, the particle diameter of described nano nickel is 1～14 nanometer, and the standard deviation of particle size uses as effective catalyst less than 1.
Described nano nickel is as the application of catalyst in the reaction of catalytic reduction p-nitrophenol, the key step of described catalytic reduction p-nitrophenol reaction is: at first the sodium borohydride reduction agent is added in the aqueous solution of p-nitrophenol, mix, then add the described nano nickel that loads on nanometer spherical polyelectrolyte brush to carry out catalytic reaction, adopt ultraviolet specrophotometer to carry out Real-Time Monitoring to whole course of reaction; Wherein, the concentration of the aqueous solution of p-nitrophenol is at 0.05～0.3 mM/l, and the concentration of sodium borohydride is 5～30 mM/ls, and the content of described nano nickel is in 0.06～0.5 mg/litre.
Advantage of the present invention is as follows: because nanometer spherical polyelectrolyte brush can be in a large number and adsorb equably counter ion, so the nano nickel that synthesize by local reduction way has the dispersiveness of excellence.Simultaneously, can control well particle size and the distribution of nano nickel by the regulation and control reduction reaction conditions, make the nano nickel with outstanding catalytic performance.The application also is applied to as a kind of effective catalyst the reaction that the catalysis p-nitrophenol is reduced to para-aminophenol with this Nano composite granules, shows good catalytic activity.
Description of drawings
Fig. 1 is the high-resolution transmission electron microscope picture of the nano nickel of preparation take nanometer spherical polyelectrolyte brush as nano-reactor;
Fig. 2 has the nanometer spherical polyelectrolyte brush of nano nickel to be reduced to the ultraviolet Real-Time Monitoring curve map of para-aminophenol reaction as the catalyst p-nitrophenol take load;
Fig. 3 is the proton nmr spectra spectrogram of the light trigger HMEM that synthesizes.
The specific embodiment
Below, further illustrate content of the present invention with embodiment, but protection scope of the present invention is not limited in embodiment.To those skilled in the art in the situation that do not deviate from the other changes and modifications that the present invention spirit and protection domain are made, within still being included in protection domain of the present invention.
Embodiment 1
Schotten-Baumann reaction preparation light trigger HMEM
30.0g light trigger 2-hydroxyl-4 '-hydroxyl-oxethyl-2-aminomethyl phenyl ethyl ketone (HMP) pour in the single port flask of 500ml, add 150ml acetone, being stirred to HMP dissolves fully, the pyridine that then adds the new purifying of 10g, continue at low temperatures to stir, then the methacrylic chloride of 13.6g (MC) is dissolved in the acetone of 50ml, and slowly be added drop-wise in reaction flask, dropwise under normal temperature and reacted 12 hours, obtain orange colour liquid, remove by filter the ecru precipitation of bottom, utilize the chromatography method to obtain pure HMEM light trigger, its proton nmr spectra spectrogram as shown in Figure 3.
The light emulsion polymerisation prepares nanometer spherical polyelectrolyte brush
230 ml deionized water, 0.24 gram dodecyl sodium sulfate (or neopelex), 0.74 gram potassium peroxydisulfate (or hydrogen peroxide) are packed in 500 milliliters of there-necked flasks.Fully after dissolving, add 10.0 gram styrene (or methyl methacrylate).Take out inflated with nitrogen 3～5 times, rotating speed is controlled at 300 rev/mins.After temperature is raised to 35 ℃, 0.15 gram sodium hydrogensulfite is dissolved in 20 ml deionized water, be added dropwise in there-necked flask fast.In course of reaction, keep temperature and rotating speed constant all the time, post-polymerization arrived latter stage in 2 hours, and the light trigger HMEM that obtain 1.0 gram embodiment 1 this moment lentamente is added drop-wise in reaction system, and rate of addition is controlled at 7 seconds/drips; Be added dropwise to complete rear continuation reaction 3 hours; Namely obtain the micro polymer milk-globule that the surface is coated with light trigger, dynamic light scattering (DLS) characterization result shows that the hydrodynamics diameter of this spherical polyelectrolyte brush kernel is 120 nanometers, and the solid content that test obtains is 3.14%.Get micro polymer milk-globule and the 1.6 gram acrylic monomers (or methacrylic acid) that 102 gram surfaces are coated with light trigger and be mixed to join in Photoreactor, adding deionized water to gross weight is 400 grams.Take out inflated with nitrogen 3～5 times, reaction is 2.5 hours under ultraviolet lighting, can obtain nanometer spherical polyelectrolyte brush, be after the bag filter of 14000 g/mols is dialysed in deionized water with molecular cut off, the demonstration of DLS characterization result, nanometer spherical polyelectrolyte brush is that 9 o'clock its hydrodynamics diameters are 250 nanometers in the pH value.
Preparation absorption has the nanometer spherical polyelectrolyte brush of nickel ion
Get 50 milliliters of the spherical polyelectrolyte brush emulsions that embodiment 2 obtains, add 0.024 gram sodium hydrate solid, fully stir after 10 hours this emulsion is placed in ultrafiltration apparatus, the nickel chloride aqueous solution that to adopt 3 liters of concentration be 0.001 mol/L (Nickel dichloride hexahydrate or four hydration nickel acetates all can) carries out ultrafiltration, make nickel ion and sodium ion generation ion exchange, enter the inside of nanometer spherical polyelectrolyte brush, carry out the ultrafiltration washing with 3 liters of deionized waters more afterwards, remove free nickel ion, namely obtained adsorbing the nanometer spherical polyelectrolyte brush that nickel ion is arranged.
Control the preparation nano nickel take nanometer spherical polyelectrolyte brush as nano-reactor
Get 50 milliliters of the emulsions of embodiment 3 gained in there-necked flask, take out inflated with nitrogen 3～5 times, 0.03 gram sodium borohydride solids is dissolved in 7.5 gram deionized waters, and slowly be added drop-wise in flask, rate of addition is 5 seconds/, controlling temperature is 30 ℃, and mixing speed is to continue reaction 2 hours under 400 rev/mins, the final nano nickel that obtains to load on nanometer spherical polyelectrolyte brush.As shown in Figure 1, adopting transmission electron microscope observation to get the nano nickel Average Particle Diameters is 7 nanometers (in other embodiment, particle size distribution is in 1～14 nanometers).
Load on the application of nano nickel in the reaction of catalytic reduction p-nitrophenol on nanometer spherical polyelectrolyte brush
at first getting 0.042 milligram of p-nitrophenol is dissolved in 3 ml deionized water, to adopt NaOH that the pH value is transferred to 10, add 1.2 milligrams of sodium borohydride solids, mix, controlling reaction temperature is 15 ℃, adding load to have the nanometer spherical polyelectrolyte brush of nano nickel to make the concentration of nano nickel is 0.163 mg/litre again, after this nano-composite catalyst adds, open ultraviolet specrophotometer course of reaction is carried out Real Time Monitoring at once, discovery is along with the prolongation in reaction time, the absorption peak strength of reactant p-nitrophenol constantly weakens, show higher catalytic activity.Whole catalytic process adopts ultraviolet specrophotometer Real Time Monitoring result as shown in Figure 2, and the absworption peak of 400 nanometers represents the reactant p-nitrophenol.
Claims (5)
1. prepare the method for nano nickel take nanometer spherical polyelectrolyte brush as reactor, it is characterized in that, comprise the steps:
(1) add deionized water, surfactant and peroxide oxidant in reactor, fully after dissolving, add polymer monomer, take out inflated with nitrogen 3～5 times, the rotating speed of stirring is controlled at 200～500 rev/mins; After temperature is raised to 30～40 ℃, the first reducing agent is dissolved in deionized water, be added dropwise to fast described reactor, polymerisation finished after 2～6 hours, obtained nanometer polymer micro emulsion ball; Wherein, polymer monomer: surfactant: peroxide oxidant: the mass ratio of the first reducing agent is 1:0.02～0.05:0.05～0.08:0.01～0.03;
(2) in step (1) the reaction later stage, lentamente light trigger is added drop-wise in reaction system, the addition of described light trigger is equivalent to 1～10% of described polymer monomer quality; Be added dropwise to complete afterreaction 2～4 hours, and namely obtained the micro polymer milk-globule that light trigger coats; Be that the bag filter of 14000 g/mols is dialysed to emulsion with molecular cut off, until the emulsion ionic strength no longer changes;
(3) the micro polymer milk-globule that the described light trigger that obtains in the step that will dialyse (2) coats mixes with water-soluble monomer and adds in Photoreactor, wherein, described water-soluble monomer addition is 25～100% of the micro polymer milk-globule solid content that coats of described light trigger; Take out inflated with nitrogen 3～5 times, reacted under ultraviolet lighting 2～5 hours, can obtain having the nanometer spherical polyelectrolyte brush of nucleocapsid structure;
(4) add inorganic base in the emulsion of the nanometer spherical polyelectrolyte brush that has nucleocapsid structure described in step (3), stirring reaction 7～24 hours, the inside that makes alkali metal ion in described inorganic base enter the nanometer spherical polyelectrolyte brush of described nucleocapsid structure forms the nanometer spherical polyelectrolyte brush that polyelectrolyte chain dissociates; The addition of described inorganic base be in described nanometer spherical polyelectrolyte brush with nucleocapsid structure the carboxyl mole 50～100%, the solid content of the nanometer spherical polyelectrolyte brush that described polyelectrolyte chain dissociates is 0.8～1.3%;
(5) nanometer spherical polyelectrolyte brush that polyelectrolyte chain described in step (4) is dissociated is placed in ultrafiltration apparatus, adopt the aqueous solution of divalent nickel salt to carry out ultrafiltration as mobile phase, make the nickel ion of described divalent nickel salt and described alkali metal ion carry out the inside that ion-exchange enters the nanometer spherical polyelectrolyte brush that described polyelectrolyte chain dissociates, form the nanometer spherical polyelectrolyte brush that absorption has nickel ion; Then, then carry out the ultrafiltration washing with deionized water, remove free nickel ion; Wherein, the concentration of the divalent nickel salt aqueous solution is 0.0001～0.002 mol/L, and consumption is 1～6 liter, and the consumption of deionized water is 1～3 liter;
(6) absorption that step (5) is obtained has the emulsion of the nanometer spherical polyelectrolyte brush of nickel ion to add in there-necked flask, takes out inflated with nitrogen 3～5 times; Second reductant solution that will be dissolved in deionized water slowly joins in there-necked flask, rate of addition is 3～7 seconds/, temperature is controlled to be 0～60 ℃, and stir speed (S.S.) is to react under 200～500 rev/mins 1～3 hour, the final nano nickel that obtains to load on nanometer spherical polyelectrolyte brush; Mole addition of described the second reducing agent is 2～5 times of nickel ion molar content, and it is 0.1～0.5% that described absorption has the mass fraction of nanometer spherical polyelectrolyte brush in reaction system of nickel ion;
Described the first reducing agent is frerrous chloride or sodium hydrogensulfite;
Described the second reducing agent is sodium borohydride or hydrazine hydrate;
Described surfactant is dodecyl sodium sulfate or neopelex; Described peroxide oxidant is hydrogen peroxide or potassium peroxydisulfate;
Described divalent nickel salt is Nickel dichloride hexahydrate or four hydration nickel acetates;
Described polymer monomer is styrene or methyl methacrylate;
Described light trigger is HMEM, and structural formula is as follows:
The chemical equation of preparation light trigger is as follows:
The step of preparation light trigger is: at first, 2 hydroxyl-4 '-hydroxyl-oxethyl-2-aminomethyl phenyl ethyl ketone is dissolved in acetone and pours reaction flask into, the pyridine that adds new purifying in this flask, then methacrylic chloride is added drop-wise in reaction flask, stirs and react end in 10～20 hours; Reacting liquid filtering, the clear liquid chromatography obtains light trigger HMEM; The mass ratio of raw material is 2 hydroxyl-4 '-hydroxyl-oxethyl-2-aminomethyl phenyl ethyl ketone: pyridine: methacrylic chloride=1:0.1～0.5:0.1～0.5.
2. method according to claim 1, is characterized in that, described inorganic base is NaOH or potassium hydroxide.
3. method according to claim 1, is characterized in that, described water-soluble monomer is acrylic or methacrylic acid.
4. method according to claim 1, is characterized in that, the particle diameter of described nano nickel is 1～14 nanometer, and the standard deviation of particle size is less than 1.
5. the application of nano nickel in the catalytic reduction p-nitrophenol that obtain of the arbitrary described method for preparing nano nickel take nanometer spherical polyelectrolyte brush as reactor of claim 1～4, it is characterized in that, the particle diameter of described nano nickel is 1～14 nanometer, and the standard deviation of particle size is less than 1; The key step of described catalytic reduction p-nitrophenol reaction is: at first the sodium borohydride reduction agent is added in the aqueous solution of p-nitrophenol, mix, then add the described nano nickel that loads on nanometer spherical polyelectrolyte brush to carry out catalytic reaction, adopt ultraviolet specrophotometer to carry out Real-Time Monitoring to whole course of reaction; Wherein, the concentration of the aqueous solution of p-nitrophenol is at 0.05～0.3 mM/l, and the concentration of sodium borohydride is 5～30 mM/ls, and the content of described nano nickel is in 0.06～0.5 mg/litre.
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| CN113956478B (en) * | 2021-10-29 | 2023-05-16 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
| CN115301293A (en) * | 2022-07-15 | 2022-11-08 | 华东理工大学 | beta-CD modified polyelectrolyte stable metal nanoparticle, and preparation method and application thereof |
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| CN101259414A (en) * | 2008-03-14 | 2008-09-10 | 南开大学 | Catalyst for p-nitrophenol hydrogenation to prepare p-aminophenol and preparation thereof |
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| JP2005023395A (en) * | 2003-07-04 | 2005-01-27 | Murata Mfg Co Ltd | Production method of nickel powder |
| JP2007009275A (en) * | 2005-06-30 | 2007-01-18 | Mitsui Mining & Smelting Co Ltd | Method for producing nickel particle, nickel particle obtained by using the production method, and electrically conductive paste using the nickel particle |
| KR100795987B1 (en) * | 2006-04-11 | 2008-01-21 | 삼성전기주식회사 | Method for Manufacturing Nickel Nano Particle |
| CN101381435B (en) * | 2008-10-22 | 2011-01-05 | 华东理工大学 | Preparation method of spherical polyelectrolyte brush and use thereof |
| CN101630555B (en) * | 2009-06-17 | 2011-11-23 | 华东理工大学 | Magnetic particles preparation method by using nanometer spherical polyelectrolyte brush as micro-reactor |
| CN101829575A (en) * | 2010-05-17 | 2010-09-15 | 天津市安凯特催化剂有限公司 | Preparation method and application of composite nano nickel catalyst |
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| Title |
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| 杜艳等.纳米镍粉的制备及其对对硝基苯酚催化加氢的影响.《精细石油化工》.2007,第24卷(第6期), |
| 纳米镍粉的制备及其对对硝基苯酚催化加氢的影响;杜艳等;《精细石油化工》;20071130;第24卷(第6期);1-5 * |
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