CN112795051A - Porous polythiophene nano film loaded with nano zero-valent iron and preparation method and application thereof - Google Patents
Porous polythiophene nano film loaded with nano zero-valent iron and preparation method and application thereof Download PDFInfo
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- 229920000123 polythiophene Polymers 0.000 title claims abstract description 114
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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Abstract
The invention provides a preparation method of a porous polythiophene nanometer film loaded with nanometer zero-valent iron, belonging to the technical field of soil remediation agents and comprising the following steps: (1) preparing a porous polythiophene nanometer film by combining an electrochemical polymerization method and a chemical oxidation method; (2) and preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method. The invention also provides the porous polythiophene nanometer film loaded with the nanometer zero-valent iron and prepared by the method, and the porous polythiophene nanometer film is used as a heavy metal polluted soil repairing agent. The porous polythiophene nanometer film loaded with the nanometer zero-valent iron solves the problems that the nanometer zero-valent iron serving as a soil remediation agent is poor in monodispersity, easy to agglomerate and easy to oxidize, and has good removal capacity for heavy metal ion pollutants in soil.
Description
Technical Field
The invention belongs to the technical field of soil remediation agents, and particularly relates to a porous polythiophene nanometer film loaded with nanometer zero-valent iron, a preparation method and application.
Background
In recent years, soil pollution worldwide has become more serious. Under the large background that the soil quality directly influences the grain production safety, the soil remediation research taking the health of the population in the whole society as a consideration obtains continuous attention. Among many soil pollutants, heavy metal ion pollutants have very typical characteristics. It is difficult to be catabolized by microbes in soil, has the characteristics of small mobility and easy accumulation in animals and plants, and affects the growth of a large number of plants on one hand, especially the normal growth of crops. On one hand, the tumor cell is concentrated in animals and plants, the continuous accumulation of the tumor cell can directly cause the animals and plants to have malignant diseases, and the concentration of the tumor cell in human bodies can also cause malignant diseases such as various tumors and the like.
Currently, research on soil remediation is underway. A large number of researches show that the nano zero-valent iron has great application space in the field of soil pollution remediation. The method has a great number of application advantages, such as low use cost, environmental friendliness and no pollution, and has a great number of application examples in the field of remediation of water body pollution, such as removal of chlorine-containing organic pollutants and heavy metal ions in water bodies. In the field of in-situ soil remediation, nano zero-valent iron is also expected. By means of the characteristic advantages, the current researchers propose that the oxidation of the nano zero-valent iron in the soil environment can be effectively overcome, and the rapid adsorption performance of the nano zero-valent iron can be enhanced, so that the possibility is provided for the future large-scale practical application of the nano zero-valent iron. Around the above problems, a subsequent series of improvement approaches such as biochar loading, montmorillonite loading, mica sheet loading, and the like have been proposed. The above improved method overcomes the application obstacle of nanometer zero-valent iron to a certain extent, however, other modification or improvement approaches are still continuously explored. The traditional organic conjugated polymer material has special advantages in consideration of improving the environmental stability and monodispersity of the nano zero-valent iron and expanding the specific surface area of the nano zero-valent iron, such as that polythiophene is used in the field of metal rust prevention and corrosion prevention. If the conjugated polymer material with high specific surface area can be prepared on the basis of the method, and the effective load of the conjugated polymer material on the nano zero-valent iron is realized, the large-scale soil remediation application of the nano powder can be promoted.
Disclosure of Invention
The invention aims to provide a porous polythiophene nanometer film loaded with nanometer zero-valent iron, a preparation method and application thereof aiming at the defects in the prior art, and solves the problems that the nanometer zero-valent iron as a soil remediation agent has poor monodispersity, is easy to agglomerate and is easy to oxidize.
The object of the invention can be achieved by the following technical measures:
the invention provides a preparation method of a porous polythiophene nanometer film loaded with nanometer zero-valent iron, which comprises the following steps:
(1) preparing a porous polythiophene nanometer film by combining an electrochemical polymerization method and a chemical oxidation method;
(2) and preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method.
Further, the process of preparing the porous polythiophene nanometer film by combining electrochemical polymerization and chemical oxidation is as follows:
preparing polythiophene by adopting cyclic voltammetry electrochemical polymerization on a CHI-660 type electrochemical workstation, and adding an oxidant to carry out chemical doping and pore-forming.
Further, in the preparation of the porous polythiophene nanometer film by combining electrochemical polymerization and chemical oxidation, a platinum sheet electrode is adopted as an auxiliary electrode, a saturated calomel electrode is adopted as a reference electrode, an electrolyte is a mixed solution of thiophene monomers and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is MnO2。
Further, the electrochemical polymerization electrical parameters are controlled as follows: the polymerization voltage is 0.2-4.0V, the scanning speed is 2-20 mV/s, and the scanning period is 15-80 circles;
the chemical parameters were controlled as follows: adding 2-20 mL of thiophene monomer into 400mL of dilute sulfuric acid, and then adding 0.02-1.80 g of MnO2An oxidizing agent.
Further, after the preparation of the porous polythiophene nanometer film by combining the electrochemical polymerization and the chemical oxidation method is finished, the method also comprises the steps of cleaning the working electrode by using dilute hydrochloric acid, ethanol and distilled water in sequence, slightly taking the product off the working electrode, and drying for later use.
Further, the process for preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
in FeSO4And adding the porous polythiophene nano-film into the solution, adding a reducing agent, filtering after the reaction is finished, washing and drying the solid-phase product to obtain the porous polythiophene nano-film loaded with the nano zero-valent iron.
Further, the reducing agent is NaBH of 0.75mol/L4Solution, FeSO4The concentration of the solution is 0.25-1 mol/L.
Further, the process for preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
taking 100mL of FeSO4Putting the solution into a three-neck flask, then adding 0.5-2.4 g of porous polythiophene nano-film, and under the protection of nitrogen, stirring and dripping 0.2-0.5 mL of NaBH at a constant speed4And (3) continuing stirring the solution for reaction for 20-80 min, filtering and separating after the reaction is finished to obtain a solid phase product, washing the solid phase product with deionized water and ethanol, and placing the solid phase product at the temperature of 60 ℃ for vacuum drying for 5-12 h to obtain the porous polythiophene nano film loaded with nano zero-valent iron.
The invention also provides the porous polythiophene nanometer film loaded with the nanometer zero-valent iron prepared by the preparation method.
The invention also provides application of the porous polythiophene nanometer film loaded with the nanometer zero-valent iron, and the porous polythiophene nanometer film is used as a heavy metal polluted soil repairing agent.
The preparation method of the porous polythiophene nanometer film loaded with the nanometer zero-valent iron has the following beneficial effects:
(1) compared with the prior art which adopts electrochemical polymerization to prepare the polythiophene film, the most common chemical oxidation method is fully utilized to prepare the porous polythiophene nano film by combining the electrochemical polymerization and the chemical oxidation method, and an oxidant (such as MnO) is added in the protonic acid environment of the electrochemical polymerization2) Oxidizing the thiophene monomer to obtain the chemically doped polythiophene compound film on the one hand, and realizing the pore-forming process on the surface of the polymer through polymerization reaction under proper oxidation conditions on the other hand, thereby enlarging the specific surface area of the material and improving the overall soil remediation performance of the material.
(2) Compared with the nano zero-valent iron loaded by the non-porous polythiophene nano film, the nano zero-valent iron loaded by the porous polythiophene nano film can reduce the environmental oxidation degree of pure nano zero-valent iron, prevent the nano zero-valent iron from being oxidized by moisture and other substances in the environment in the early stage of application and prolong the application period of the nano zero-valent iron; on the other hand, the zero-valent iron nanoparticles can be effectively prevented from agglomerating by loading the oxidized polythiophene film, the monodispersity and the subsequent adsorption performance of the zero-valent iron nanoparticles are improved, and the aim of enhancing the soil remediation performance of the zero-valent iron nanoparticles is fulfilled.
(3) The porous polythiophene nanometer film loaded with nanometer zero-valent iron has better removal capacity on heavy metal ion pollutants in soil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of a porous polythiophene nanometer film loaded with nanometer zero-valent iron prepared in example 1 of the present invention;
FIG. 2 is a distribution diagram of iron elements of the porous polythiophene nanometer film loaded with nanometer zero-valent iron prepared in example 1 of the present invention;
FIG. 3 is a photograph of a porous polythiophene nanometer film loaded with nanometer zero-valent iron prepared in example 1 of the present invention;
FIG. 4 is an infrared spectrum of the porous polythiophene nanometer film loaded with nano zero-valent iron prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In order to make the description of the present disclosure more complete and complete, the following description is given for illustrative purposes with respect to the embodiments and examples of the present invention; it is not intended to be the only form in which the embodiments of the invention may be practiced or utilized. The embodiments are intended to cover the features of the various embodiments as well as the method steps and sequences for constructing and operating the embodiments. However, other embodiments may be utilized to achieve the same or equivalent functions and step sequences.
The invention provides a preparation method of a porous polythiophene nanometer film loaded with nanometer zero-valent iron, which comprises the following steps:
(1) preparing a porous polythiophene nanometer film by combining an electrochemical polymerization method and a chemical oxidation method;
(2) and preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method.
According to the invention, the nano zero-valent iron is loaded on the porous polythiophene nanometer film, so that on one hand, the loss of the nano zero-valent iron can be greatly limited, compared with the conventional process, the protection on the nano zero-valent iron is more excellent, the 'non-effective oxidation' degree of the nano zero-valent iron is reduced, the high reaction activity of the nano zero-valent iron is maintained, the oxidation by non-target pollutants such as water in the environment is prevented, and the service life of the nano zero-valent iron is prolonged. Meanwhile, the porous polymer nano film is loaded, so that the agglomeration phenomenon can be effectively prevented, the dispersibility, the mechanical strength and the adsorption effect of the nano zero-valent iron particles in a water phase are improved, and the nano zero-valent iron particles have better removing capacity on heavy metal ion pollutants.
The process for preparing the porous polythiophene nanometer film by combining the electrochemical polymerization and the chemical oxidation method comprises the following steps:
preparing polythiophene by adopting cyclic voltammetry electrochemical polymerization on a CHI-660 type electrochemical workstation, and adding an oxidant to carry out chemical doping and pore-forming.
In some embodiments, in the preparation of the porous polythiophene nanometer film by combining electrochemical polymerization and chemical oxidation, a platinum sheet electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, an electrolyte is a mixed solution of thiophene monomers and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is MnO2。
Specifically, the electrochemical polymerization electrical parameters are controlled as follows: the polymerization voltage is 0.2-4.0V, the scanning speed is 2-20 mV/s, and the scanning period is 15-80 circles;
the chemical parameters were controlled as follows: adding 2-20 mL of thiophene monomer into 400mL of dilute sulfuric acid, and then adding 0.02-1.80 g of MnO2An oxidizing agent.
In some embodiments, after the preparation of the porous polythiophene nanometer film by combining the electrochemical polymerization and the chemical oxidation method is completed, the method further comprises the steps of sequentially cleaning the working electrode by using dilute hydrochloric acid, ethanol and distilled water, slightly taking the product from the working electrode, and drying the product for later use.
The process for preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
in FeSO4And adding the porous polythiophene nano-film into the solution, adding a reducing agent, filtering after the reaction is finished, washing and drying the solid-phase product to obtain the porous polythiophene nano-film loaded with the nano zero-valent iron.
In some embodiments, the reducing agent is 0.75mol/L NaBH4Solution, FeSO4The concentration of the solution is 0.25-1 mol/L.
Specifically, the process for preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
taking 100mL of FeSO4Putting the solution into a three-neck flask, then adding 0.5-2.4 g of porous polythiophene nano-film, and under the protection of nitrogen, stirring and dripping 0.2-0.5 mL of NaBH at a constant speed4And (3) continuing stirring the solution for reaction for 20-80 min, filtering and separating after the reaction is finished to obtain a solid phase product, washing the solid phase product with deionized water and ethanol, and placing the solid phase product at the temperature of 60 ℃ for vacuum drying for 5-12 h to obtain the porous polythiophene nano film loaded with nano zero-valent iron.
Example 1
The preparation process of the porous polythiophene nanometer film loaded with the nanometer zero-valent iron comprises the following steps:
(1) preparation of porous polythiophene nanometer film by combining electrochemical polymerization and chemical oxidation method
Preparing polythiophene film on CHI-660 type electrochemical workstation by adopting cyclic voltammetry electropolymerization, wherein MnO is adopted2As an oxidizing agent. In a three-electrode system, a platinum sheet electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and an electrolyte is a mixed solution of thiophene and dilute sulfuric acid (the concentration is 0.26 mol/L). The electrochemical polymerization conditions are as follows: the polymerization voltage was 0.54V, the scan rate was 6.5mV/s, the scan period was 25 cycles, and the polymerization conditions were: 2.5mL of thiophene monomer, followed by 0.08g of MnO, were added to 400mL of dilute sulfuric acid (concentration 0.26mol/L)2And after the polymerization is finished, taking out the working electrode, sequentially cleaning the working electrode by using dilute hydrochloric acid, ethanol and distilled water, gently taking down the polymer film from the working electrode, and drying the polymer film for later use.
(2) Preparation of porous polythiophene nanometer film loaded with nanometer zero-valent iron by liquid phase reduction method
100mL of 0.38mol/L FeSO was taken4Putting the solution into a three-neck flask, then adding 0.85g of porous polythiophene membrane powder into the solution, and adding 0.32mL of 0.75mol/L NaBH under the protection of nitrogen and under the mechanical stirring (the rotating speed is 120r/min)4Dropping the solution into three-neck flask at uniform speed, stirring for reaction for 35min, filtering and separating the obtained solid phase product, washing with deionized water and ethanol, and vacuum drying at 60 deg.CAnd 6h, obtaining the porous polythiophene nanometer film loaded with the nanometer zero-valent iron.
Fig. 1 is an SEM image of the nano zero-valent iron-supported porous polythiophene nano-membrane prepared in this example, fig. 2 is a distribution diagram of an iron element thereof, fig. 3 is a photograph of an entity thereof, and fig. 4 is an infrared spectrum thereof. As can be seen from FIGS. 1 to 3, the porous polythiophene nanometer film loaded with the nano zero-valent iron is brown black powder, and the polythiophene nanometer film is of a porous structure, and the nano zero-valent iron is loaded on the porous structure, so that the aggregation phenomenon is avoided. As can be seen from FIG. 4, at 1571cm-1Stretching vibration of C ═ C bond with polythiophene benzene ring at 1521cm-1992cm of S-C stretching vibration in the presence of polythiophene-1And 604cm-1Is due to the out-of-plane deformation vibration peak of the C-H bond in the thiophene ring.
Example 2
The preparation process of the porous polythiophene nanometer film loaded with the nanometer zero-valent iron comprises the following steps:
(1) preparation of porous polythiophene nanometer film by combining electrochemical polymerization and chemical oxidation method
Preparing polythiophene film on CHI-660 type electrochemical workstation by adopting cyclic voltammetry electropolymerization, wherein MnO is adopted2As an oxidizing agent. In a three-electrode system, a platinum sheet electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and an electrolyte is a mixed solution of thiophene and dilute sulfuric acid (the concentration is 0.85 mol/L). The electrochemical polymerization conditions are as follows: the polymerization voltage is 0.5V, the scanning rate is 12mV/s, the scanning period is 70 circles, and the polymerization conditions are as follows: to 400mL of dilute sulfuric acid (concentration 0.85mol/L) was added 16mL of thiophene monomer, followed by 1.4g of MnO2And after the polymerization is finished, taking out the working electrode, sequentially cleaning the working electrode by using dilute hydrochloric acid, ethanol and distilled water, gently taking down the polymer film from the working electrode, and drying the polymer film for later use.
(2) Preparation of porous polythiophene nanometer film loaded with nanometer zero-valent iron by liquid phase reduction method
100mL of 0.75mol/L FeSO was taken4Putting the solution into a three-neck flask, adding 2.2g of porous polythiophene membrane powder into the solution, and stirring under the protection of nitrogen and mechanical stirring (the rotating speed is 120 r/m)in), 0.45mL of 0.75mol/L NaBH was added4Dropping the solution into a three-neck flask at a constant speed, continuously stirring and reacting for 60min, filtering and separating the obtained solid phase product, washing with deionized water and ethanol, and vacuum drying at 60 ℃ for 9h to obtain the porous polythiophene nano film loaded with nano zero-valent iron.
The SEM picture, iron element distribution diagram, and physical photograph of the nano zero-valent iron-loaded porous polythiophene nano-membrane prepared in this example and the ir spectrogram are the same as those in example 1, and the drawings are not repeated.
Example 3
The preparation process of the porous polythiophene nanometer film loaded with the nanometer zero-valent iron comprises the following steps:
(1) preparation of porous polythiophene nanometer film by combining electrochemical polymerization and chemical oxidation method
Preparing polythiophene film on CHI-660 type electrochemical workstation by adopting cyclic voltammetry electropolymerization, wherein MnO is adopted2As an oxidizing agent. In a three-electrode system, a platinum sheet electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and an electrolyte is a mixed solution of thiophene and dilute sulfuric acid (the concentration is 1.2 mol/L). The electrochemical polymerization conditions are as follows: the polymerization voltage is 4.0V, the scanning rate is 16mV/s, the scanning period is 80 circles, and the polymerization conditions are as follows: to 400mL of dilute sulfuric acid (1.2 mol/L) was added 20mL of thiophene monomer, followed by 1.8g of MnO2And after the polymerization is finished, taking out the working electrode, sequentially cleaning the working electrode by using dilute hydrochloric acid, ethanol and distilled water, gently taking down the polymer film from the working electrode, and drying the polymer film for later use.
(2) Preparation of porous polythiophene nanometer film loaded with nanometer zero-valent iron by liquid phase reduction method
100mL of 1mol/L FeSO was taken4Putting the solution into a three-neck flask, then adding 2.4g of porous polythiophene membrane powder into the solution, and adding 0.5mL of 0.75mol/L NaBH under the protection of nitrogen and under the mechanical stirring (the rotating speed is 120r/min)4Dropping the solution into a three-neck flask at a constant speed, continuously stirring for reacting for 80min, filtering and separating the obtained solid phase product, washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 12h to obtain the loadA porous polythiophene nanometer film of nanometer zero-valent iron.
The SEM picture, iron element distribution diagram, and physical photograph of the nano zero-valent iron-loaded porous polythiophene nano-membrane prepared in this example and the ir spectrogram are the same as those in example 1, and the drawings are not repeated.
Comparative example
The difference from example 1 is that only the porous polythiophene nano-film of example 1 was prepared, and the nano zero-valent iron loading treatment was not performed on the porous polythiophene nano-film.
The porous polythiophene nanometer films loaded with nanometer zero-valent iron prepared in examples 1-3 and the porous polythiophene nanometer film in the comparative example are applied to heavy metal contaminated soil remediation and used as a heavy metal contaminated soil remediation agent, and the test performance is shown in the following table 1:
TABLE 1 soil samples before and after remediation of heavy metal content test results
Wherein the soil sample is taken from polluted soil around the Wuhan Steel Industrial Port in Hubei as a sample, the pH value of the soil before remediation is 6.8 +/-0.3, and the pH value is 7.1 +/-0.3 after the remediation agent is added. The porous polythiophene nanometer films loaded with nano zero-valent iron prepared in examples 1-3 and the porous polythiophene nanometer films in the comparative examples are used as heavy metal contaminated soil remediation agents, and are applied in a broadcasting mode according to the application amount of 25kg per mu, then deeply turned for 20cm, and remedied for 2 weeks.
As can be seen from the table 1, the porous polythiophene nanometer film loaded with nanometer zero-valent iron provided by the invention is used as a heavy metal contaminated soil remediation agent, and has a good remediation effect on heavy metal contamination treatment.
The preparation method of the porous polythiophene nanometer film loaded with the nanometer zero-valent iron has the following beneficial effects:
(1) the porous polythiophene nanometer film is prepared by combining electrochemical polymerization and chemical oxidation method, and the polythiophene nanometer film is prepared by adopting electrochemical polymerization in the prior artIn contrast, thin films are prepared by the most common chemical oxidation method in the protonic acid environment of electrochemical polymerization by an oxidizing agent (e.g., MnO)2) Oxidizing the thiophene monomer to obtain the chemically doped polythiophene compound film on the one hand, and realizing the pore-forming process on the surface of the polymer through polymerization reaction under proper oxidation conditions on the other hand, thereby enlarging the specific surface area of the material and improving the overall soil remediation performance of the material.
(2) Compared with the nano zero-valent iron loaded by the non-porous polythiophene nano film, the nano zero-valent iron loaded by the porous polythiophene nano film can reduce the environmental oxidation degree of pure nano zero-valent iron, prevent the nano zero-valent iron from being oxidized by moisture and other substances in the environment in the early stage of application and prolong the application period of the nano zero-valent iron; on the other hand, the zero-valent iron nanoparticles can be effectively prevented from agglomerating by loading the oxidized polythiophene film, the monodispersity and the subsequent adsorption performance of the zero-valent iron nanoparticles are improved, and the aim of enhancing the soil remediation performance of the zero-valent iron nanoparticles is fulfilled.
(3) The porous polythiophene nanometer film loaded with nanometer zero-valent iron has better removal capacity on heavy metal ion pollutants in soil.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a porous polythiophene nanometer film loaded with nanometer zero-valent iron is characterized by comprising the following steps:
(1) preparing a porous polythiophene nanometer film by combining an electrochemical polymerization method and a chemical oxidation method;
(2) and preparing the porous polythiophene nanometer film loaded with the nanometer zero-valent iron by adopting a liquid phase reduction method.
2. The preparation method of the nano zero-valent iron-loaded porous polythiophene nano-film according to claim 1, wherein the process of preparing the porous polythiophene nano-film by combining electrochemical polymerization and chemical oxidation is as follows:
preparing polythiophene by adopting cyclic voltammetry electrochemical polymerization on a CHI-660 type electrochemical workstation, and adding an oxidant to carry out chemical doping and pore-forming.
3. The method for preparing the nano zero-valent iron-loaded porous polythiophene nano-film according to claim 2, wherein in the preparation of the porous polythiophene nano-film by combining electrochemical polymerization and chemical oxidation, a platinum sheet electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, an electrolyte is a mixed solution of thiophene monomers and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is MnO (MnO), in a three-electrode system2。
4. The preparation method of the nano zero-valent iron-loaded porous polythiophene nano-film according to claim 3, wherein electrochemical polymerization electrical parameters are controlled as follows: the polymerization voltage is 0.2-4.0V, the scanning speed is 2-20 mV/s, and the scanning period is 15-80 circles;
the chemical parameters were controlled as follows: adding 2-20 mL of thiophene monomer into 400mL of dilute sulfuric acid, and then adding 0.02-1.80 g of MnO2An oxidizing agent.
5. The method for preparing the nano zero-valent iron-loaded porous polythiophene nano-membrane according to claim 1, wherein after the preparation of the porous polythiophene nano-membrane by combining electrochemical polymerization and chemical oxidation, the method further comprises the steps of sequentially cleaning a working electrode by using dilute hydrochloric acid, ethanol and distilled water, slightly taking a product off the working electrode, and drying the product for later use.
6. The method for preparing the nano zero-valent iron-loaded porous polythiophene nano-membrane according to claim 1, wherein the process for preparing the nano zero-valent iron-loaded porous polythiophene nano-membrane by using a liquid phase reduction method comprises the following steps:
in FeSO4Adding the porous polythiophene nanometer film into the solution, adding the reducing agent, and finishing the reactionAnd then filtering, washing and drying the solid phase product to obtain the porous polythiophene nanometer film loaded with the nanometer zero-valent iron.
7. The preparation method of the nano zero-valent iron-loaded porous polythiophene nano-film according to claim 6, wherein the reducing agent is 0.75mol/L of NaBH4Solution, FeSO4The concentration of the solution is 0.25-1 mol/L.
8. The method for preparing the nano zero-valent iron-loaded porous polythiophene nano-membrane according to claim 7, wherein the process for preparing the nano zero-valent iron-loaded porous polythiophene nano-membrane by using a liquid phase reduction method comprises the following steps:
taking 100mL of FeSO4Putting the solution into a three-neck flask, then adding 0.5-2.4 g of porous polythiophene nano-film, and under the protection of nitrogen, stirring and dripping 0.2-0.5 mL of NaBH at a constant speed4And (3) continuing stirring the solution for reaction for 20-80 min, filtering and separating after the reaction is finished to obtain a solid phase product, washing the solid phase product with deionized water and ethanol, and placing the solid phase product at the temperature of 60 ℃ for vacuum drying for 5-12 h to obtain the porous polythiophene nano film loaded with nano zero-valent iron.
9. The porous polythiophene nanometer film loaded with nanometer zero-valent iron and prepared by the preparation method of any one of claims 1 to 8.
10. The use of the nano zero-valent iron-loaded porous polythiophene nano-film according to claim 9 as a heavy metal contaminated soil remediation agent.
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