CN109881368B - Preparation method of composite nanofiber membrane with coaxial structure and containing zero-valent iron nanoparticles - Google Patents
Preparation method of composite nanofiber membrane with coaxial structure and containing zero-valent iron nanoparticles Download PDFInfo
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Abstract
The invention discloses a composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles, which is prepared by using polyacrylonitrile as a shell layer material and an iron source as a core layer material and sequentially adopting coaxial electrostatic spinning and high-temperature annealing reduction technologies. The obtained composite nanofiber has uniform diameter and smooth surface; the polyacrylonitrile of the sheath layer is converted into a carbon material after high-temperature annealing treatment, so that the polyacrylonitrile not only can protect the zero-valent Fe nano particles of the core layer from being oxidized by air, but also can be used as an adsorption material to improve the removal effect of organic pollutants and heavy metal ions before and after degradation and reduction; the obtained composite material has excellent degradation performance and stability for catalyzing organic dyes, promotes the application of the composite material in the field of environmental remediation such as organic pollutant degradation and reduction of toxic heavy metal ions, and is favorable for realizing controllable conditions of degradation time; and the related preparation method is simple and has low synthesis cost.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of a composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles.
Background
Azo dyes are the most widely used synthetic dyes in textile printing and dyeing processes, are used for dyeing and printing various natural and synthetic fibers and coloring paints, plastics, rubbers and the like, are not easily decomposed in natural environment, can be converted into toxic and carcinogenic substances, and seriously harm the health and life safety of human beings.
Various methods have been developed to remove and degrade azo dye contamination in water bodies, such as electrochemical degradation, biodegradation, chemical oxidation, and the like. However, these methods have advantages and disadvantages, and are difficult to be popularized and applied in a large scale at low cost. The Fenton-like reaction based on Fenton reaction and improved Fenton-like reaction is considered to be one of the methods with large-scale and low-cost popularization and application prospects.
Fenton, scientist, 1894, sent out through experimentsNow is Fe2+Can promote H2O2Oxidative degradation of tartaric acid. Due to Fe2+By catalytic action of (2) to (H)2O2The oxidizing ability of (a) is remarkably improved. Thus, it is called Fe2+And H2O2The Fenton reagent has the following reaction equation:
Fe2++H2O2→Fe3++OH-+·OH
the capability of degrading pollutants by the hydroxyl radicals generated by the reaction is higher than that of a common oxidant, the oxidation rate is high, and the degradation range is wide. The Fenton reaction equipment is simple, and the experimental conditions are mild. However, in the catalytic degradation process of organic pollutants, the catalytic degradation reaction is required to be continuously carried out, so that the Fenton reaction must be controllably carried out. Researches find that the zero-valent iron nanoparticles serving as the Fenton-like reagent have very high catalytic activity, can catalyze the degradation of various organic pollutants, and can reduce and reduce the pollution of toxic heavy metal ions through the high reduction capacity of the zero-valent iron nanoparticles. The application of the zero-valent iron nanoparticles in the environmental remediation fields of organic pollutant degradation, toxic heavy metal ion reduction and the like is known as a technology with the most application prospect. However, zero-valent iron is easily oxidized, which is not favorable for storage and transportation, and simultaneously, the catalytic efficiency is also reduced; and in the sewage treatment process, the release of zero-valent iron is difficult to control, so that the catalytic reaction is uncontrollable.
Disclosure of Invention
The invention mainly aims to provide a composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles, aiming at the defects in the prior art, the composite nanofiber membrane has excellent organic dye degradation and toxic heavy metal ion reduction performances, and the related preparation method is simple, easy to operate, low in cost and suitable for popularization and application.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles comprises the following steps:
1) dissolving polyacrylonitrile in an organic solvent, and uniformly stirring to obtain a mixed solution I; dissolving an iron source in an organic solvent, and uniformly stirring to obtain a mixed solution II;
2) standing and defoaming the mixed solution I and the mixed solution II, respectively placing the mixed solution I and the mixed solution II in an injector, taking the mixed solution I as a sheath layer spinning solution and the mixed solution II as a core layer spinning solution, and carrying out electrostatic spinning by adopting a coaxial electrostatic spinning instrument to prepare a nanofiber composite membrane;
3) and pre-oxidizing the obtained nanofiber composite membrane, and calcining the membrane in a reducing atmosphere to obtain the composite nanofiber membrane with a coaxial structure and containing the zero-valent iron nanoparticles.
In the scheme, the organic solvent is one or more of N, N-dimethylformamide, dimethyl sulfone, triethylene glycol and the like.
In the scheme, the iron source is one or more of ferric triacetylacetonate, ferroferric oxide, ferric chloride and the like.
In the scheme, the concentration of polyacrylonitrile in the mixed solution I is 10-16 wt%; the concentration of the iron source in the mixed solution II is 1-6 wt%.
In the scheme, the standing and defoaming time is 30-60 min.
In the scheme, the electrostatic spinning process parameters comprise: the spinning temperature is 20-30 ℃, the relative humidity is 45-65%, the spinning positive voltage is 6-10 KV, and the negative voltage is 0-2.5 KV; the injection speed of the sheath spinning solution is 0.04-0.08 mm/min; the injection speed of the core layer spinning solution is 0.01-0.02 mm/min, the receiving distance is 14-20 cm, and the specification of the disposable injector is 5 ml.
Preferably, the outer needle adopted by the sheath layer spinning solution is No. 17, and the inner needle adopted by the core layer spinning solution is No. 23.
In the scheme, the pre-oxidation temperature is 250-280 ℃, and the time is 2-3 h; the preoxidation process enables the sheath layer to form a trapezoidal structure, and is beneficial to improving the stability of the sheath layer.
In the scheme, the reducing atmosphere is argon-hydrogen atmosphere or carbon monoxide argon atmosphere, wherein the volume fraction of hydrogen or carbon monoxide is 5-10%.
In the scheme, the calcining temperature is 500-600 ℃, and the time is 2-4 h.
Preferably, the calcination process comprises: firstly, heating to 45-55 ℃ from room temperature at the speed of 3-5 ℃/min, preserving heat for 20-30 min, then heating to 500-600 ℃ at the speed of 3-5 ℃/min, and preserving heat for 2-4 h.
According to the composite nanofiber membrane with the coaxial structure and containing the zero-valent iron nanoparticles prepared by the scheme, the composite fibers are smooth in surface, uniform in diameter, random in orientation and free of obvious defects, the structure is coaxial, the diameter of the coaxial fibers is 390-680 nm, the outer layer is made of carbon materials, the core layer is made of the zero-valent iron nanoparticles, and the mass percentage of the zero-valent iron nanoparticles is 0.98-3.69%; the catalyst has excellent optical, mechanical, electronic and energy storage capacities, and has good application prospects in the fields of gas adsorption, adsorption of sulfur-containing and nitrogen-containing substances in oil, electrode materials, catalyst carriers and the like.
The principle of the invention is as follows:
the invention successfully prepares PAN/Fe (acac) with a coaxial structure by using common and cheap PAN as a sheath layer (outer layer) and iron source solutions such as ferric triacetylacetone and the like as a core layer spinning solution and adopting a coaxial electrostatic spinning technology3The composite nanofiber membrane is subjected to high-temperature annealing reduction treatment, PAN is converted into a porous carbon material through high-temperature annealing, the zero-valent Fe nano particles in the core layer can be protected and prevented from being oxidized by air, and the porous carbon material can be used as an adsorbing material to improve the removal effect of organic pollutants and heavy metal ions before and after degradation and reduction, so that the obtained composite material shows excellent catalytic organic dye degradation performance and stability; in addition, ferric ions are contained in the core layer of the composite material and are matched with zero-valent Fe nano particles for use, so that the effective combination of the Fenton reaction and the Fenton-like reaction technology can be realized, the degradation efficiency of the composite material is further effectively improved, and the application of the composite material in the field of environment restoration such as organic pollutant degradation and toxic heavy metal ion reduction is promoted.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly provides a method for preparing the composite nanofiber membrane which has a coaxial structure and contains zero-valent iron nano particles by using polyacrylonitrile as a shell layer material and an iron source as a core layer material and sequentially adopting coaxial electrostatic spinning and a high-temperature annealing reduction technology, and innovatively combines the electrostatic spinning technology, the coaxial coating structure, a Fenton reaction and a Fenton-like reaction technology, so that the catalytic degradation performance and the stability of the obtained composite material can be effectively improved, the degradation time can be effectively regulated and controlled, and the degradation process can be controllably regulated.
2) The preparation method provided by the invention is simple, convenient to operate, low in cost and suitable for popularization and application.
3) The composite material obtained by the invention has excellent catalytic organic dye degradation performance and toxic heavy metal ion reduction performance, and has stable catalytic performance and wide applicability.
Drawings
FIG. 1 is a scanning electron micrograph of the product obtained in example 1.
FIG. 2 is a photoelectron spectrum of the product obtained in example 1.
FIG. 3 is a graph showing the degradation spectrum of the product obtained in example 1.
FIG. 4 is a scanning electron micrograph of the product obtained in example 2.
FIG. 5 is a photoelectron spectrum of the product obtained in example 2.
FIG. 6 is a graph showing the degradation spectrum of the product obtained in example 2.
FIG. 7 is a scanning electron micrograph of the product obtained in example 3.
FIG. 8 is a photoelectron spectrum of the product obtained in example 3.
FIG. 9 is a graph showing the degradation spectrum of the product obtained in example 3.
FIG. 10 is a transmission electron microscope image of the composite fiber in the product obtained in example 3.
FIG. 11 is a graph showing Fe contents of products obtained in examples 1 to 3.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles is prepared by the following steps:
1) 0.6610g of polyacrylonitrile is dissolved in 4mL of DMF, magnetic stirring is carried out for 12h, and a mixed solution I (PAN sheath spinning solution) is obtained after uniform mixing; 0.1102g of Fe (acac)3Dissolving in 1mL DMF, magnetically stirring for 12h, and mixing to obtain mixed solution II (Fe (acac)3Core layer spinning solution);
2) standing and defoaming the obtained mixed solution I and the mixed solution II, respectively measuring 4mL of the mixed solution I and the mixed solution II in a 5mL syringe, and discharging bubbles in the syringe; adopt coaxial electrostatic spinning appearance to miscella I is sheath spinning solution, and miscella II is sandwich layer spinning solution, packs into electrostatic spinning machine with two syringes in fixed, sheathes the coaxial syringe needle of electrostatic spinning (the outer syringe needle is No. 17, and interior syringe needle is No. 23), and the distance of adjustment syringe needle and receiver is 16cm, connects the power, sets for the injection parameter, and adjustment voltage and humidity carry out electrostatic spinning according to standard operation, and concrete parameter includes: the spinning temperature is 30 ℃, the relative humidity is 60%, the spinning positive voltage is 8KV, the negative voltage is-2.5 KV, the injection speed of the sheath spinning solution is 0.05mm/min, the injection speed of the core spinning solution is 0.0125mm/min, and the specification of the adopted disposable injector is 5 ml;
3) placing the composite fiber membrane obtained in the step 2) in a forced air drying oven, and pre-oxidizing for 2.5h at 250 ℃; and then placing the membrane in an argon-hydrogen atmosphere (the volume fraction of hydrogen is 5%) and a high-temperature tube furnace to heat to 550 ℃ and calcine for 3h, and then naturally cooling to obtain the composite nanofiber membrane with the coaxial structure and containing the zero-valent iron nanoparticles.
FIG. 1 is a scanning electron micrograph of the product obtained in this example, and the result shows that the obtained product is a composite nanofiber membrane with uniform diameter; FIG. 2 is a photoelectron spectrum of the product obtained in this example, showing Fe in the core layer of the product3+Is successfully reduced and the core layer is simultaneously coated with Fe3+、Fe2+And Fe0. FIG. 11 is a graph showing the iron content of the product obtained in this example, and the result shows that the mass percentage of iron in the product obtained is 0.98%.
Taking 10mg of the composite nanofiber membrane obtained in the embodiment, placing the composite nanofiber membrane in 18mL of deionized water, adding 2mL of 0.1g/L methylene blue aqueous solution and 1mL of hydrogen peroxide, placing the mixed solution in a constant-temperature shaking box at 37 ℃, taking 1mL of liquid in a 1.5mL centrifuge tube when 1, 2, 3, 4, 5, 6, 9 and 12 hours, centrifuging at 8000r/min for 5min, taking 200uL of supernatant in a 96-well plate, and detecting the absorbance value at 664nm, wherein the result is shown in figure 3.
FIG. 3 is a graph of the spectrum obtained by degrading methylene blue with the product obtained in this example, and the result shows that the methylene blue is completely degraded after 12 h.
Example 2
A composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles is prepared by the following steps:
1) 0.6688g of polyacrylonitrile is dissolved in 4mL of DMF, magnetic stirring is carried out for 12h, and a mixed solution I (PAN sheath spinning solution) is obtained after uniform mixing; 0.1672g of Fe (acac)3Dissolving in 1mL DMF, magnetically stirring for 12h, and mixing to obtain mixed solution II (Fe (acac)3Core layer spinning solution);
2) standing and defoaming the obtained mixed solution I and the mixed solution II, respectively measuring 4mL of the mixed solution I and the mixed solution II in a 5mL syringe, and discharging bubbles in the syringe; adopt coaxial electrostatic spinning appearance to miscella I is sheath spinning solution, and miscella II is sandwich layer spinning solution, packs into electrostatic spinning machine with two syringes in fixed, sheathes the coaxial syringe needle of electrostatic spinning (the outer syringe needle is No. 17, and interior syringe needle is No. 23), and the distance of adjustment syringe needle and receiver is 16cm, connects the power, sets for the injection parameter, and adjustment voltage and humidity carry out electrostatic spinning according to standard operation, and concrete parameter includes: the spinning temperature is 25 ℃, the relative humidity is 55%, the spinning positive voltage is 9KV, the negative voltage is-1.5 KV, the injection speed of the sheath spinning solution is 0.05mm/min, the injection speed of the core spinning solution is 0.0125mm/min, and the specification of the adopted disposable injector is 5 ml;
3) placing the composite fiber membrane obtained in the step 2) in a forced air drying oven, and pre-oxidizing for 2.5h at 250 ℃; and then placing the membrane in a high-temperature tube furnace under argon-hydrogen atmosphere (the volume fraction of hydrogen is 5%) to heat up to 50 ℃ at the speed of 5 ℃/min and keep the temperature for 30min, then heating up to 550 ℃ at the speed of 5 ℃/min and keeping the temperature for 3h, and then naturally cooling to obtain the composite nanofiber membrane with the coaxial structure and containing the zero-valent iron nanoparticles.
FIG. 4 is a scanning electron micrograph of the product obtained in this example, which shows that the product obtained is a composite nanofiber membrane with uniform diameter; FIG. 5 is a photoelectron spectrum of the product obtained in this example, showing Fe in the core layer of the product3+Is successfully reduced, and the core layer is coated with Fe3+、Fe2+And Fe0. FIG. 11 is a graph showing the iron content of the product obtained in this example, and the result shows that the mass percentage of iron in the product obtained is 2.26%.
Taking 10mg of the composite nanofiber membrane obtained in the embodiment, placing the composite nanofiber membrane in 18mL of deionized water, adding 2mL of 0.1g/L methylene blue aqueous solution and 1mL of hydrogen peroxide, placing the mixed solution in a constant-temperature shaking box at 37 ℃, taking 1mL of liquid in a 1.5mL centrifuge tube when 1, 2, 3, 4, 5, 6, 9 and 12 hours, centrifuging at 8000r/min for 5min, taking 200uL of supernatant in a 96-well plate, and detecting the absorbance value at 664nm, wherein the result is shown in figure 6.
FIG. 6 is a graph of the spectrum obtained by degrading methylene blue with the product obtained in this example, and the result shows that the methylene blue is completely degraded after 9 h.
Example 3
A composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles is prepared by the following steps:
1) 0.6768g of polyacrylonitrile is dissolved in 4mL of DMF, magnetic stirring is carried out for 12h, and a mixed solution I (PAN sheath spinning solution) is obtained after uniform mixing; 0.2256g of Fe (acac)3Dissolving in 1mL DMF, magnetically stirring for 12h, and mixing to obtain mixed solution II (Fe (acac)3Core layer spinning solution);
2) standing and defoaming the obtained mixed solution I and the mixed solution II, respectively measuring 4mL of the mixed solution I and the mixed solution II in a 5mL syringe, and discharging bubbles in the syringe; adopt coaxial electrostatic spinning appearance to miscella I is sheath spinning solution, and miscella II is sandwich layer spinning solution, packs into electrostatic spinning machine with two syringes in fixed, sheathes the coaxial syringe needle of electrostatic spinning (the outer syringe needle is No. 17, and interior syringe needle is No. 23), and the distance of adjustment syringe needle and receiver is 16cm, connects the power, sets for the injection parameter, and adjustment voltage and humidity carry out electrostatic spinning according to standard operation, and concrete parameter includes: the spinning temperature is 20 ℃, the relative humidity is 50%, the spinning positive voltage is 7.6KV, the negative voltage is 0KV, the injection speed of the sheath spinning solution is 0.05mm/min, the injection speed of the core spinning solution is 0.0125mm/min, and the specification of the adopted disposable injector is 5 ml;
3) placing the composite fiber membrane obtained in the step 2) in a forced air drying oven, and pre-oxidizing for 2.5h at 250 ℃; and then placing the membrane in a high-temperature tube furnace under argon-hydrogen atmosphere (the volume fraction of hydrogen is 5%) to heat up to 50 ℃ at the speed of 5 ℃/min and keep the temperature for 30min, then heating up to 550 ℃ at the speed of 5 ℃/min and keeping the temperature for 3h, and then naturally cooling to obtain the composite nanofiber membrane with the coaxial structure and containing the zero-valent iron nanoparticles.
FIG. 7 is a scanning electron micrograph of the product obtained in this example, which shows that the product obtained is a composite nanofiber membrane with uniform diameter; FIG. 8 is a photoelectron spectrum of the product obtained in this example, showing Fe in the core layer of the product3+Is successfully reduced, and the core layer is coated with Fe3+、Fe2+And Fe0. FIG. 11 is a graph showing the iron content of the product obtained in this example, and the result shows that the mass percentage of iron in the product obtained is 3.69%.
Taking 10mg of the composite nanofiber membrane obtained in the embodiment, placing the composite nanofiber membrane in 18mL of deionized water, adding 2mL of 0.1g/L methylene blue aqueous solution and 1mL of hydrogen peroxide, placing the mixed solution in a constant-temperature shaking box at 37 ℃, taking 1mL of liquid in a 1.5mL centrifuge tube when 1, 2, 3, 4, 5, 6, 9 and 12 hours, centrifuging at 8000r/min for 5min, taking 200uL of supernatant in a 96-well plate, and detecting the absorbance value at 664nm, wherein the result is shown in figure 9.
FIG. 9 is a graph of the spectrum obtained by degrading methylene blue with the product obtained in this example, and the result shows that most of the methylene blue is degraded after 6 hours; before 9h, the methylene blue was completely degraded. FIG. 10 is a TEM image of the product obtained in this example, and it was found that the product obtained contained nano Fe particles with a size of 5-10 nm.
The invention can be realized by all the listed raw materials, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials; the examples are not to be construed as limiting the scope of the invention. The upper and lower limit values and interval values of the process parameters can realize the invention, and the embodiments are not listed.
Claims (7)
1. A preparation method of a composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles is characterized by comprising the following steps:
1) dissolving polyacrylonitrile in an organic solvent, and uniformly stirring to obtain a mixed solution I; dissolving an iron source in an organic solvent, and uniformly stirring to obtain a mixed solution II;
2) standing and defoaming the mixed solution I and the mixed solution II, respectively placing the mixed solution I and the mixed solution II in an injector, taking the mixed solution I as a sheath layer spinning solution and the mixed solution II as a core layer spinning solution, and carrying out electrostatic spinning by adopting a coaxial electrostatic spinning instrument to prepare a nanofiber composite membrane;
3) pre-oxidizing the obtained nanofiber composite membrane, and calcining the obtained nanofiber composite membrane in a reducing atmosphere to obtain a composite nanofiber membrane with a coaxial structure and containing zero-valent iron nanoparticles;
the organic solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide and triethylene glycol;
the iron source is one or more of ferric triacetylacetonate, ferroferric oxide and ferric chloride.
2. The preparation method according to claim 1, wherein the concentration of polyacrylonitrile in the mixed solution I is 10-16 wt%; the concentration of the iron source in the mixed solution II is 1-6 wt%.
3. The method of claim 1, wherein the electrospinning process parameters comprise: the spinning temperature is 20-30 ℃, the relative humidity is 45-65%, the spinning positive voltage is 6-10 KV, and the negative voltage is 0-2.5 KV; the injection speed of the sheath spinning solution is 0.04-0.08 mm/min; the injection speed of the core layer spinning solution is 0.01-0.02 mm/min, and the receiving distance is 14-20 cm.
4. The preparation method according to claim 1, wherein the pre-oxidation temperature is 250-280 ℃ and the time is 2-3 h.
5. The method according to claim 1, wherein the reducing atmosphere is an argon-hydrogen atmosphere or a carbon monoxide-argon atmosphere, and the volume fraction of hydrogen or carbon monoxide is 5-10%.
6. The preparation method according to claim 1, wherein the calcination temperature is 500 to 600 ℃ and the calcination time is 2 to 4 hours.
7. The composite nanofiber membrane with the coaxial structure and containing the zero-valent iron nanoparticles prepared by the preparation method of any one of claims 1 to 6, wherein the composite fibers in the composite nanofiber membrane are in the coaxial structure, the diameter of the coaxial fibers is 390 to 680nm, the outer layer is made of carbon material, and the core layer is made of the zero-valent iron nanoparticles, wherein the mass percentage of the zero-valent iron nanoparticles is 0.98 to 3.69 percent.
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