CN111974453B - Cobalt iron prussian blue derivative/carbon nanofiber composite material and preparation method and application thereof - Google Patents
Cobalt iron prussian blue derivative/carbon nanofiber composite material and preparation method and application thereof Download PDFInfo
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- CN111974453B CN111974453B CN202010466854.4A CN202010466854A CN111974453B CN 111974453 B CN111974453 B CN 111974453B CN 202010466854 A CN202010466854 A CN 202010466854A CN 111974453 B CN111974453 B CN 111974453B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a cobalt iron prussian blue derivative/carbon nanofiber composite material, which is prepared by preparing an electrospinning precursor solution by using a cobalt iron prussian blue analogue and a high-molecular polymer as main raw materials, and performing electrostatic spinning, preheating oxidation and carbonization treatment. According to the invention, the cobalt iron prussian blue derivative is used as a precursor, the cobalt iron prussian blue derivative/carbon nanofiber composite material is prepared by adopting an electrostatic spinning technology, the formed Fe/Co oxide and N doping effect act together to remarkably improve the catalytic activity of the obtained composite material, the introduced metal oxide carbon-based framework with high porosity and high specific surface area can further effectively improve the catalytic activity and adsorption capacity, and meanwhile, the overflow of active metal ions is effectively reduced, so that the obtained composite material can effectively give consideration to excellent catalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and particularly relates to a cobalt iron prussian blue derivative/carbon nanofiber composite material as well as a preparation method and application thereof.
Background
In recent years, with the development of industry and social progress, environmental deterioration has become an important problem that restricts the development of human beings. The Fenton-like reaction of activating persulfate is favored by researchers as a novel advanced oxidation technology for degrading organic pollutants. The development of efficient and environmentally friendly fenton-like catalysts and the exploration of the mechanism of the fenton-like reaction are the focus and hot point of the present research in this field. PB (prussian blue)/PBA (prussian blue analogue) is considered as hexacyanometallate or a class of Metal Organic Framework (MOF), and has great potential in the catalyst-related field due to the characteristics of low cost, easy preparation, inherent open framework and designable composition and the like. But the pure PBA particle structure is unstable and tends to collapse.
In order to solve the technical problems, the PB/PBA is generally carbonized into the nano microspheres after being etched, but the process is complex and has low realization degree; the oxide with a shell structure can also be prepared by using the single metal PB particles, but the catalytic effect is obviously reduced. Most of the traditional means are simple oxidation or simple carbonization of PB/PBA, and due to the instability of particles, although the catalytic activity of the oxidized catalyst can be improved to a certain extent, a large amount of metal ions overflow to cause secondary pollution to a water body; although the overflow of metal ions can be reduced by the carbonized particles, the activity of the catalyst is reduced; it is difficult to effectively take good catalytic performance and stability into consideration. In addition, the MOF (metal organic framework) catalyst is in powder or granular form, and is dispersed in a suspension system formed by a substrate solution in the catalytic process, so that the MOF catalyst is difficult to separate and recover, and the MOF catalyst is limited in wide application.
Disclosure of Invention
The invention mainly aims to provide a cobalt iron prussian blue derivative/carbon nanofiber composite material aiming at the defects in the prior art, which has stronger stability, higher catalytic activity and higher repeated availability, and the related preparation method is simple and has important application prospects in the fields of catalysis, pollution control and the like.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
the cobalt iron prussian blue derivative/carbon nano fiber composite material is prepared by using cobalt iron prussian blue analogue and high molecular polymer as main raw materials to prepare an electrospinning precursor solution, and performing electrostatic spinning, preheating oxidation and carbonization treatment.
In the scheme, the cobalt-iron prussian blue analogue is obtained by taking iron salt, cobalt salt, a complexing stabilizer and water as raw materials and carrying out a standing reaction at normal temperature.
The preparation method of the cobalt iron prussian blue derivative/carbon nanofiber composite material comprises the following steps:
1) Uniformly mixing ferric salt, cobalt salt, a complexing stabilizer and water to obtain a precursor solution, then carrying out standing reaction at normal temperature, washing and drying to obtain a cobalt-iron Prussian blue analogue;
2) Preparing an electrospinning precursor solution by using the cobalt iron prussian blue analogue and a high molecular polymer as main raw materials, and performing electrostatic spinning, preheating oxidation and carbonization treatment to obtain the cobalt iron prussian blue derivative/carbon nanofiber composite material.
In the above scheme, the ferric salt is selected from one of potassium ferricyanide, ferric nitrate, etc.; the cobalt salt is selected from cobalt nitrate, cobalt chloride, cobalt sulfate, etc.
In the above scheme, the complexing stabilizer is one of trisodium citrate, polyvinylpyrrolidone (PVP), and the like.
In the scheme, the molar ratio of the ferric salt to the cobalt salt is 1 (1-3).
In the scheme, the molar ratio of the ferric salt to the complexing stabilizer is 1 (2-3).
In the scheme, the high molecular polymer is one or more of polyacrylonitrile and polyvinylpyrrolidone.
In the scheme, the mass ratio of the cobalt iron Prussian blue analogue to the high molecular polymer is 1 (4-7); the high molecular polymer accounts for 10-15% of the mass of the electrospinning precursor solution.
In the above scheme, the solvent adopted in the electrospinning precursor solution is dimethylformamide
In the scheme, the normal-temperature standing reaction time is 16-24h.
In the scheme, in the electrostatic spinning process, the spinning voltage is 15-20kV, the receiving distance is 15-20cm, and the driving speed of electrostatic spinning is 0.5-1.0mL/h.
In the scheme, the preheating oxidation temperature is 200-250 ℃, and the time is 1-2h; the carbonization treatment step comprises the steps of firstly heating to 400-450 ℃ under the protective atmosphere, and then preserving heat for 1-2h.
The cobalt iron Prussian blue derivative/carbon nanofiber composite material obtained by the scheme is applied to catalytic degradation of organic pollutants in water, has a good catalytic effect on bisphenol A, is mild in required catalytic conditions and good in catalytic stability, and has potential application prospects in the fields of catalysis, pollution control and the like.
The principle of the invention is as follows: 1) According to the invention, a cobalt iron Prussian blue derivative is used as a precursor, firstly, a cubic framework structure, oxide stability and an electrostatic spinning technology of the cobalt iron Prussian blue derivative are utilized to effectively and uniformly fix a cobalt iron Prussian blue analogue on electrostatic spinning, the load capacity of the cobalt iron Prussian blue analogue is improved, then, by controlling heat treatment, on the basis of effectively keeping the cubic framework structure of the cobalt iron Prussian blue derivative, metal element oxidation and polymer carbonization are synchronously realized to obtain a metal oxide carbon-based framework with high porosity and high specific surface area, and the introduced cubic framework structure, porous structure and carbon layer are wrapped to increase the activity of a catalyst and reduce the overflow of metal ions; the introduced pore channel structure can promote the full contact of organic pollutants and cobalt-iron composite oxide active substances, and the carbon nano-fiber promotes the adsorption of a substrate, thereby achieving the effects of adsorption-catalytic degradation; in addition, the introduced Fe and Co (active substances) are interacted on the carrier and effectively interacted between the active substances and the carrier, so that the Co and the Fe can be uniformly distributed on the porous carbon carrier, the overflow of metal ions is reduced, and the activity and the stability of the obtained catalyst are further ensured; meanwhile, the introduced carbon layer can synchronously realize nitrogen doping, so that the reaction performance of the carbon material for activating persulfate is improved;
2) At present, the composite material based on the cobalt iron prussian blue derivative/carbon nano fiber is generally prepared into an electrostatic spinning film firstly, and then prussian blue analogue material grows on the surface of the film, but the preparation method is not beneficial to ensuring the activity and stability of the obtained catalyst; the cobalt-iron Prussian blue derivative/carbon nanofiber composite material has a 1D nanofiber structure, has a high axial ratio, and is favorable for rapid and long-distance electron transfer, and the porous nanofiber structure formed by carbonization treatment and the retained metal oxide framework structure can improve the specific surface area of the obtained composite material, promote the adsorption effect on a substrate, more effectively expose more active sites, ensure the effective load of active technical oxides, and enable the obtained composite material to show excellent catalytic activity and stability.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, the cobalt iron prussian blue derivative is used as a precursor, the cobalt iron prussian blue derivative/carbon nanofiber composite material is prepared by adopting an electrostatic spinning technology, the catalytic activity of the obtained composite material can be obviously improved under the combined action of Fe/Co oxide and N doping effect, the introduced metal oxide carbon-based framework with high porosity and high specific surface area can further effectively improve the catalytic activity and adsorption capacity, and meanwhile, the overflow of active metal ions is effectively reduced, so that the obtained composite material can effectively give consideration to excellent catalytic activity and stability, and the related preparation method is simple, the catalytic operation is convenient, and the preparation method is suitable for popularization and application.
2) The cobalt iron prussian blue derivative/carbon nanofiber composite material prepared by the invention can show excellent catalytic performance and stability on bisphenol A phenolic substances, is mild in catalytic condition, good in stability and easy to recover, and has potential application prospects in the fields of catalysis, pollution control and the like.
Drawings
FIG. 1 is an SEM image of (a) CoFe Prussian analogue/nanofiber composite CoFe-PBA @ NF prepared in example 1 of the present invention;
FIG. 2 shows CoFe of CoFePrussian blue derivative/carbon nanofiber composite prepared in example 1 of the present invention 2 O 4 XRD pattern of/CNF;
FIG. 3 shows CoFe-PBA @ NF and CoFe obtained in example 1 of the present invention 2 O 4 CNF, co-Fe composite Oxidation obtained in comparative example 1Substance (CoFe) 2 O 4 ) CoFe-PBA/CNF obtained in comparative example 2, fe obtained in comparative example 3 x O y High Performance Liquid Chromatography (HPLC) graph of CNF catalyzed bisphenol A with time, wherein C 0 Initial concentration of bisphenol A solution, C t The concentration value of the bisphenol A solution after the time t, wherein t is the time;
FIG. 4 shows CoFe obtained in example 1 of the present invention 2 O 4 Data plot for CNF catalytic stability experiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A cobalt iron Prussian blue derivative/carbon nanofiber composite material is prepared by the following steps:
1) Adding 2mmol of potassium ferricyanide into 100mL of water, adding 2mmol of cobalt nitrate and 4mmol of trisodium citrate into 100mL of water, fully stirring for dissolving, then mixing the two obtained solutions, uniformly stirring, and standing at normal temperature for reaction for 24 hours; then carrying out centrifugation, washing and drying to obtain the cobalt iron Prussian blue analogue;
2) Adding 0.20g of cobalt iron Prussian blue analogue and 1.36g of polyacrylonitrile into 9.45g of N, N-Dimethylformamide (DMF), and uniformly stirring to obtain an electro-spinning precursor solution;
3) Placing the obtained electrospinning precursor solution into a 10mL plastic injector with a needle head for electrostatic spinning, wherein the set working voltage is 20kV direct-current high-voltage electricity, the distance between the needle head and a receiving plate is 20cm, the environmental humidity is 30-50% in the electrospinning process, the flow rate of the electrospinning precursor solution is controlled to be 1.0mL/h by an injection pump, and the cobalt iron prussian analogue/nanofiber composite material (CoFe-PBA @ NF) is obtained through electrostatic spinning;
4) Pre-oxidizing the obtained CoFe-PBA @ NF to 250 ℃, keeping the temperature for 2h, then continuously heating to 400 ℃ in nitrogen atmosphere, and continuously keeping the temperature for 2h to obtain the cobalt iron prurusStrobilanthes derivative/carbon nanofiber composite (CoFe) 2 O 4 /CNF)。
The SEM picture of the CoFe Prussian analogue/nanofiber composite material CoFe-PBA @ NF obtained in the embodiment is shown in figure 1, and it can be seen that the CoFe Prussian blue analogue particles are uniformly loaded on the nanofiber membrane, and the diameter of the nanofiber is about 300-400 nm.
FIG. 2 is an XRD pattern of the final product obtained in this example, and it is revealed that the obtained product is a composite material of Co/Fe oxide and carbon.
Example 2
A cobalt iron Prussian blue derivative/carbon nanofiber composite material is prepared by the following steps:
1) Adding 2mmol of potassium ferricyanide into 100mL of water, adding 2mmol of cobalt nitrate and 4mmol of polyvinylpyrrolidone into 100mL of water, fully stirring and dissolving, then mixing the two obtained solutions, uniformly stirring, and standing at normal temperature for reaction for 24 hours; then carrying out centrifugation, washing and drying to obtain the cobalt iron Prussian blue analogue;
2) Adding 0.20g of cobalt iron Prussian blue analogue particles and 1.36g of polyacrylonitrile into 9.45g of N, N-Dimethylformamide (DMF) solution, and uniformly stirring to obtain an electrospinning precursor solution;
3) Placing the obtained electrospinning precursor solution into a 10mL plastic injector with a needle head for electrostatic spinning, wherein the set working voltage is 20KV flow high voltage, the distance between the needle head and a receiving plate is 15cm, the environmental humidity is 30-50% in the electrospinning process, the flow rate of the electrospinning precursor solution is controlled to be 1.0mL/h by an injection pump, and the ferrocobalprussian analogue/nanofiber composite material (2-CoFe-PBA @ NF) is obtained through electrostatic spinning;
4) Pre-thermal oxidizing the obtained CoFe-PBA @ NF to 250 ℃, keeping the temperature for 2h, then continuously heating to 400 ℃ in nitrogen atmosphere, and continuously keeping the temperature for 2h to obtain the cobalt iron Prussian blue derivative/carbon nanofiber composite material (2-CoFe) 2 O 4 /CNF). In the experimental process, the PBAs prepared by using different complexes have no difference in morphology and no obvious difference in performance, and a series of experiments and representations are performed by taking trisodium citrate as an example.
Example 3
A cobalt iron Prussian blue derivative/carbon nanofiber composite material is prepared by the following steps:
1) Adding 2mmol of potassium ferricyanide into 100mL of water, adding 4mmol of cobalt nitrate and 4mmol of trisodium citrate into 100mL of water, fully stirring for dissolving, then mixing the two obtained solutions, uniformly stirring, and standing at normal temperature for reaction for 24 hours; then carrying out centrifugation, washing and drying to obtain the cobalt iron Prussian blue analogue;
2) Adding 0.20g of cobalt iron Prussian blue analogue and 1.36g of polyacrylonitrile into 9.45g of N, N-Dimethylformamide (DMF), and uniformly stirring to obtain an electro-spinning precursor solution;
3) Placing the obtained electrospinning precursor solution into a 10mL plastic syringe with a needle for electrostatic spinning, wherein the set working voltage is 20kV direct-current high-voltage electricity, the distance between the needle and a receiving plate is 20cm, the environment humidity is 30-50% in the electrospinning process, the flow rate of the electrospinning precursor solution is controlled to be 1.0mL/h by an injection pump, and the ferrocobalt prussian analogue/nanofiber composite material is obtained by electrostatic spinning;
4) Pre-thermal oxidizing the obtained CoFe-PBA @ NF to 250 ℃, keeping the temperature for 2h, then continuously heating to 400 ℃ in nitrogen atmosphere, and continuously keeping the temperature for 2h to obtain the CoFePrussian blue derivative/carbon nanofiber composite material (named 3-CoFe) 2 O 4 /CNF)
Comparative example 1
A cobalt-iron composite oxide material is prepared by the following steps:
1) Adding 2mmol of potassium ferricyanide into 100mL of water, adding 2mmol of cobalt nitrate and 4mmol of trisodium citrate into 100mL of water, fully stirring for dissolving, then mixing the two solutions, stirring for five minutes, and standing for 24 hours. Centrifuging, washing and drying to obtain cobalt iron Prussian blue analogue particles;
2) Putting the obtained Prussian blue analogue particles into a quartz boat, calcining the Prussian blue analogue particles in air to 400 ℃, and preserving the heat for 2 hours to obtain the cobalt-iron composite oxide (CoFe) 2 O 4 )。
Comparative example 2
Cobalt iron Prussian blue analogue/carbon nanofiber composite material
1) Adding 2mmol of potassium ferricyanide into 100mL of water, adding 2mmol of cobalt nitrate and 4mmol of trisodium citrate into 100mL of water, fully stirring for dissolving, then mixing the two obtained solutions, uniformly stirring, and standing at normal temperature for reaction for 24 hours; then carrying out centrifugation, washing and drying to obtain the cobalt iron Prussian blue analogue;
2) Adding 0.20g of cobalt iron Prussian blue analogue and 1.36g of polyacrylonitrile into 9.45g of N, N-Dimethylformamide (DMF), and uniformly stirring to obtain an electro-spinning precursor solution;
3) Placing the obtained electrospinning precursor solution into a 10mL plastic syringe with a needle for electrospinning, wherein the set working voltage is 20kV direct-current high-voltage electricity, the distance between the needle and a receiving plate is 20cm, the environmental humidity is 30-50% in the electrospinning process, the flow rate of the electrospinning precursor solution is controlled to be 1.0mL/h by an injection pump, and the CoFe Prussian analogue/nanofiber composite (CoFe-PBA @ NF) is obtained through electrospinning;
4) Heating the obtained CoFe-PBA @ NF to 400 ℃ in the nitrogen atmosphere, and then continuing to preserve heat for 2 hours to obtain the CoFe Prussian blue analogue/carbon nanofiber composite material (CoFe-PBA/CNF)
Comparative example 3
Iron-iron prussian blue derivative/carbon nanofiber composite material
1) Adding 2mmol of potassium ferricyanide into 100mL of water, adding 2mmol of ferric nitrate and 4mmol of trisodium citrate into 100mL of water, fully stirring for dissolving, then mixing the two solutions, stirring for five minutes, and standing for 24 hours. Centrifuging, washing and drying to obtain iron Prussian blue particles
2) Adding 0.20g of iron Prussian blue analogue particles and 1.36g of polyacrylonitrile into 9.45g of N, N-Dimethylformamide (DMF) solution, and uniformly stirring to obtain an electrospinning precursor solution;
3) Placing the obtained electrospinning precursor solution into a 10mL plastic syringe with a needle for electrospinning, wherein the set working voltage is 20kV direct-current high-voltage electricity, the distance between the needle and a receiving plate is 20cm, the environmental humidity is 30-50% in the electrospinning process, the flow rate of the electrospinning precursor solution is controlled to be 1.0mL/h by an injection pump, and the ferrum Prussian blue analogue/nanofiber composite material (FeFe-PBA @ NF) is obtained by electrospinning
4) Carrying out pre-thermal oxidation on the obtained FeFe-PBA @ NF until the temperature is 250 ℃, keeping the temperature for 2h, then continuously heating to 400 ℃ in the nitrogen atmosphere, and continuously keeping the temperature for 2h to obtain the Fe-Fe Prussian blue derivative/carbon nanofiber composite material (Fe) x O y /CNF)
Application example 1
The CoFe obtained in example 1 was separately added 2 O 4 CoFe-PBA @ NF,/CNF and CoFe-PBA @ NF, co-Fe composite oxide (CoFe) obtained in comparative example 1 2 O 4 ) CoFe-PBA/CNF obtained in comparative example 2 Fe obtained in comparative example 3 x O y /CNF * The method is applied to catalyzing bisphenol A and comprises the following specific steps:
1) Preparing a bisphenol A solution of 20mg/L, taking 20mL of the bisphenol A solution to a glass bottle, and then adding 100mg/L potassium Peroxymonosulfate (PMS);
2) After potassium hydrogen Peroxymonosulfate (PMS) is dissolved, 0.5g/L of CoFe is respectively added into the bisphenol A solution 2 O 4 /CNF、CoFe-PBA@NF、CoFe 2 O 4 、CoFe-PBA/CNF、Fe x O y a/CNF; sampling every 1min to measure bisphenol A solution, and measuring peak area by high performance liquid chromatography to obtain degradation concentration.
FIG. 3 is a High Performance Liquid Chromatography (HPLC) graph of a bisphenol A solution over time, which shows that the catalyst obtained in example 1 can degrade the bisphenol A solution quickly within 2 min.
Application example 2
The catalyst CoFe Prussian blue derivative/carbon nano-fiber composite material CoFe obtained in example 1 2 O 4 The method is characterized in that the method comprises the following steps of 6 times of repetition and application to a bisphenol A solution:
1) Preparing a bisphenol A solution with the concentration of 20mg/L, putting 20mL of the bisphenol A solution into a glass bottle, and then adding 0.15g/L potassium hydrogen Peroxymonosulfate (PMS);
2) After potassium hydrogen Peroxymonosulfate (PMS) is dissolved, 0.5g/LCoFe is added into the bisphenol A solution 2 O 4 a/CNF; sampling every 1min to measure the peak area of the concentration of the bisphenol A solution until the degradation is finished;
3) After the catalytic experiment was completed, coFe was taken out with a magnet 2 O 4 The CNF fiber membrane is washed by ethanol for a plurality of times, the catalytic experiment is repeated under other conditions after drying, the experiment is repeated for 6 times, and the data of the catalytic experiment of each time are recorded.
FIG. 4 shows CoFe as a catalyst in example 2 2 O 4 The results of the catalytic data graph of 6 times of experiments repeated by applying the CNF to the bisphenol A show that the catalyst obtained by the invention has mild required catalytic conditions and good catalytic stability; coFe 2 O 4 The cycle number of the prussian blue derived composite oxide is at most 4, and the cycle performance is increasingly poor; the CoFe-PBA/CNF can be circulated for 5 times at most, and the circulation performance of each time is poor (the CoFe-PBA/CNF can be degraded by 60% at most, and the degradation time is more than 5 min); the number of cycles of CoFe-PBA @ NF did not exceed 4, and the cycling performance became worse.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (9)
1. The cobalt iron prussian blue derivative/carbon nanofiber composite material is characterized in that an electrospinning precursor solution is prepared by taking a cobalt iron prussian blue analogue and a high molecular polymer as main raw materials, and the composite material is prepared by electrostatic spinning, preheating oxidation and carbonization;
the mass ratio of the cobalt iron Prussian blue analogue to the high molecular polymer is 1 (4-7);
the preheating oxidation temperature is 200-250 ℃, and the time is 1-2h; the carbonization treatment step comprises the steps of firstly heating to 400-450 ℃ under the protective atmosphere, and then preserving heat for 1-2h.
2. The cofeb blue derivative/carbon nanofiber composite material as claimed in claim 1, wherein the cofeb blue analogue is obtained by carrying out a normal temperature standing reaction on a ferric salt, a cobalt salt, a complexing stabilizer and water as raw materials.
3. The method for preparing the cobalt iron prussian blue derivative/carbon nanofiber composite material as set forth in claim 1 or 2, comprising the steps of:
1) Uniformly mixing ferric salt, cobalt salt, a complexing stabilizer and water to obtain a precursor solution, then carrying out standing reaction at normal temperature, washing and drying to obtain a cobalt-iron Prussian blue analogue;
2) Preparing an electrospinning precursor solution by using the cobalt iron prussian blue analogue and a high molecular polymer as main raw materials, and performing electrostatic spinning, preheating oxidation and carbonization treatment to obtain the cobalt iron prussian blue derivative/carbon nanofiber composite material.
4. The preparation method according to claim 3, wherein the iron salt is one of potassium ferricyanide and ferric nitrate; the cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt sulfate; the high molecular polymer is one or more of polyacrylonitrile and polyvinylpyrrolidone.
5. The preparation method of claim 3, wherein the molar ratio of the iron salt to the cobalt salt is 1 (1-3); the molar ratio of the ferric salt to the complexing stabilizer is 1 (2-3).
6. The preparation method according to claim 3, wherein the high molecular weight polymer accounts for 10-15% of the mass of the electrospinning precursor solution.
7. The preparation method according to claim 3, wherein the reaction time is 16 to 24 hours at the room temperature.
8. The method according to claim 3, wherein in the electrospinning process, the spinning voltage is 15 to 20kV, the receiving distance is 15 to 20cm, and the driving speed of electrospinning is 0.5 to 1.0mL/h.
9. Use of the cobalt iron prussian blue derivative/carbon nanofiber composite material prepared according to any one of claims 1 to 2 or 3 to 8 in catalytic degradation of organic pollutants in water.
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| CN113908878B (en) * | 2021-08-12 | 2023-03-24 | 南京大学 | Preparation method and application of bimetallic Prussian blue analogue catalyst |
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