CN111501203B - Preparation method of catalytic nanofiber membrane - Google Patents

Preparation method of catalytic nanofiber membrane Download PDF

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CN111501203B
CN111501203B CN201910089414.9A CN201910089414A CN111501203B CN 111501203 B CN111501203 B CN 111501203B CN 201910089414 A CN201910089414 A CN 201910089414A CN 111501203 B CN111501203 B CN 111501203B
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dopamine
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CN111501203A (en
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裴小强
刘戈
郭国良
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Ningbo Fotile Kitchen Ware Co Ltd
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Ningbo Fotile Kitchen Ware Co Ltd
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
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    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • D—TEXTILES; PAPER
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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    • D06M2101/02—Natural fibres, other than mineral fibres
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract

The invention relates to a preparation method of a catalytic nanofiber membrane, which is characterized by comprising the following steps: dissolving a polymer in a solvent, and stirring for 3-12 hours at the temperature of room temperature-80 ℃ to prepare a uniform and transparent polymer solution A with the concentration of 5-30 wt%; dissolving dopamine in a Tris-HCl buffer solution with the concentration of 5-50 mM to prepare a dopamine solution B with the concentration of 0.5-10 g/L, and adjusting the pH value of the solution B to 8.0-8.8; respectively filling the solution A and the solution B into a container A and a container B of electrostatic spinning equipment, wherein a nozzle of the container A is used for spinning, a nozzle of the container B is used for spraying, and a dopamine composite nanofiber web is obtained on a collector; and (3) immersing the dopamine composite nanofiber net into a catalyst aqueous solution for 1-12 hours, then washing away floating objects by using deionized water, and drying at the temperature of 20-70 ℃ for 5-12 hours to obtain the catalytic nanofiber membrane with ozonolysis and formaldehyde decomposition functions.

Description

Preparation method of catalytic nanofiber membrane
Technical Field
The invention relates to the field of air purification, in particular to a preparation method of an ozone and formaldehyde catalytic composite nanofiber membrane.
Background
CN201310309595.4 discloses an electrostatic spinning preparation method of manganese dioxide/polyacrylonitrile-based oxidative decomposition formaldehyde type nanofiber membrane, which comprises the following steps: (1) preparing nano manganese dioxide by using potassium permanganate and cyclohexanol through a hydrothermal method, wherein the diameter of the nano manganese dioxide is 50-600 nm; (2) mixing Polyacrylonitrile (PAN) and nano Manganese Dioxide (MD), dissolving in N-N Dimethylformamide (DMF), and stirring to obtain uniformly dispersed electrostatic spinning solution; wherein the mass ratio of MD to PAN is 0.01-0.5: 1; (3) and (3) performing electrostatic spinning by using the prepared electrostatic spinning solution to obtain the manganese dioxide/polyacrylonitrile (MD/PAN) based formaldehyde oxidative decomposition type nanofiber membrane. The nanofiber membrane has the function of oxidizing and decomposing formaldehyde.
However, in the nanofiber membrane, the nano manganese dioxide is directly added into the spinning solution, so that the spinnability of the original spinning solution is reduced, and a part of Mn ions are wrapped in the inside of the fiber, so that the effective utilization rate is reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a catalytic nanofiber membrane which is high in effective utilization rate, can remove particles and can decompose ozone and formaldehyde aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a catalytic nanofiber membrane is characterized by comprising the following steps:
1) preparation of dopamine composite nanofiber
Dissolving a polymer in a solvent, and stirring for 3-12 hours at the temperature of room temperature-80 ℃ to prepare a uniform and transparent polymer solution A with the concentration of 5-30 wt%;
the polymer is selected from at least one of polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polysulfone PSF, polystyrene, cellulose acetate and chitosan;
the solvent is at least one selected from water, ethanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
dissolving dopamine in a Tris-HCl buffer solution with the concentration of 5-50 mM to prepare a dopamine solution B with the concentration of 0.5-10 g/L, and adjusting the pH value of the solution B to 8.0-8.8;
respectively filling the solution A and the solution B into a container A and a container B for electrostatic spinning, wherein a nozzle of the container A is filled for spinning, and a nozzle of the container B is used for spraying, so that a dopamine composite nanofiber web is obtained on a collector;
2) preparation of catalytic composite nanofibers
Preparing an aqueous catalyst solution, saidKMnO in aqueous solution4The concentration is 0.005-0.5 mol/L, and the concentration of the metal salt is 0.005-0.05 mmol/L;
the metal salt is a noble metal salt
Immersing the dopamine composite nanofiber net prepared in the step 1) into a catalyst water solution for 1-12 hours, then washing away floating objects by using deionized water, and drying at 20-70 ℃ for 5-12 hours to obtain the catalytic nanofiber membrane with ozonolysis and formaldehyde decomposition functions.
The noble metal salt is selected from at least one of chloroplatinic acid, chloroauric acid or chloropalladic acid.
The electrostatic spinning in the step 1) comprises the following technological parameters: the flow rate of the injection pump is 3-200 mu L/min, the distance between the needle and the collector is 5-25 cm, the applied voltage is 8-30 KV, the rotating speed of the collector is 300-3000rpm, the spinning temperature is 20-30 ℃, the humidity is 40-70%, and the fiber web is collected on the non-woven fabric.
The flow rate of the injection pump is 5-20 mu L/min, and the voltage is 15-25 KV.
The technological parameters of the electrostatic spraying in the step 1) are as follows: the flow rate of the injection pump B is 0.5-10 mL/h, the distance between a needle head 22G and the collector is 10-25 cm, the voltage applied to the feed liquid side is + 5-20 KV, and the voltage of a receiving roller is-3.0 KV.
The flow rate of the injection pump B is 0.5-5 mL/h, and the voltage is + 5-10 KV.
Compared with the prior art, the method has the advantages that the dopamine composite nanofiber is prepared by combining electrostatic spinning and electrostatic spraying and then is soaked in KMnO4And carrying out oxidation-reduction reaction with a noble metal salt solution to simultaneously form MnOx and noble metal simple substance nano structures on the surface of the modified nano fiber, namely the composite ozone and formaldehyde catalytic nano fiber. The key point of the invention is that the surface of the nanofiber with high specific surface area prepared by electrostatic spinning and spraying is provided with reductive self-polymerizable organic molecules which have strong reducibility and biological adhesion, the dopamine modified nanofiber enters precursor potassium permanganate and noble metal salt solution, and the surface of the nanofiber filament is successfully subjected to the reductive property of dopamineThe MnOx with ozone catalytic activity and the noble metal simple substance nanostructure with formaldehyde catalytic activity are formed, and the noble metal simple substance formaldehyde catalyst can utilize the relative humidity in the air, so that the competitive adsorption effect of the relative humidity in the air on the ozone catalyst can be effectively weakened when the noble metal simple substance is catalytically compounded with the MnOx ozone, and the humidity resistance of the ozone catalyst is improved. Compared with the conventional ozone catalyst, the catalyst has extremely high specific surface area and catalytic activity point positions, is favorable for the decomposition of ozone, and can be used for preparing a composite filter screen by one-step molding with a particulate matter filter screen when preparing air purification and fresh air filter screen products, so that the preparation process and cost of the air purification and fresh air filter screens are greatly reduced.
Drawings
FIG. 1 is an SEM photograph of nanofibers in example 1 of the present invention;
FIG. 2 is an SEM photograph of catalytic nanofibers in example 1 of the present invention;
fig. 3 is a partially enlarged view of fig. 2.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
(1) preparation of nanofibers
Dissolving 12g of polyacrylonitrile in 88g of N, N-dimethylformamide DMF solvent, stirring for 3h at 40 ℃ and the rotating speed of 500rpm to prepare a uniform and transparent polymer solution A;
dissolving dopamine in 10mM Tris-HCl buffer solution to prepare 3g/L dopamine solution B, and adjusting the pH value to 8.5;
respectively loading the solution A and the solution B into two containers of electrostatic spinning equipment, adjusting electrostatic parameters, fixing the flow rate of a solution A injection pump at 15 mu L/min, applying a voltage of 15KV, and setting the distance between a needle and a collector at 15 cm; the flow rate of the injection pump of the solution B is fixed at 1mL/h, the applied voltage is 8KV, the distance between the needle and the collector is 10cm, the rotating speed of the collector is 300rpm, the spinning temperature is 30 ℃, the humidity is 50%, the collector is wrapped with non-woven fabrics, and the dense dopamine composite nanofiber membrane is collected on the non-woven fabric support layer.
Scanning the prepared dopamine composite nanofiber by an electron microscope, and taking a photograph as shown in figure 1.
(2) Preparation of catalytic nanofibers
Soaking the above nanofibers in KMnO solution containing 0.05mol/L4And dissolving the solution containing chloroplatinic acid of 0.01mmol/L for 10 hours, then washing the solution for 3 times by using deionized water, and airing the solution at room temperature to prepare the catalytic nanofiber with the function of decomposing ozone and formaldehyde.
The prepared catalytic nano-fiber is subjected to electron microscope scanning, and the photos are shown in fig. 2 and fig. 3.
As can be seen from fig. 1 and 2 (fig. 3), after being soaked in the catalyst solution, nano particles of MnOx and elemental platinum with the size of 100-160 nm are generated in situ on the surface of the nanofiber membrane and are attached to the surface of the fiber and between the fibers, so that the performance of the catalyst is greatly improved.
The mechanism of ozone decomposition:
(1) first, O3And MnO with MnOXThe vacancy on the surface of the catalyst is combined and dissociative adsorption is carried out, and an oxygen atom is inserted into the oxygen vacancy to form O2-And release one oxygen molecule;
(2) then, another gaseous ozone molecule is reacted with O2-Reacting to form peroxide O in an adsorbed state2 2-Simultaneously release a gaseous oxygen molecule O2；
(3) Finally, peroxide O2 2-And decomposing to form an oxygen molecule, desorbing from the surface of the catalyst, recovering oxygen vacancies, and continuing to participate in the next reaction.
O3+V0→O2+O2-
O3+O2-→O2+O2 2-
O2 2-→O2+V0
Wherein: v0Representing the oxygen vacancies at the surface of the catalyst.
In addition, in the MnOx catalyst, the chemical valence of Mn affects the surfaceThe number of active sites, Mn, was found3 +/Mn4+The larger the value of (A), the lower the average chemical valence of Mn, the more surface oxygen vacancies and the better the catalytic performance.
And carrying out performance test on the prepared composite nanofiber.
Firstly, ozone catalytic performance: the sample size is 15cm multiplied by 15cm, and the sample is put into a testing device, and the airspeed is adjusted to 150000h-1The ozone inlet gas concentration is c0Was 10 ppm. Detecting the concentration c of ozone at the outlet of the pipeline by adopting a Model 202Serial ozone analyzer, detecting the outlet stable concentration, and calculating the ozone removal rate according to the following formula:
Figure BDA0001962806480000041
secondly, formaldehyde catalytic performance: the sample size is 15cm multiplied by 15cm, and the sample is put into a testing device, and the airspeed is adjusted to 150000h-1The feed concentration of formaldehyde was c0 and was 1 ppm. The method comprises the following steps of detecting the concentration c of formaldehyde at the outlet of a pipeline by adopting British Stanford PPM400ST, detecting the stable concentration of the outlet, and calculating the formaldehyde removal rate according to the following formula:
Figure BDA0001962806480000042
thirdly, the filtering performance of the particles is as follows:
the filtering performance of the composite nanofiber membrane is tested by adopting a TSI 8130 type automatic filter material tester, the sample size is 15cm multiplied by 15cm, NaCl aerosol with the mass median diameter of generated particle particles being 0.26um is generated, and the air flow speed is 32L/min.
The filtering efficiency eta of the particles is obtained by testing the concentration of the particles at two ends of the membrane
Figure BDA0001962806480000043
C1As outlet aerosol concentration, C2Is the inlet aerosol concentration.
(3) And (4) performance test results: the catalytic decomposition efficiency of ozone of the sample is 90%, the catalytic efficiency of formaldehyde is 77%, and the filtering performance of PM0.3 is 99%.
Example 2:
(1) preparation of nanofibers
Dissolving 16 polyvinylidene fluoride in 84N, N-dimethylformamide DMF solvent, stirring at 60 ℃ for 12h at the rotating speed of 500rpm, and preparing uniform and transparent polymer solution A;
dissolving dopamine in 10mM Tris-HCl solution buffer solution to prepare 2g/L dopamine solution B, and adjusting the pH value to 8.5;
respectively loading the 2 solutions A and B into two containers of electrostatic spinning equipment, adjusting electrostatic parameters, fixing the flow rate of a solution A injection pump at 20 μ L/min, applying a voltage of 20KV, and setting the distance between a needle and a collector to be 10 cm; the flow rate of the injection pump of the solution B is fixed at 2mL/h, the applied voltage is 15KV, the distance between the needle and the collector is 10cm, the rotating speed of the collector is 300rpm, the spinning temperature is 30 ℃, the humidity is 50%, the collector is wrapped with non-woven fabrics, and the dense dopamine composite nanofiber is collected on the non-woven fabric support layer.
(2) Preparation of catalytic nanofibers
Soaking the nano-fiber in 0.1mol/L KMnO4And dissolving the mixture in 0.01mmol/L chloroauric acid solution for 10h, then washing the mixture for 3 times by using deionized water, and airing the mixture at room temperature to obtain the composite ozone catalytic nanofiber.
(3) And (3) performance testing: the catalytic decomposition efficiency of ozone of the sample is 91%, the catalytic efficiency of formaldehyde is 55%, and the filtering performance of PM0.3 is 92%.
Example 3:
(1) preparation of nanofibers
Dissolving 22 cellulose acetate CA in N, N-dimethylformamide DMF solvent, stirring at 60 deg.C for 12 hr at 500rpm to obtain uniform transparent polymer solution;
dissolving dopamine in 10mM Tris-HCl solution buffer solution to prepare 2g/L dopamine solution B, and adjusting the pH value to 8.5;
respectively loading the 2 solutions A and B into two containers of electrostatic spinning equipment, adjusting electrostatic parameters, fixing the flow rate of a solution A injection pump at 50 mu L/min, applying a voltage of 18KV, and setting the distance between a needle and a collector at 15 cm; the flow rate of the injection pump of the solution B is fixed at 2mL/h, the applied voltage is 15KV, the distance between the needle and the collector is 10cm, the rotating speed of the collector is 300rpm, the spinning temperature is 30 ℃, the humidity is 50%, the collector is wrapped with non-woven fabrics, and the dense dopamine composite nanofiber is collected on the non-woven fabric support layer.
(2) Preparation of catalytic nanofibers
Soaking the nanofibers in KMnO 0.01mol/L4And 0.01mmol/L chloropalladate solution for 10 hours, then washing for 3 times by deionized water, and airing at room temperature to prepare the composite ozone catalytic nanofiber.
(3) And (3) performance testing: the catalytic decomposition efficiency of ozone of the sample is 85%, the catalytic efficiency of formaldehyde is 62%, and the filtering performance of PM0.3 is 95%.

Claims (4)

1. A preparation method of a catalytic nanofiber membrane is characterized by comprising the following steps:
1) preparation of dopamine composite nanofiber
Dissolving a polymer in a solvent, and stirring for 3-12 hours at the temperature of room temperature-80 ℃ to prepare a uniform and transparent polymer solution A with the concentration of 5-30 wt%;
the polymer is selected from at least one of polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polysulfone PSF, polystyrene, cellulose acetate and chitosan;
the solvent is at least one selected from water, ethanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
dissolving dopamine in a Tris-HCl buffer solution with the concentration of 5-50 mM to prepare a dopamine solution B with the concentration of 0.5-10 g/L, and adjusting the pH value of the solution B to 8.0-8.8;
respectively filling the solution A and the solution B into a container A and a container B of electrostatic spinning equipment, wherein a nozzle of the container A is used for spinning, a nozzle of the container B is used for spraying, and a dopamine composite nanofiber web is obtained on a collector;
2) preparation of catalytic nanofibers
Preparing catalyst aqueous solution in which KMnO is contained4The concentration is 0.005-0.5 mol/L, and the concentration of the metal salt is 0.005-0.05 mmol/L;
the metal salt is a noble metal salt
Immersing the dopamine composite nanofiber net prepared in the step 1) into a catalyst water solution for 1-12 hours, then washing away floating objects by using deionized water, and drying at 20-70 ℃ for 5-12 hours to obtain the catalytic nanofiber membrane with ozonolysis and formaldehyde decomposition functions.
2. The method of claim 1, wherein the noble metal salt is at least one selected from chloroplatinic acid, chloroauric acid, and chloropalladic acid.
3. The method for preparing catalytic nanofiber membrane according to claim 1 or 2, characterized in that the electrostatic spinning process parameters of the container a in step 1) are: the flow rate of the injection pump is 3-200 mu L/min, the distance between the needle and the collector is 5-25 cm, the applied voltage is 8-30 KV, the rotating speed of the collector is 300-3000rpm, the spinning temperature is 20-30 ℃, and the humidity is 40-70%;
the technological parameters of electrostatic spraying in the step 1) are as follows: the flow rate of the injection pump B is 0.5-10 mL/h, the distance between a needle and the collector is 10-25 cm, the voltage applied to the feed liquid side is + 5-20 KV, and the voltage of a receiving roller is-3.0 KV;
collecting the web on a nonwoven.
4. The method for preparing the catalytic nanofiber membrane according to claim 3, wherein in the electrostatic spinning process parameters of the solution A, the flow rate of the injection pump is 5-20 μ L/min, and the voltage is 15-25 KV;
in the technological parameters of electrostatic spraying with the solution B, the flow rate of the injection pump B is 0.5-5 mL/h, and the voltage is + 5-10 KV.
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