CN111185243B - Composite silver carbon fiber catalyst and preparation method thereof - Google Patents
Composite silver carbon fiber catalyst and preparation method thereof Download PDFInfo
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- CN111185243B CN111185243B CN202010029828.5A CN202010029828A CN111185243B CN 111185243 B CN111185243 B CN 111185243B CN 202010029828 A CN202010029828 A CN 202010029828A CN 111185243 B CN111185243 B CN 111185243B
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 86
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/394—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention provides a composite silver carbon fiber catalyst and a preparation method thereof, wherein the preparation method comprises the steps of firstly adopting a composite plasticizer containing silver nitrate to swell and modify polyvinyl alcohol, then carrying out melt spinning on the plasticized polyvinyl alcohol through extrusion-spinning equipment, and then carrying out PVA/AgNO treatment on the obtained PVA/AgNO3And carrying out thermal transformation reaction on the composite fiber to finally obtain the composite silver carbon fiber catalyst. The technical scheme of the invention has simple process steps, is suitable for large-scale industrial production, and the prepared composite silver carbon fiber catalyst product is pure and has the excellent characteristics of high efficiency, recycling and easy separation and recovery when being applied to the reduction of catalytic p-nitrophenol.
Description
Technical Field
The invention belongs to the technical field of fiber catalysts, particularly relates to a silver fiber catalyst, and particularly relates to a composite silver carbon fiber catalyst and a preparation method thereof.
Background
The nano silver particles are an important member of the noble metal nano particles, have very stable physical and chemical properties such as unique optical, electrical and catalytic properties, and can be widely applied to physics, photoelectricity, information storage, antibiosis, catalytic materials, battery electrode materials, low-temperature heat conduction materials and conductive materials. It is noteworthy that silver nanoparticles, as a noble metal particle with a large specific surface area, show its unique potential in the catalytic field of reactions in liquid phase, but are prone to agglomeration due to the interaction between nanoparticles. Therefore, in order to exert its inherent excellent catalytic performance, there has been a study of supporting silver nanoparticles in various types of matrices, and fibers, films, foams, and the like are widely used due to their large porosity and supported area. The fiber is a one-dimensional material with high aspect ratio, good permeability and large specific surface area, and a great deal of research is carried out in the direction of loading silver nanoparticles as a catalyst material.
The silver-containing nano composite material is prepared by dispersing presynthesized silver nanoparticles into a high molecular solution and realizing the loading of the fibers on the silver nanoparticles through a spinning technology, but the silver nanoparticles can be agglomerated in the spinning process due to the high viscosity of the high molecular material, and the silver nanoparticles are wrapped by the high molecular material in the fibers to cause the agglomerationThe distribution uniformity of the silver particles on the surface of the substrate is reduced, and the appearance and the like of the silver particles are not well controlled, so that the catalytic efficiency of the catalyst is greatly reduced. To solve the above problems, Liu et al (Liu Y, Jiang G, Li L, et al. silver nanoparticles supported on electrophoretic nitrile rubbers of bacteria of the genus for catalytic applications [ J]MRS Communications,2016,6(01):31-40.) discloses that the load of silver nanoparticles on polyacrylonitrile fibers is realized by adopting an electrostatic spinning and silver mirror reaction-based post-treatment technology, and the method is used for catalytic experiments of p-nitrophenol, and realizes complete reaction and continuous and efficient 7-time circulation of p-nitrophenol with a certain concentration within 1 hour. In order to realize the uniform distribution of the silver nano particles on the surface of the catalyst, the catalytic efficiency is improved to 0.375min-1.g-1. ZHao et al (Alginate fibers embedded with silver nanoparticles as an effective catalyst for the reduction of 4-nitrophenol [ J)]RSC adv.2015,5(61): 49534) 49540) silver mirror reaction is utilized to prepare alginic acid fiber with silver-containing surface, the alginic acid fiber is used for reduction catalysis of p-nitrophenol, the complete reaction is successfully realized within 15 minutes, simultaneously, the stable catalytic reaction of ten cycles is completed, and the catalytic efficiency is improved to 69.2min-1.g-1(ii) a Baruah et al (Baruah B. in Situ and furniture Synthesis of Silver nanoparticies on Baby Wipe and Their Applications in Catalysis and SERS [ J.]Rsc Advances,2016,6(6):5016--1.g-1The reduction reaction of p-nitrophenol is completed within 6 minutes. Torkamani et al (Torkamani F, Azizian S.Green and simple synthesis of Ag nanoparticles loaded on to cellular fibers as effect and low-cost catalyst for reduction of 4-nitrophenol [ J]Journal of Molecular Liquids,2016,214:270-275.) silver ions are loaded on the fabric through reduction of ethanol ultraviolet light, so that reduction of p-nitrophenol within 325s is realized, and the catalytic efficiency reaches 0.06min- 1.g-1. Tianxianglan et al (Tianxiang L, Rui A, Zheng L, et al. furniture failure of a bioglass-based film with interwoven fibers network)structure as heterogeneous catalysis platform[J]The silver-containing collagen composite membrane is prepared by self-assembling modified silver nanoparticles synthesized in situ and collagen fibers, the interwoven network structure of the silver-containing collagen composite membrane provides higher specific surface area for the assembly of the silver particles, the silver-containing collagen composite membrane has excellent catalytic activity in the reduction of p-nitrophenol, and the catalytic efficiency reaches 0.91min-1.g-1And the high stability of the cross-linked composite membrane enables the composite catalyst to be recycled for up to ten cycles.
As described in the above-mentioned technical documents, in order to prepare a silver-containing nanoparticle composite fiber catalyst with high catalytic performance, the prior research focuses on achieving uniform dispersion of silver nanoparticles and preventing agglomeration due to surface tension of the particles, increasing the total exposure of the catalyst matrix to the silver nanoparticles, and simultaneously achieving the recycling of the strong adhesion of the silver nanoparticles in the matrix. Therefore, although the methods of self-assembly, coating reduction, in-situ reduction, etc. are mostly performed on the fiber substrate, modification of the silver nanoparticles to increase the adhesion between the silver nanoparticles and the substrate blurs the surface microstructure of the particles, thereby reducing the catalytic activity of the silver nanoparticles to some extent. Meanwhile, the process has the problems of high cost, incomplete surface modification reaction and the like, so that the purity of the catalyst is problematic. (Patel A C, Li S, Wang C, et al. electrospining of Porous silicon Nanoparticles composites for Catalytic Applications [ J ]. Chemistry of Materials,2007,19(6):1231-1238.)
PVA has excellent chemical stability, thermal stability, good water solubility, and the like, and is widely used in paints, adhesives, textile slurries, dispersants, films, fibers, and the like. The molecular chain of PVA contains a large amount of hydroxyl, and lone-pair electrons of oxygen atoms on the hydroxyl can enter a vacant orbit d or f of metal ions to form coordination bonds, so that PVA is often used as a stabilizer for preventing metal nanoparticles from agglomerating and a weaker reducing agent in the preparation process of the metal nanoparticles. Therefore, many studies at home and abroad adopt in-situ reductionPreparing PVA/Ag nano composite material, and preparing PVA/AgNO by blending PVA water solution and silver nitrate solution3The composite material is then treated by post-treatment methods such as UV irradiation, chemical reduction, microwave treatment and conventional heat treatment to reduce silver ions in a PVA matrix (Yong G, Bai S, Hu S, et al]Rsc Advances,2016,6(61), the size, distribution and morphology of the silver nanoparticles produced can also be adjusted by varying the treatment conditions, such as time and temperature, during the in situ reduction. The composite material containing the nano silver particles can be prepared by utilizing the interaction between the polyvinyl alcohol and the silver nitrate, but the contact area between the silver particles and the reaction liquid is reduced to a certain extent due to the wrapping of the polymer matrix around the nano silver particles, and the catalytic activity of the nano silver particles can be correspondingly reduced due to the reduction of the active reaction area.
Therefore, it is very important to find a preparation method of the silver-containing nanoparticle composite fiber catalyst with simple process and high catalytic efficiency.
Disclosure of Invention
The invention aims to solve the problems in the background art and provides a composite silver carbon fiber catalyst and a preparation method thereof, the preparation method has simple process steps and is suitable for large-scale industrial production, the prepared composite silver carbon fiber catalyst product is pure, and the composite silver carbon fiber catalyst has the excellent characteristics of high efficiency, recycling and easy separation and recovery when being applied to catalysis such as reduction of p-nitrophenol, selective oxidation of benzyl alcohol and the like.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
The preparation method of the composite silver carbon fiber catalyst comprises the following steps of:
(1) using silver nitrate (AgNO)3) The swelling modification of the composite plasticizer is 50-70 parts of polyvinyl alcohol (PVA), and the composite plasticizer comprises the following components:
2.5 to 15 parts of silver nitrate,
30-40 parts of water;
(2) carrying out melt spinning on the plasticized polyvinyl alcohol obtained in the step (1) through an extrusion-spinning device to obtain PVA/AgNO3Composite fibers;
(3) mixing PVA/AgNO obtained in the step (2)3And carrying out thermal transformation reaction on the composite fiber, namely carrying out oxidation reduction reaction on the polyvinyl alcohol and the silver nitrate, carrying out thermal oxidative degradation on the polyvinyl alcohol to form carbon, and reducing the silver nitrate into metal silver particles and nitrogen oxide by the polyvinyl alcohol to finally obtain the composite silver carbon fiber catalyst.
The polyvinyl alcohol can be a general industrial product, and further preferably has a polymerization degree of 500-2400 and an alcoholysis degree of 85-99%.
In general, the swelling modification described in step (1) is a prior art means of plasticization, and the specific technical means thereof can be referred to the relevant prior art documents (e.g., Chen N, Li L, Wang Q. New technology for thermal processing of poly (vinyl alcohol) [ J ]. Polymer Materials Science & Engineering,2014,36(7-8): 283. 290./Angel, Li, Chening, Weiwei, Liujiahua, Huazhengkun; a method for preparing high performance polyvinyl alcohol fibers,/Angel, Li, Chening, et al. research on thermoplastic processing of polyvinyl alcohol [ J. Science and Engineering of high molecular Materials, 2014,30(2): 192. 197. Li. fusion spinning of high modulus polyvinyl alcohol fibers and properties [ D ]. Sichuan ], university for the purpose of enabling melt spinning of high modulus polyvinyl alcohol fibers, in order to better illustrate the invention and provide a preferable technical scheme, the swelling modification comprises the following specific steps:
will contain silver nitrate (AgNO)3) The composite plasticizer is added into polyvinyl alcohol for mixing, stirred and mixed for 10-30 minutes at the temperature of 20-90 ℃, and then sealed and kept stand for 1-2 days, so that the plasticized polyvinyl alcohol is obtained.
Wherein, water in the composite plasticizer is used as a solvent of silver nitrate, and in order to inhibit evaporation of water components of the composite plasticizer during melt spinning and realize overheating of water in polyvinyl alcohol, the applicant of the present invention specifically refers to the prior patent issued by the applicant of the present invention "a method for preparing high performance polyvinyl alcohol fiber" (application No. 200510057435.0) and "a novel plasticizing method for thermoplastic processing of polyvinyl alcohol film" (application No. CN01107094.3), preferably, the composite plasticizer further comprises the following components:
0.5 to 5 parts of a nitrogen-containing organic solvent,
or/and
0.5-10 parts of a polyhydric alcohol organic solvent.
Further preferably, the nitrogen-containing organic solvent is caprolactam or acetamide; the polyalcohol organic solvent is glycerol or ethylene glycol or polyethylene glycol with molecular weight less than or equal to 800.
In general, the melt spinning performed by the extrusion-spinning apparatus in the step (2) is melt spinning performed by using an existing extrusion-spinning apparatus, and in general, the plasticized polyvinyl alcohol obtained in the step (1) is processed into round or special-shaped polyvinyl alcohol fibers with uniform texture and fineness of 60 to 200dtex, in order to better illustrate the invention, a preferable technical scheme is provided, and the process parameters of the melt spinning performed by the extrusion-spinning apparatus are as follows: the spinning temperature is 130-180 ℃, the aperture of a spinneret plate is 0.12-0.4 mm, the drawing ratio of the spinneret plate is 1-4 times, the side blowing cooling temperature is 10-80 ℃, and the humidity is 65-85%.
Generally, under the condition that the oxidation-reduction reaction of the polyvinyl alcohol and the silver nitrate is performed in the step (3), the polyvinyl alcohol is thermally and oxidatively degraded to carbon, and the silver nitrate is reduced to metallic silver particles and nitrogen oxide by the polyvinyl alcohol, a person skilled in the art can select suitable conditions for the thermal-variation reaction according to factors such as different silver nitrate contents in raw materials, different melt spinning process conditions, and the like, and preferably, the thermal-variation reaction in the step (3) has the following reaction conditions for better describing the invention and providing reference for relevant process parameters: the temperature is 200-600 ℃, the reaction time is 3-60 min, and the atmosphere is any one of nitrogen, oxygen and argon;
the composite silver carbon fiber catalyst prepared by the method is applied to catalytic reaction of reduction of p-nitrophenol for catalyzingThe efficiency is improved to 80-200 min-1g-1And good catalytic stability is kept, and the catalyst can be recycled for more than 8 times.
The principle of the invention is as follows: the method is characterized in that the complexation of lone pair electrons of oxygen atoms on polyvinyl alcohol hydroxyl and silver ion empty tracks is utilized, polyvinyl alcohol solution is adopted to plasticize polyvinyl alcohol powder, hydrogen bonds are reconstructed by water molecules and hydroxyl groups on polyvinyl alcohol molecular chains, a compound complex is formed by silver ions and the hydroxyl groups to destroy the original molecular hydrogen bonds between the molecular chains, the crystallinity of the polyvinyl alcohol is reduced, a thermoplastic processing window is obtained, the double plasticization is beneficial to melt spinning of the polyvinyl alcohol/silver nitrate composite material, meanwhile, the addition of small molecules is beneficial to stable flowing of a composite melt, and stable continuous melt spinning of the polyvinyl alcohol/silver nitrate composite material is realized. Meanwhile, the complexing action of hydroxyl and silver ions can realize the uniform dispersion of silver nitrate in a polyvinyl alcohol matrix, the thermal change reaction of the silver nitrate and the polyvinyl alcohol matrix is initiated at the temperature of 200-600 ℃, the polyvinyl alcohol matrix is oxidized and degraded into carbon, the silver nitrate is reduced into silver particles and nitric oxide, in the reaction process, the volatilization of gas molecules is beneficial to forming the appearance of a loose carbon layer, and the silver particles are uniformly fixed in the loose carbon layer. The prepared composite silver carbon fiber catalyst is used for reducing p-nitrophenol, and the loose carbon layer structure is beneficial to the immersion of reaction liquid and fully contacts and reacts with internal silver particles, so that the catalytic efficiency of the catalyst is greatly improved.
The invention has the following advantages:
(1) according to the technical scheme, double plasticization of polyvinyl alcohol is carried out by utilizing the destruction of hydrogen bonds in the PVA after swelling modification and the complexing action of silver nitrate and PVA hydroxyl, so that the polyvinyl alcohol meets the thermoplastic processing requirement of the polyvinyl alcohol on one hand, and the uniform dispersion of the silver nitrate in a polyvinyl alcohol matrix is realized on the other hand;
(2) the technical scheme of the invention breaks through the technical prejudice that the uniform dispersion of silver nanoparticles and the prevention of agglomeration caused by the surface tension of the particles can be better realized only by considering the self-assembly, the coating reduction and the in-situ reduction on a fiber matrix in the cognition of the prior art, and provides a brand-new preparation method of the composite silver carbon fiber catalyst;
(3) in the technical scheme of the invention, the water solubility of the silver nitrate enables the silver nitrate to be well dissolved in the composite modifier, thereby preparing AgNO3Uniformly distributed PVA/AgNO3The composite fiber ensures the uniform distribution of the next step of thermotropic nano silver particles;
(4) according to the technical scheme, the polyvinyl alcohol is thermally oxidized and degraded into the microporous carbon layer network after the thermal transformation reaction, so that the reaction liquid can be immersed conveniently, the silver nano particles are compositely deposited in the microporous carbon layer network, the reaction area of the nano silver particles and the reaction liquid of the silver carbon fibers under the catalysis condition is increased, and the catalysis efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of the preparation steps and applications of example 1 of the present invention.
FIG. 2 shows PVA/AgNO obtained in step (2) of example 1 of the present invention3And (3) a cross-sectional electron microscope photograph of the composite fiber.
FIG. 3 shows PVA/AgNO obtained in step (2) of example 1 of the present invention3Surface electron microscope photograph of the composite fiber.
Fig. 4 is an electron microscope photograph of the composite silver carbon fiber catalyst prepared in example 1 of the present invention.
FIG. 5 is an electron microscope photograph of the surface morphology of the composite silver carbon fiber catalyst prepared in example 1 of the present invention.
Fig. 6 is an electron microscope photograph of the inside of the composite silver carbon fiber catalyst fiber prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
It is noted that the catalytic reaction for the selective reduction of p-nitrophenol described in the following examples, the reaction conditions were:
0.01g of p-nitrophenol (4-NP) was dissolved in 50g of deionized water, and then 0.326g of sodium hydrogen borate (NaBH)4) Adding into solution, and mixingThe color of the solution changed from colorless to bright yellow. Then, 1mg of the composite silver carbon fiber catalyst was added to 15g of the mixed solution. The catalytic reduction of 4-NP is carried out under room temperature visible light, and the reaction change in the whole catalytic process is recorded by the peak appearance condition of an ultraviolet visible spectrophotometer within the range of 200-500 nm.
Example 1
The preparation method of the composite silver carbon fiber catalyst comprises the following steps of:
(1) using silver nitrate (AgNO)3) 50 parts of PVA1799 is modified by swelling of the composite plasticizer, and the composite plasticizer comprises the following components:
the swelling modification is that the mixture is stirred and mixed for 30 minutes at the temperature of 20 ℃ and then sealed and kept stand for 1 day
(2) Carrying out melt spinning on the plasticized polyvinyl alcohol obtained in the step (1) through an extrusion-spinning device to obtain PVA/AgNO3The composite fiber has the following technological parameters: spinning temperature is 130 ℃, the aperture of a spinneret plate is 0.3mm, the drawing ratio of a spinning nozzle is 2 times, the cooling temperature of side air blowing is 60 ℃, and the humidity is 65%;
(3) mixing PVA/AgNO obtained in the step (2)3And carrying out thermal transformation reaction on the composite fiber at 600 ℃ for 3min in an oxygen atmosphere to obtain the composite silver carbon fiber catalyst.
The obtained composite silver carbon fiber catalyst is used in the catalytic reaction of the selective reduction of p-nitrophenol, and the catalytic efficiency is 200min-1g-1The reaction can be stably circulated for 10 times.
Example 2
The preparation method of the composite silver carbon fiber catalyst comprises the following steps of:
(1) using silver nitrate (AgNO)3) The composite plasticizer is prepared by swelling and modifying 60 parts of PVA0599, and comprises the following components:
the swelling modification is that the mixture is stirred and mixed for 20 minutes at the temperature of 40 ℃ and then sealed and kept stand for 1.5 days
(2) Carrying out melt spinning on the plasticized polyvinyl alcohol obtained in the step (1) through an extrusion-spinning device to obtain PVA/AgNO3The composite fiber has the following technological parameters: the spinning temperature is 150 ℃, the aperture of a spinneret plate is 0.2mm, the stretch ratio of a spinning nozzle is 4 times, the side-blowing cooling temperature is 80 ℃, and the humidity is 85%;
(3) mixing PVA/AgNO obtained in the step (2)3And carrying out thermal transformation reaction on the composite fiber at 400 ℃ in an oxygen atmosphere for 10min to obtain the composite silver carbon fiber catalyst.
The obtained composite silver carbon fiber catalyst is used in the catalytic reaction of the selective reduction of p-nitrophenol, and the catalytic efficiency is 150min-1g-1The reaction can be stably circulated for 8 times.
Example 3
The preparation method of the composite silver carbon fiber catalyst comprises the following steps of:
(1) using silver nitrate (AgNO)3) 50 parts of PVA1788 is modified by swelling of the composite plasticizer, and the composite plasticizer comprises the following components:
3 parts of silver nitrate, namely 3 parts of silver nitrate,
30 parts of water, namely, water,
the swelling modification is that the mixture is stirred and mixed for 10 minutes at the temperature of 20 ℃ and then sealed and kept stand for 1 day
(2) Carrying out melt spinning on the plasticized polyvinyl alcohol obtained in the step (1) through an extrusion-spinning device to obtain PVA/AgNO3The composite fiber has the following technological parameters: spinning temperature is 130 ℃, the aperture of a spinneret plate is 0.15mm, the drawing ratio of a spinning nozzle is 1 time, the side-blowing cooling temperature is 20 ℃, and the humidity is 65%;
(3) mixing PVA/AgNO obtained in the step (2)3And carrying out thermal transformation reaction on the composite fiber at 200 ℃ for 60min in the nitrogen atmosphere to obtain the composite silver carbon fiber catalyst.
Catalyzing the obtained composite silver carbon fiberThe agent is used in the catalytic reaction of the selective reduction of p-nitrophenol, and the catalytic efficiency is 90min-1g-1The reaction can be stably circulated for 8 times.
Example 4
The preparation method of the composite silver carbon fiber catalyst comprises the following steps of:
(1) using silver nitrate (AgNO)3) The composite plasticizer is prepared by swelling and modifying 70 parts of PVA2488, and comprises the following components:
15 parts of silver nitrate, namely silver nitrate,
10 parts of polyethylene glycol (with the molecular weight of 200),
40 parts of water, namely 40 parts of water,
the swelling modification is that the mixture is stirred and mixed for 30 minutes at the temperature of 80 ℃ and then sealed and kept stand for 2 days
(2) Carrying out melt spinning on the plasticized polyvinyl alcohol obtained in the step (1) through an extrusion-spinning device to obtain PVA/AgNO3The composite fiber has the following technological parameters: the spinning temperature is 180 ℃, the aperture of a spinneret plate is 0.4mm, the drawing ratio of a spinning nozzle is 4 times, the side-blowing cooling temperature is 60 ℃, and the humidity is 85%;
(3) mixing PVA/AgNO obtained in the step (2)3And carrying out thermal transformation reaction on the composite fiber at 300 ℃ for 5min under the argon atmosphere to obtain the composite silver carbon fiber catalyst.
The obtained composite silver carbon fiber catalyst is used in the catalytic reaction of the selective reduction of p-nitrophenol, and the catalytic efficiency is 80min-1g-1The reaction can be stably circulated for 8 times.
Claims (8)
1. The preparation method of the composite silver carbon fiber catalyst is characterized by comprising the following steps of:
(1) 50-70 parts of polyvinyl alcohol is subjected to swelling modification by using a silver nitrate-containing composite plasticizer, and the composite plasticizer comprises the following components:
2.5 to 15 parts of silver nitrate,
30-40 parts of water;
(2) carrying out melt spinning on the plasticized polyvinyl alcohol obtained in the step (1) through an extrusion-spinning device to obtain PVA/AgNO3Composite fibers;
(3) mixing PVA/AgNO obtained in the step (2)3And carrying out thermal transformation reaction on the composite fiber, namely carrying out oxidation reduction reaction on the polyvinyl alcohol and the silver nitrate, carrying out thermal oxidative degradation on the polyvinyl alcohol to form carbon, and reducing the silver nitrate into metal silver particles and nitrogen oxide by the polyvinyl alcohol to finally obtain the composite silver carbon fiber catalyst.
2. The method of claim 1, wherein: the polymerization degree of the polyvinyl alcohol in the step (1) is 500-2400, and the alcoholysis degree is 85-99%.
3. The method of claim 1, wherein: and (2) the swelling modification in the step (1) is to add a composite plasticizer containing silver nitrate into polyvinyl alcohol for mixing, stir and mix for 10-30 minutes at 20-90 ℃, and then seal and stand for 1-2 days to obtain plasticized polyvinyl alcohol.
4. The method of claim 1, wherein: the composite plasticizer in the step (1) further comprises the following components:
0.5 to 5 parts of a nitrogen-containing organic solvent,
or/and
0.5-10 parts of a polyhydric alcohol organic solvent.
5. The method according to claim 4, wherein: the nitrogen-containing organic solvent is caprolactam or acetamide; the polyalcohol organic solvent is glycerol or ethylene glycol or polyethylene glycol with molecular weight less than or equal to 800.
6. The method of claim 1, wherein: the process parameters of the melt spinning through the extrusion-spinning equipment in the step (2) are as follows: the spinning temperature is 130-180 ℃, the aperture of a spinneret plate is 0.12-0.4 mm, the drawing ratio of the spinneret plate is 1-4 times, the side blowing cooling temperature is 10-80 ℃, and the humidity is 65-85%.
7. The method of claim 1, wherein: the thermal transformation reaction in the step (3) has the following reaction conditions: the temperature is 200-600 ℃, the reaction time is 3-60 min, and the atmosphere is any one of nitrogen, oxygen and argon.
8. A composite silver carbon fiber catalyst prepared by the preparation method according to any one of claims 1 to 7.
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