CN104389110B - Embed polyelectrolyte fibrofelt of zeroth order Nanoscale Iron and preparation method thereof - Google Patents
Embed polyelectrolyte fibrofelt of zeroth order Nanoscale Iron and preparation method thereof Download PDFInfo
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- CN104389110B CN104389110B CN201410575224.5A CN201410575224A CN104389110B CN 104389110 B CN104389110 B CN 104389110B CN 201410575224 A CN201410575224 A CN 201410575224A CN 104389110 B CN104389110 B CN 104389110B
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Abstract
The invention discloses a kind of polyelectrolyte fibrofelt for embedding zeroth order Nanoscale Iron and preparation method thereof.This method comprises the following steps：1) aqueous solution of the aqueous solution of soluble ferric iron salt and polymer dielectric is uniformly mixed so as to obtain after spinning solution, carries out electrostatic spinning, obtain nanofiber mats；2) under anaerobic, by the aqueous solution and step 1 of reducing agent) gained nanofiber mats reacted, reaction finish obtains it is described embed zeroth order Nanoscale Iron polyelectrolyte fibrofelt.Fibrofelt prepared by this method, water stability is good, can effectively fix nano-iron particle, secondary pollution will not be produced in actual applications, is easy to get to recycling, and nano-iron particle is uniformly dispersed, and particle diameter is smaller, does not occur agglomeration.
Description
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of polyelectrolyte fibrofelt for embedding zeroth order Nanoscale Iron and its preparation
Method.
Background technology
In recent years because nano material is different from the peculiar property of traditional material, nanometer technology is set to be obtained in environmental science
Obtained and be widely applied.Nanoscale Iron increasingly draws attention because of its special performance.Because nano iron particles particle diameter is smaller, this causes
It possesses some new capabilities better than common Zero-valent Iron, and such as specific surface area is big, high adsorption capacity, the strong advantage of reproducibility.
Late 1980s, nano zero-valence iron particle is paid close attention to as a kind of effective Dehalogenation reduction agent by people.Recent study
It was found that, Nanoscale Iron can be catalyzed a variety of organohalogen compounds of reduction, such as halogenated alkane, alkenyl halide, halogenated aromatic, organochlorine agriculture
The persistent organic pollutants such as medicine, these pollutants can be converted into nontoxic or low toxicity compound, can while improving it
Biochemical, is that further biodegradation creates favorable conditions.
Nanoscale Iron it is unstable and it is easy reunite, cause itself easily to aoxidize with strong reducing property, so as to lose to pollutant
Reducing power；Nanoscale Iron is nano material simultaneously, and it also can not be ignored to biological eco-toxicity, and be not easily recycled, and cause two
Secondary pollution, therefore have many modifications studied and be directed to Nanoscale Iron.Existing method of modifying mainly has double gold such as Pd/Fe, Ni/Fe
Category method, can slow down Nanoscale Iron and be oxidized, keep the reproducibility of iron；With chitosan, polymethyl methacrylate (PMMA) etc.
Organic matter parcel Nanoscale Iron can also increase its dispersiveness and inoxidizability；Magnetic nano iron provides think of for the recovery of material
Road.
The content of the invention
It is an object of the invention to provide a kind of polyelectrolyte fibrofelt for embedding zeroth order Nanoscale Iron and preparation method thereof.
The method of the polyelectrolyte fibrofelt for the preparation embedding zeroth order Nanoscale Iron that the present invention is provided, comprises the following steps：
1) aqueous solution of the aqueous solution of soluble ferric iron salt and polymer dielectric is uniformly mixed so as to obtain after spinning solution, carries out electrostatic
Spinning, obtains nanofiber mats；
2) under anaerobic, by the aqueous solution and step 1 of reducing agent) gained nanofiber mats reacted, reacted
Finish the polyelectrolyte fibrofelt for obtaining the embedding zeroth order Nanoscale Iron.
The step 1 of the above method) in, soluble ferric iron salt is FeSO4·7H2O or FeCl3；
The concentration of the aqueous solution of the soluble ferric iron salt is 0.02M~0.06M, specially 0.04M；
The polymer dielectric is the polyvinyl alcohol of polyvinyl alcohol, specially model PVA-1799；The polyethylene
The degree of polymerization of alcohol is 1700, and alcoholysis degree is 99%；
In the spinning solution, the mass percentage concentration of polymer dielectric is 6-10%, specially 7.4%.
The step 1) in electrostatic spinning step, spinning temperature is normal temperature；Between syringe needle and the aluminium foil for collecting fibrofelt
Distance is 8cm-12cm；The flow of spinning solution is 5 μ l/min-15 μ l/min.Voltage changes with the change of flow and distance.
It is powered under conditions of polymer solution or several on tape kilovolts of melt to tens of thousands of volt high-pressure electrostatics in the step
Polymer drop is accelerated under the active force of electric field in the Taylor conical points of capillary.When electric field force is sufficiently large, polymerization
Thing liquid drop can overcome surface tension formation injection thread.Solvent evaporation or solidification, finally fall in receiving device in course of injection
On, form non-woven fabrics nanofiber mats.
The step 2) in, reducing agent is NaBH4Or KBH4；The concentration of the aqueous solution of the reducing agent is the solubility
4-6 times of the concentration of aqueous solution of molysite.In reaction progress, fibrofelt is gradually changed into black from light yellow.
In the step, the aqueous solution of reducing agent is added drop-wise to step 1) on gained nanofiber mats when, in nanofiber mats
Etal molysite is in strong reductant (NaBH4、KBH4) in the presence of, elemental metals iron particle is reduced into, specific reaction is as follows：
Fe2++2BH4 -+6H2O→Fe+2B(OH)3+7H2↑
In addition, the polyelectrolyte fibrofelt for the embedding zeroth order Nanoscale Iron that the invention described above is provided, falls within the guarantor of the present invention
Protect scope.Wherein, in the polyelectrolyte fibrofelt, the particle diameter of zeroth order nano iron particles is 5nm~10nm.
The invention provides a kind of polyelectrolyte fibrofelt for embedding zeroth order Nanoscale Iron and preparation method thereof.This method without
It is crosslinked, water insoluble and embedded nano iron fibrofelt is can obtain after being reduced with reducing agent, and the fibrofelt is not dissolved in
Water, water stability is good, can effectively fix nano-iron particle, secondary pollution is not likely to produce in actual applications, easily reclaims profit
With nano-iron particle is uniformly dispersed, and particle diameter is smaller, does not occur agglomeration.
Brief description of the drawings
The figures of the polyelectrolyte fibrofelt SEM containing molysite that Fig. 1 is prepared for the present invention；
The SEM figures for the embedding zeroth order nano-iron particle polyelectrolyte fibrofelt that Fig. 2 is prepared for the present invention；
The EDS figures for the embedding zeroth order nano-iron particle polyelectrolyte fibrofelt that Fig. 3 is prepared for the present invention；
The TEM figures for the embedding zeroth order nano-iron particle polyelectrolyte fibrofelt that Fig. 4 is prepared for the present invention.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed.
The model of polyvinyl alcohol used in following embodiments is PVA-1799, and the degree of polymerization is 1700, and alcoholysis degree is 99%.
Embodiment 1
1) 8g PVAC polyvinylalcohols -1799 are weighed in 90ml water, 90 DEG C of heating on magnetic stirring apparatus are placed in, after dissolving
To the aqueous solution of PVAC polyvinylalcohol -1799；
0.556g FeSO is weighed again4·7H2O, is dissolved in 10ml deionized waters, obtains FeSO4·7H2The O aqueous solution；
By FeSO4·7H2The O aqueous solution is poured into the aqueous solution of PVAC polyvinylalcohol -1799, is stirred, that is, is gathered
Vinyl alcohol PVA-1799 mass percentage concentration is 7.4%, and iron salt concentration is 0.02mol/L spinning solution, then at normal temperatures
Electrostatic spinning is carried out, the distance between aluminium foil of the syringe needle with collecting fibrofelt is 12cm, and the flow of spinning solution is 7 μ l/min, just
Voltage is 12.3KV, and negative voltage is 7kv, obtains nanofiber mats；
2) 0.302g NaBH are weighed4, it is placed in 100ml deionized waters, configuration obtains 0.08mol/L NaBH4It is water-soluble
After liquid, by NaBH4The aqueous solution be progressively added dropwise in step 1) gained nanofiber mats on, yellow fibers felt is changed into black, reaction
After completely, then black fiber felt is put into vacuum drying chamber and dried, obtain the embedded nano iron particle that the present invention is provided
Polyelectrolyte fibrofelt.
1st, SEM test result
SEM results are shown：The nanofiber diameter for wrapping up molysite is 354nm, even thickness；Fibrofelt table after titration
Face form generation changes, into latticed, and absorption binding site is more.
Itself EDS and TEM testing result is compared with Example 1 without substantive difference, and here is omitted.
2nd, EDS test results
EDS profiling results shown in Fig. 3 confirms that elemental iron is distributed in the polyelectrolyte fiber of embedding zeroth order nano-iron particle
In felt.
3rd, TEM test results
TEM test results shown in Fig. 4 shows that the pattern for the nano iron particles being embedded in fibrofelt is circle, shows that this is received
The valence state of rice iron particle is zero-valent state；Because if the ferro element of zero-valent state is oxidized, then the pattern of particle is not circular, but
Tip-like or sheet, therefore comprehensive EDS results understand that the present invention has successfully prepared the polyelectrolyte fiber of embedding zeroth order Nanoscale Iron
Felt, and in the polyelectrolyte fibrofelt, the particle diameter of zeroth order nano iron particles is between 5nm~10nm.
Embodiment 2
1) 8g PVAC polyvinylalcohols -1799 are weighed in 90ml water, 90 DEG C of heating on magnetic stirring apparatus are placed in, after dissolving
To the aqueous solution of PVAC polyvinylalcohol -1799；
0.8125g FeCl is weighed again3, it is dissolved in 10ml deionized waters, obtains FeCl3The aqueous solution；
By FeCl3The aqueous solution pour into the aqueous solution of PVAC polyvinylalcohol -1799, stir, that is, obtain polyvinyl alcohol
PVA-1799 mass percentage concentration is 7.4%, and iron salt concentration is 0.05mol/L spinning solution, is then carried out at normal temperatures quiet
Electrospun, syringe needle is with collecting the distance between aluminium foil of fibrofelt for 10cm, and the flow of spinning solution is 5 μ l/min, and positive voltage is
11KV, negative voltage is 10kv, obtains nanofiber mats；
2) 1.136g NaBH are weighed4, it is placed in 100ml deionized waters, configuration obtains 0.3mol/L NaBH4The aqueous solution
Afterwards, by NaBH4The aqueous solution be progressively added dropwise in step 1) gained nanofiber mats on, yellow fibers felt is changed into black, has reacted
Black fiber felt, is then put into vacuum drying chamber and dries by Quan Hou, obtains the poly- of the embedded nano iron particle that the present invention is provided
Electrolyte fibrofelt.
Obtained using SEM observations, wrap up a diameter of 142nm of the nanofiber of molysite, even thickness, the fibre after titration
Dimension felt configuration of surface is changed, and into latticed, adsorbs binding site many
Received using SEM (ESEM), EDS (power dissipation spectrum), TEM (transmission electron microscope), sign present invention gained embedding
The result difference of the polyelectrolyte fibrofelt of rice iron particle is as follows：
1st, SEM test result
SEM test result shows：As shown in figure 1, the single nanofiber light of the polyelectrolyte prepared using electrostatic spinning
It is sliding uniform, without a beading, do not sticked together between fiber, with substantial amounts of pore structure.
As shown in Fig. 2 the fibrofelt configuration of surface after titration is changed, network structure is formd, surface is thick
Rough, specific surface area is big, there is more absorption binding sites.
Itself EDS and TEM testing result is compared with Example 1 without substantive difference, and here is omitted.
In summary, the present invention has successfully prepared the polyelectrolyte fibrofelt of embedding zeroth order Nanoscale Iron, and in the poly- electricity
Solve in matter fibrofelt, the particle diameter of zeroth order nano iron particles is between 5nm~10nm.
Claims (5)
1. a kind of method for the polyelectrolyte fibrofelt for preparing embedding zeroth order Nanoscale Iron, is following steps：
1）The aqueous solution of the aqueous solution of soluble ferric iron salt and polymer dielectric is uniformly mixed so as to obtain after spinning solution, Static Spinning is carried out
Silk, obtains nanofiber mats；
The soluble ferric iron salt is FeSO4·7H2O or FeCl3；
In spinning solution, the concentration of the aqueous solution of the soluble ferric iron salt is 0.02M ~ 0.06M；
The polymer dielectric is polyvinyl alcohol；The degree of polymerization of the polyvinyl alcohol is 1700 ± 50, and alcoholysis degree is 99%；
In the spinning solution, the mass percentage concentration of polymer dielectric is 6-10%；
2）Under anaerobic, by the aqueous solution of reducing agent and step 1）Gained nanofiber mats are reacted, and reaction is finished
To the polyelectrolyte fibrofelt of the embedding zeroth order Nanoscale Iron.
2. according to the method described in claim 1, it is characterised in that：The step 1）In electrostatic spinning step, spinning temperature is
Normal temperature；The distance between the aluminium foil of syringe needle with collecting fibrofelt is 8cm-12cm；The flow of spinning solution is 5 μ l/min-15 μ l/
min。
3. method according to claim 1 or 2, it is characterised in that：The step 2）In, reducing agent is NaBH4Or KBH4；
The concentration of the aqueous solution of the reducing agent is 4-6 times of the concentration of aqueous solution of the soluble ferric iron salt.
4. the polyelectrolyte fibrofelt for the embedding zeroth order Nanoscale Iron that any methods describeds of claim 1-3 are prepared.
5. polyelectrolyte fibrofelt according to claim 4, it is characterised in that：In the polyelectrolyte fibrofelt, zeroth order
The particle diameter of nano iron particles is 5nm ~ 10nm.
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| CN101445291B (en) * | 2008-12-25 | 2011-06-22 | 东华大学 | In-situ preparation method for functional nullvalent nano-iron/polyelectrolyte composite fibrofelt |
| CN101624757B (en) * | 2009-08-14 | 2011-04-27 | 东华大学 | Preparation of MWCNTs reinforced zero-value nano iron/electrostatic spinning nano fiber felt |
| KR101306859B1 (en) * | 2011-01-06 | 2013-09-10 | 서울대학교산학협력단 | Method for generating nanofiber sheets of lithium titanium oxide-carbon hybrid composite, nanofiber sheets using thereof, lithium ion battery and hybrid supercapacitor having nanofiber sheets |
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