CN112795052A - Porous polyaniline nano-film loaded with nano zero-valent iron and preparation method and application thereof - Google Patents
Porous polyaniline nano-film loaded with nano zero-valent iron and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000002120 nanofilm Substances 0.000 title claims abstract description 97
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 28
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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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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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
- C08J9/40—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention provides a preparation method of a porous polyaniline nano-film loaded with nano zero-valent iron, belonging to the technical field of soil remediation agents and comprising the following steps: (1) preparing a porous polyaniline nano-film by combining an electrochemical polymerization method and a chemical oxidation method; (2) and preparing the porous polyaniline nano-film loaded with the nano zero-valent iron by adopting a liquid phase reduction method. The invention also provides the porous polyaniline nano-film loaded with the nano zero-valent iron prepared by the method and the application of the porous polyaniline nano-film as a heavy metal polluted soil remediation agent. The porous polyaniline nano-film loaded with the nano zero-valent iron solves the problems of poor monodispersity, easy agglomeration and easy oxidation of the nano zero-valent iron as a soil remediation agent, and has better removal capability on 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 polyaniline nano-film loaded with nano zero-valent iron, and a preparation method and application thereof.
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 a plurality of soil pollutants, heavy metal ion pollutants have the very typical characteristics of being difficult to be decomposed and metabolized by microorganisms in soil, having the characteristics of small mobility and easy enrichment and accumulation in animals and plants, and influencing the growth of a large number of plants, particularly 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, for example, the polyaniline 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 polyaniline nano-film loaded with nano zero-valent iron, a preparation method and application thereof aiming at the defects in the prior art, and solves the problems of poor monodispersity, easy agglomeration and easy oxidation of the nano zero-valent iron as a soil remediation agent.
The object of the invention can be achieved by the following technical measures:
the invention provides a preparation method of a porous polyaniline nano-film loaded with nano zero-valent iron, which comprises the following steps:
(1) preparing a porous polyaniline nano-film by combining an electrochemical polymerization method and a chemical oxidation method;
(2) and preparing the porous polyaniline nano-film loaded with the nano zero-valent iron by adopting a liquid phase reduction method.
Further, the process of preparing the porous polyaniline nano-film by combining electrochemical polymerization and chemical oxidation is as follows:
preparing polyaniline by electrochemical polymerization with cyclic voltammetry on a CHI-660 type electrochemical workstation, and adding an oxidant to carry out chemical doping and pore-forming.
Furthermore, in the preparation of the porous polyaniline nano-film by combining electrochemical polymerization and chemical oxidation methods, a platinum sheet electrode is adopted as an auxiliary electrode and a saturated calomel electrode is adopted as a reference electrode in a three-electrode system,the electrolyte is a mixed solution of aniline monomer and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and the oxidant is V2O5。
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 aniline monomer into 400mL dilute sulfuric acid, and then adding 0.02-1.80 g V2O5An oxidizing agent.
Further, after the preparation of the porous polyaniline nano-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 polyaniline nano-film loaded with the nano zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
in FeSO4And adding the porous polyaniline 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 polyaniline 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 polyaniline nano-film loaded with the nano 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 polyaniline 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 product at 60 ℃ for vacuum drying for 5-12 h to obtain the porous polyaniline nano-film loaded with the nano zero-valent iron.
The invention also provides the porous polyaniline nano-film loaded with the nano zero-valent iron prepared by the preparation method.
The invention also provides application of the porous polyaniline nano-film loaded with the nano zero-valent iron, and the porous polyaniline nano-film is used as a heavy metal polluted soil remediation agent.
The preparation method of the porous polyaniline nano-film loaded with the nano zero-valent iron has the following beneficial effects:
(1) compared with the prior art which adopts electrochemical polymerization to prepare the polyaniline film, the most common chemical oxidation method is fully utilized to prepare the porous polyaniline nano film by combining the electrochemical polymerization and the chemical oxidation method, and an oxidant (such as V) is used in the protonic acid environment of the electrochemical polymerization2O5) Oxidizing aniline monomer to obtain chemically doped polyaniline compound film, and polymerizing under proper oxidizing condition to form pore forming in the surface of polymer and to enlarge the specific surface area of the material and raise the soil repairing performance of the material.
(2) Compared with the nano zero-valent iron loaded by the non-porous polyaniline nano film, the nano zero-valent iron loaded by the porous polyaniline 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 load of the oxidized polyaniline film can effectively prevent the agglomeration of the zero-valent iron nano particles, improve the monodispersity and the subsequent adsorption performance of the zero-valent iron nano particles, and achieve the purpose of enhancing the soil remediation performance of the zero-valent iron nano particles.
(3) The porous polyaniline nano-film loaded with the nano zero-valent iron has better removal capability 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 polyaniline nano-film loaded with nano-zero-valent iron prepared in example 1 of the present invention;
FIG. 2 is a distribution diagram of iron elements of the porous polyaniline nano-film loaded with nano-zero-valent iron prepared in example 1 of the present invention;
FIG. 3 is a photograph of a porous polyaniline nano-film loaded with nano-zero-valent iron prepared in example 1 of the present invention;
FIG. 4 is an infrared spectrum of the porous polyaniline nano-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 polyaniline nano-film loaded with nano zero-valent iron, which comprises the following steps:
(1) preparing a porous polyaniline nano-film by combining an electrochemical polymerization method and a chemical oxidation method;
(2) and preparing the porous polyaniline nano-film loaded with the nano zero-valent iron by adopting a liquid phase reduction method.
According to the invention, the nano zero-valent iron is loaded on the porous polyaniline nano film, so that on one hand, the loss of the nano zero-valent iron can be greatly limited, compared with the conventional process, the nano zero-valent iron is more excellent in protection, 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 nano zero-valent iron is prevented from being oxidized by non-target pollutants such as water in the environment, 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 polyaniline nano-film by combining electrochemical polymerization and chemical oxidation comprises the following steps:
preparing polyaniline by electrochemical polymerization with cyclic voltammetry 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 polyaniline 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 aniline monomer and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is V2O5。
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 aniline monomer into 400mL dilute sulfuric acid, and then adding 0.02-1.80 g V2O5An oxidizing agent.
In some embodiments, after the preparation of the porous polyaniline nano-film by combining the electrochemical polymerization and the chemical oxidation methods, the method further comprises sequentially cleaning the working electrode with dilute hydrochloric acid, ethanol and distilled water, gently removing the product from the working electrode, and drying the product for later use.
The process for preparing the porous polyaniline nano-film loaded with the nano zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
in FeSO4Adding a porous polyaniline 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 polyaniline nano-loaded with nano zero-valent ironRice film.
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 polyaniline nano-film loaded with the nano 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 polyaniline 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 product at 60 ℃ for vacuum drying for 5-12 h to obtain the porous polyaniline nano-film loaded with the nano zero-valent iron.
Example 1
The preparation process of the porous polyaniline nano-film loaded with the nano zero-valent iron comprises the following steps:
(1) preparation of porous polyaniline nano-film by combining electrochemical polymerization and chemical oxidation method
Preparing polyaniline film by electropolymerization on CHI-660 type electrochemical workstation by adopting cyclic voltammetry, wherein V is adopted2O5As 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 aniline and dilute sulfuric acid (the concentration is 0.2 mol/L). The electrochemical polymerization conditions are as follows: the polymerization voltage is 0.4V, the scanning rate is 2mV/s, the scanning period is 15 circles, and the polymerization conditions are as follows: to 400mL of dilute sulfuric acid (concentration 0.2mol/L) was added 2.5mL of aniline monomer, followed by 0.02g V2O5And 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) Preparing porous polyaniline nano-film loaded with nano zero-valent iron by adopting liquid phase reduction method
100mL of 0.30mol/L FeSO is taken4The solution was placed in a three-necked flask, and 0.6g of porous polyaniline was added to the solutionFilm powder, under the protection of nitrogen and mechanical stirring (the rotating speed is 120r/min), 0.25mL of 0.75mol/L NaBH4Dripping the solution into a three-neck flask at a constant speed, then continuously stirring and reacting for 25min, filtering and separating the obtained solid phase product, washing the solid phase product with deionized water and ethanol, and drying the solid phase product in vacuum at the temperature of 60 ℃ for 8h to obtain the porous polyaniline nano-film loaded with nano zero-valent iron.
Fig. 1 is an SEM image of the porous polyaniline nano-film loaded with nano zero-valent iron prepared in this example, fig. 2 is a distribution diagram of iron elements thereof, fig. 3 is a photograph of an actual object thereof, and fig. 4 is an infrared spectrum thereof. As can be seen from FIGS. 1-3, the porous polyaniline nano-film loaded with nano zero-valent iron is in the form of black powder, and the polyaniline nano-film is in a porous structure, and the nano zero-valent iron is loaded on the porous structure, so that no agglomeration phenomenon occurs. As can be seen from FIG. 4, at 1578cm-1C-C bond stretching vibration with polyaniline benzene ring at 1487cm-1There is N-H stretching vibration of polyaniline, 832cm-1And 509cm-1Is due to the out-of-plane deformation vibration peak of the C-H bond in the benzene ring.
Example 2
The preparation process of the porous polyaniline nano-film loaded with the nano zero-valent iron comprises the following steps:
(1) preparation of porous polyaniline nano-film by combining electrochemical polymerization and chemical oxidation method
Preparing polyaniline film by electropolymerization on CHI-660 type electrochemical workstation by adopting cyclic voltammetry, wherein V is adopted2O5As 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 aniline and dilute sulfuric acid (the concentration is 0.35 mol/L). The electrochemical polymerization conditions are as follows: the polymerization voltage is 0.8V, the scanning rate is 6mV/s, the scanning period is 30 circles, and the polymerization conditions are as follows: to 400mL of dilute sulfuric acid (concentration 0.35mol/L) was added 4.5mL of aniline monomer, followed by 0.15g V2O5And 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) Preparing porous polyaniline nano-film loaded with nano zero-valent iron by adopting liquid phase reduction method
100mL of 0.45mol/L FeSO was taken4Putting the solution into a three-neck flask, adding 1.0g of porous polyaniline film powder into the solution, and adding 0.2mL of 0.75mol/L NaBH under the protection of nitrogen and under the mechanical stirring (the rotating speed is 120r/min)4Dripping the solution into a three-neck flask at a constant speed, then continuously stirring and reacting for 35min, filtering and separating the obtained solid phase product, washing the solid phase product with deionized water and ethanol, and drying the solid phase product in vacuum at the temperature of 60 ℃ for 6h to obtain the porous polyaniline nano-film loaded with nano zero-valent iron.
The SEM picture, iron element distribution diagram, and physical photograph of the porous polyaniline nano-film loaded with nano zero-valent iron prepared in this example and the infrared spectrogram are the same as those in example 1, and the drawings are not repeated.
Example 3
The preparation process of the porous polyaniline nano-film loaded with the nano zero-valent iron comprises the following steps:
(1) preparation of porous polyaniline nano-film by combining electrochemical polymerization and chemical oxidation method
Preparing polyaniline film by electropolymerization on CHI-660 type electrochemical workstation by adopting cyclic voltammetry, wherein V is adopted2O5As 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 aniline and dilute sulfuric acid (the concentration is 1.0 mol/L). The electrochemical polymerization conditions are as follows: the polymerization voltage is 3.0V, the scanning rate is 15mV/s, the scanning period is 50 circles, and the polymerization conditions are as follows: to 400mL of dilute sulfuric acid (1.0 mol/L) was added 12mL of aniline monomer, followed by 1.5g V2O5And 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) Preparing porous polyaniline nano-film loaded with nano zero-valent iron by adopting liquid phase reduction method
100mL of 0.90mol/L FeSO is taken4Placing the solution in a three-neck flask, and adding the solution1.8g of porous polyaniline film powder, under the protection of nitrogen and mechanical stirring (the rotating speed is 120r/min), 0.4mL of 0.75mol/L NaBH4Dripping the solution into a three-neck flask at a constant speed, then continuously stirring and reacting for 70min, filtering and separating the obtained solid phase product, washing the solid phase product with deionized water and ethanol, and drying the solid phase product in vacuum at the temperature of 60 ℃ for 10h to obtain the porous polyaniline nano-film loaded with nano zero-valent iron.
The SEM picture, iron element distribution diagram, and physical photograph of the porous polyaniline nano-film loaded with nano zero-valent iron prepared in this example and the infrared 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 polyaniline nano-film in example 1 was prepared, and the nano zero-valent iron loading treatment was not performed on the porous polyaniline nano-film.
The porous polyaniline nano-films loaded with nano zero-valent iron prepared in examples 1-3 and the porous polyaniline nano-films in comparative examples are applied to heavy metal contaminated soil remediation and used as heavy metal contaminated soil remediation agents, and the test performances are 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 polyaniline nano-films loaded with nano zero-valent iron prepared in examples 1-3 and the porous polyaniline nano-films in the comparative examples, which are used as heavy metal contaminated soil remediation agents, are applied by spraying 25kg per mu, then deeply turned for 20cm, and remediated for 2 weeks.
As can be seen from Table 1, the porous polyaniline nano-film loaded with nano-zero-valent iron provided by the invention is used as a heavy metal polluted soil remediation agent, and has a good remediation effect on heavy metal pollution treatment.
The preparation method of the porous polyaniline nano-film loaded with the nano zero-valent iron has the following beneficial effects:
(1) compared with the prior art which adopts electrochemical polymerization to prepare the polyaniline film, the most common chemical oxidation method is fully utilized to prepare the porous polyaniline nano film by combining the electrochemical polymerization and the chemical oxidation method, and an oxidant (such as V) is used in the protonic acid environment of the electrochemical polymerization2O5) Oxidizing aniline monomer to obtain chemically doped polyaniline compound film, and polymerizing under proper oxidizing condition to form pore forming in the surface of polymer and to enlarge the specific surface area of the material and raise the soil repairing performance of the material.
(2) Compared with the nano zero-valent iron loaded by the non-porous polyaniline nano film, the nano zero-valent iron loaded by the porous polyaniline 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 load of the oxidized polyaniline film can effectively prevent the agglomeration of the zero-valent iron nano particles, improve the monodispersity and the subsequent adsorption performance of the zero-valent iron nano particles, and achieve the purpose of enhancing the soil remediation performance of the zero-valent iron nano particles.
(3) The porous polyaniline nano-film loaded with the nano zero-valent iron has better removal capability 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 polyaniline nano-film loaded with nano zero-valent iron is characterized by comprising the following steps:
(1) preparing a porous polyaniline nano-film by combining an electrochemical polymerization method and a chemical oxidation method;
(2) and preparing the porous polyaniline nano-film loaded with the nano zero-valent iron by adopting a liquid phase reduction method.
2. The method for preparing the nano zero-valent iron-loaded porous polyaniline nano-film according to claim 1, which is characterized in that the process of preparing the porous polyaniline nano-film by combining electrochemical polymerization and chemical oxidation is as follows:
preparing polyaniline by electrochemical polymerization with cyclic voltammetry 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 polyaniline nano-film according to claim 2, wherein in the preparation of the porous polyaniline nano-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 aniline monomer and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is V2O5。
4. The method for preparing the nano zero-valent iron-loaded porous polyaniline nano-film as claimed in claim 3, wherein 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 aniline monomer into 400mL dilute sulfuric acid, and then adding 0.02-1.80 g V2O5An oxidizing agent.
5. The method for preparing the nano zero-valent iron-loaded porous polyaniline nano-film according to claim 1, which is characterized by further comprising the steps of cleaning the working electrode with dilute hydrochloric acid, ethanol and distilled water in sequence after the porous polyaniline nano-film is prepared by combining electrochemical polymerization and chemical oxidation, slightly taking the product off the working electrode, and drying the product for later use.
6. The method for preparing the nano zero-valent iron-loaded porous polyaniline nano-film according to claim 1, wherein the liquid phase reduction method is adopted to prepare the nano zero-valent iron-loaded porous polyaniline nano-film in the following steps:
in FeSO4And adding the porous polyaniline 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 polyaniline nano-film loaded with the nano zero-valent iron.
7. The method for preparing the nano zero-valent iron-loaded porous polyaniline nano-film as claimed in claim 6, wherein the reducing agent is NaBH of 0.75mol/L4Solution, FeSO4The concentration of the solution is 0.25-1 mol/L.
8. The method for preparing the nano zero-valent iron-loaded porous polyaniline nano-film according to claim 7, wherein the liquid phase reduction method is adopted to prepare the nano zero-valent iron-loaded porous polyaniline nano-film in the following steps:
taking 100mL of FeSO4Putting the solution into a three-neck flask, then adding 0.5-2.4 g of porous polyaniline 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 product at 60 ℃ for vacuum drying for 5-12 h to obtain the porous polyaniline nano-film loaded with the nano zero-valent iron.
9. The porous polyaniline nano-film loaded with nano zero-valent iron prepared by the preparation method of any one of claims 1 to 8.
10. The use of the nano zero-valent iron-loaded porous polyaniline nanofilm as claimed in claim 9, which is used as a remediation agent for heavy metal contaminated soil.
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