CN112852436B - Porous polyimidazole nano-film loaded with nano zero-valent iron, and preparation method and application thereof - Google Patents

Porous polyimidazole nano-film loaded with nano zero-valent iron, and preparation method and application thereof Download PDF

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CN112852436B
CN112852436B CN202011617964.2A CN202011617964A CN112852436B CN 112852436 B CN112852436 B CN 112852436B CN 202011617964 A CN202011617964 A CN 202011617964A CN 112852436 B CN112852436 B CN 112852436B
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valent iron
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CN112852436A (en
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陈勇
曹楠
李涛
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Suzhou Shanshui Lintian Environmental Protection Technology Co ltd
Suzhou Zhongke Advanced Technology Research Institute Co Ltd
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Abstract

The invention provides a preparation method of a porous polyimidazole nano-film loaded with nano zero-valent iron, which belongs to the technical field of soil restoration agents and comprises the following steps: (1) Preparing a porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation; (2) The porous polyimidazole nano-film loaded with nano zero-valent iron is prepared by adopting a liquid phase reduction method. The invention also provides a porous polyimidazole nano film loaded with nano zero-valent iron prepared by the method, and the porous polyimidazole nano film is used as a heavy metal contaminated soil restoration agent. The porous polyimidazole nano film loaded with nano zero-valent iron solves the problems of poor monodispersity, easy agglomeration and easy oxidation of nano zero-valent iron serving as a soil restoration agent, and has better removal capability for heavy metal ion pollutants in soil.

Description

Porous polyimidazole nano-film loaded with nano zero-valent iron, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of soil restoration agents, and particularly relates to a porous polyimidazole nano-film loaded with nano zero-valent iron, a preparation method and application thereof.
Background
In recent years, soil pollution worldwide has become serious. Under the large background that the soil quality directly influences the grain production safety, the soil restoration research taking the health of the whole society as the consideration is paid attention to. Among the many soil pollutants, heavy metal ion pollutants have extremely typical characteristics. The plant growth regulator is difficult to catabolize by microorganisms in soil, has the characteristics of small mobility and easiness in enrichment and accumulation in animals and plants, and can influence the growth of a large number of plants, especially the normal growth of crops. On the one hand, the plant and animal diseases are enriched in the body, the continuous accumulation of the plant and animal diseases can directly cause malignant diseases of the plant and animal diseases, and the malignant diseases such as multiple types of tumors and the like are enriched in the body.
Currently, soil remediation research is on the go. A large number of researches show that the nano zero-valent iron has a great application space in the field of soil pollution remediation. The method has a great number of application advantages, such as low use cost, no pollution, and a great number of application examples in the field of water pollution restoration, such as removal of chlorine-containing organic pollutants and heavy metal ions in water. In the field of in situ remediation of soil, nano zero-valent iron is also expected. Based on the characteristic advantages, the current researchers propose that the oxidation of nano zero-valent iron in the soil environment can be effectively overcome, the rapid adsorption performance of the nano zero-valent iron can be enhanced, and the method is possible for large-scale practical application in the future. In the surrounding of the above problems, a series of subsequent improvement approaches have been proposed successively, such as biochar loading, montmorillonite loading, mica sheet loading, and the like. The improved method overcomes the application obstacle of the nano zero-valent iron to a certain extent, and other modification or improvement approaches are still continuously explored. 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, the traditional organic conjugated polymer material has special advantages, such as the application of the polyimidazole in the field of rust prevention and corrosion prevention of metals. If the conjugated polymer material with high specific surface can be prepared based on the method, and the effective load of the conjugated polymer material on the nano zero-valent iron can be realized, the application of the nano powder in soil restoration in a large range can be promoted.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a porous polyimidazole nano film loaded with nano zero-valent iron, and a preparation method and application thereof, and solves the problems of poor monodispersity, easy agglomeration and easy oxidation of nano zero-valent iron serving as a soil restoration agent.
The aim of the invention can be achieved by the following technical measures:
the invention provides a preparation method of a porous polyimidazole nano-film loaded with nano zero-valent iron, which comprises the following steps:
(1) Preparing a porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation;
(2) The porous polyimidazole nano-film loaded with nano zero-valent iron is prepared by adopting a liquid phase reduction method.
Further, the process of preparing the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation method comprises the following steps:
the polyimidazole is prepared by adopting cyclic voltammetry electrochemical polymerization on a CHI-660 type electrochemical workstation, and oxidant is added in the polyimidazole for chemical doping and pore-forming.
Further, in the preparation of the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation, under a three-electrode system, 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 imidazole monomer and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is MnO 2 。
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 are controlled as follows: 2-20 mL of imidazole monomer is added into 400mL of dilute sulfuric acid, and then 0.02-1.80 g of MnO is added 2 An oxidizing agent.
Further, after the preparation of the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation, the method further comprises the steps of cleaning a working electrode by dilute hydrochloric acid, ethanol and distilled water in sequence, gently removing a product from the working electrode, and drying for later use.
Further, the preparation process of the porous polyimidazole nano-film loaded with nano zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
in FeSO 4 Adding a porous polyimidazole nano film into the solution, adding a reducing agent, filtering after the reaction is finished, washing and drying a solid phase product to obtain the porous polyimidazole nano film loaded with nano zero-valent iron.
Further, the reducing agent is NaBH of 0.75mol/L 4 Solution, feSO 4 The concentration of the solution is 0.25-1 mol/L.
Further, the preparation process of the porous polyimidazole nano-film loaded with nano zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
taking 100mL of FeSO 4 Placing the solution into a three-neck flask, then adding 0.5-2.4 g of porous polyimidazole nano film, stirring and dripping 0.2-0.5 mL of NaBH at uniform speed under the protection of nitrogen 4 And (3) continuously 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 vacuum drying at 60 ℃ for 5-12 h to obtain the porous polyimidazole nano-film loaded with nano zero-valent iron.
The invention also provides a porous polyimidazole nano film loaded with nano zero-valent iron, which is prepared by the preparation method.
The invention also provides application of the porous polyimidazole nano film loaded with nano zero-valent iron, and the porous polyimidazole nano film is used as a heavy metal contaminated soil restoration agent.
The preparation method of the porous polyimidazole nano-film loaded with nano zero-valent iron has the following beneficial effects:
(1) The porous polyimidazole nano-film is prepared by combining electrochemical polymerization and chemical oxidation method, and compared with the polyimidazole film prepared by adopting electrochemical polymerization in the prior art, the porous polyimidazole nano-film is prepared by fully utilizing the most common chemical oxidation method, and oxidizing agent (such as MnO 2 ) The imidazole monomer is oxidized to obtain a chemically doped polyimidazole compound film on one hand, and on the other hand, the pore-forming process of the polymer surface is realized through polymerization reaction under proper oxidation conditions, so that the specific surface area of the material is enlarged, and the overall soil restoration performance of the material is improved.
(2) Compared with nano zero-valent iron loaded by a porous polyimidazole nano film, the nano zero-valent iron loaded by the porous polyimidazole nano film can reduce the environmental oxidation degree of pure nano zero-valent iron, prevent the pure nano zero-valent iron from being oxidized by moisture and other substances in the environment in the early application period and prolong the application period of the pure nano zero-valent iron; on the other hand, through the load of the oxidized polyimidazole film, the aggregation of the zero-valent iron nano particles can be effectively prevented, the monodispersity and the subsequent adsorption performance of the zero-valent iron nano particles are improved, and the aim of enhancing the soil restoration performance of the zero-valent iron nano particles is fulfilled.
(3) The porous polyimidazole nano film loaded with nano zero-valent iron has better removal capability for heavy metal ion pollutants in soil.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a porous polyimidazole nano-film loaded with nano-zero-valent iron prepared in example 1 of the present invention;
FIG. 2 is a graph showing the distribution of iron elements in the porous nano-imidazole film loaded with nano-zero-valent iron prepared in example 1 of the present invention;
FIG. 3 is an infrared spectrum of a porous polyimidazole 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 for purposes of illustration only and are not intended to limit the scope of the invention.
In order that the present disclosure may be more fully described and fully understood, the following description is provided by way of illustration of embodiments and specific examples of the present invention; this is not the only form of practicing or implementing the invention as embodied. The description covers the features of the embodiments and 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 sequences of steps.
The invention provides a preparation method of a porous polyimidazole nano-film loaded with nano zero-valent iron, which comprises the following steps:
(1) Preparing a porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation;
(2) The porous polyimidazole nano-film loaded with nano zero-valent iron is prepared by adopting a liquid phase reduction method.
According to the invention, by loading the nano zero-valent iron on the porous polyimidazole nano film, 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 better protected, the degree of 'non-effective oxidation' of the nano zero-valent iron is reduced, the high reactivity of the nano zero-valent iron is maintained, the nano zero-valent iron is prevented from being oxidized by non-target pollutants in the environment such as moisture, and the service life of the nano zero-valent iron is prolonged. Meanwhile, through the loading of the porous polymer nano film, the agglomeration phenomenon can be effectively prevented, the dispersibility, the mechanical strength and the adsorption effect of the nano zero-valent iron particles in the water phase are improved, and the porous polymer nano film has better capability of removing heavy metal ion pollutants.
Wherein, the process of preparing the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation method is as follows:
the polyimidazole is prepared by adopting cyclic voltammetry electrochemical polymerization on a CHI-660 type electrochemical workstation, and oxidant is added in the polyimidazole for chemical doping and pore-forming.
In some embodiments, in the preparation of the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation, under a three-electrode system, 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 imidazole monomer and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is MnO 2 。
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 are controlled as follows: 2-20 mL of imidazole monomer is added into 400mL of dilute sulfuric acid, and then 0.02-1.80 g of MnO is added 2 An oxidizing agent.
In some embodiments, after the preparation of the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation, the method further comprises the steps of sequentially cleaning the working electrode with dilute hydrochloric acid, ethanol and distilled water, gently removing the product from the working electrode, and drying for later use.
The preparation method of the porous polyimidazole nano film loaded with nano zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
in FeSO 4 Adding a porous polyimidazole nano film into the solution, adding a reducing agent, filtering after the reaction is finished, washing and drying a solid phase product to obtain the porous polyimidazole nano film loaded with nano zero-valent iron.
In some embodiments, the reducing agent is NaBH 0.75mol/L 4 Solution, feSO 4 The concentration of the solution is 0.25-1 mol/L.
Specifically, the preparation process of the porous polyimidazole nano-film loaded with nano zero-valent iron by adopting a liquid phase reduction method comprises the following steps:
taking 100mL of FeSO 4 Placing the solution into a three-neck flask, then adding 0.5-2.4 g of porous polyimidazole nano film, stirring and dripping 0.2-0.5 mL of NaBH at uniform speed under the protection of nitrogen 4 And (3) continuously 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 vacuum drying at 60 ℃ for 5-12 h to obtain the porous polyimidazole nano-film loaded with nano zero-valent iron.
Example 1
The preparation process of the porous polyimidazole nano-film loaded with nano zero-valent iron comprises the following steps:
(1) Method for preparing porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation
Preparation of polyimidazole film by cyclic voltammetry electropolymerization on CHI-660 electrochemical workstation with MnO therebetween 2 As an oxidizing agent. Under 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 the electrolyte is a mixed solution of imidazole and dilute sulfuric acid (the concentration is 0.24 mol/L). The electrochemical polymerization conditions are as follows: polymerization voltage of 1.4V, scanning rate of 2.6mV/s, scanning period of 18 circles, and polymerization conditionsThe method comprises the following steps: to 400mL of dilute sulfuric acid (0.24 mol/L concentration) was added 2.8mL of imidazole monomer followed by 0.12g of MnO 2 And taking out the working electrode after polymerization, cleaning the working electrode by dilute hydrochloric acid, ethanol and distilled water in sequence, gently taking the polymer film off the working electrode, and drying for later use.
(2) Porous polyimidazole nano-film loaded with nano zero-valent iron by adopting liquid phase reduction method
100mL of 0.32mol/L FeSO is taken 4 Placing the solution in a three-neck flask, adding 0.6g of porous polyimidazole film powder into the solution, and stirring mechanically under nitrogen protection (rotation speed is 120 r/min) to obtain 0.24mL of 0.75mol/L NaBH 4 And (3) dripping the solution into a three-neck flask at a constant speed, then continuing to stir and react for 35min, filtering and separating the obtained solid phase product, washing with deionized water and ethanol, and vacuum drying for 5h at 60 ℃ to obtain the porous polyimidazole nano-film loaded with nano zero-valent iron.
Fig. 1 is an SEM image of a porous polyimidazole nano-film loaded with nano-zero-valent iron prepared in this example, fig. 2 is an iron element distribution diagram thereof, and fig. 3 is an infrared spectrum thereof. From fig. 1-2, it can be seen that the polyimidazole nano-film has a porous structure, and nano zero-valent iron is loaded on the porous structure without agglomeration phenomenon. As can be seen from FIG. 3, at 1580cm -1 Stretching vibration of C=C bond with imidazole ring at 1513cm -1 N-C stretching vibration of polyimidazole with 975cm -1 562cm -1 The vibration peak is caused by the out-of-plane deformation of the C-H bond in the imidazole ring.
Example 2
The preparation process of the porous polyimidazole nano-film loaded with nano zero-valent iron comprises the following steps:
(1) Method for preparing porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation
Preparation of polyimidazole film by cyclic voltammetry electropolymerization on CHI-660 electrochemical workstation with MnO therebetween 2 As an oxidizing agent. Under 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 the electrolyte is a mixed solution of imidazole and dilute sulfuric acid (the concentration is 0.85 mol/L). Electrochemical polymeric stripThe piece is: the polymerization voltage was 2.3V, the scanning rate was 12mV/s, the scanning period was 36 cycles, and the polymerization conditions were: to 400mL of dilute sulfuric acid (0.85 mol/L concentration) was added 8.4mL of imidazole monomer followed by 0.65g of MnO 2 And taking out the working electrode after polymerization, cleaning the working electrode by dilute hydrochloric acid, ethanol and distilled water in sequence, gently taking the polymer film off the working electrode, and drying for later use.
(2) Porous polyimidazole nano-film loaded with nano zero-valent iron by adopting liquid phase reduction method
100mL of 0.75mol/L FeSO was taken 4 Placing the solution in a three-neck flask, adding 1.7g of porous polyimidazole film powder into the solution, and stirring mechanically under nitrogen protection (rotation speed is 120 r/min) to obtain 0.45mL of 0.75mol/L NaBH 4 And (3) dripping the solution into a three-neck flask at a constant speed, then continuing to stir and react for 60min, filtering and separating the obtained solid phase product, washing with deionized water and ethanol, and vacuum drying for 9h at 60 ℃ to obtain the porous polyimidazole nano-film loaded with nano zero-valent iron.
The SEM image, the iron element distribution map and the infrared spectrogram of the porous polyimidazole nano-film loaded with nano zero-valent iron prepared in the embodiment are the same as those in the embodiment 1, and the drawings are not repeated.
Example 3
The preparation process of the porous polyimidazole nano-film loaded with nano zero-valent iron comprises the following steps:
(1) Method for preparing porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation
Preparation of polyimidazole film by cyclic voltammetry electropolymerization on CHI-660 electrochemical workstation with MnO therebetween 2 As an oxidizing agent. Under 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 the electrolyte is a mixed solution of imidazole 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 speed is 20mV/s, the scanning period is 80 circles, and the polymerization conditions are as follows: to 400mL of dilute sulfuric acid (1.2 mol/L concentration) was added 20mL of imidazole monomer followed by 1.8g of MnO 2 Taking out the working electrode after polymerization, sequentially using dilute hydrochloric acidAnd (3) cleaning with ethanol and distilled water, slightly removing the polymer film from the working electrode, and drying for later use.
(2) Porous polyimidazole nano-film loaded with nano zero-valent iron by adopting liquid phase reduction method
100mL of 1mol/L FeSO was taken 4 Placing the solution in a three-neck flask, adding 2.4g of porous polyimidazole film powder into the solution, and stirring mechanically under nitrogen protection (rotation speed is 120 r/min) to obtain 0.5mL of 0.75mol/L NaBH 4 And (3) dripping the solution into a three-neck flask at a constant speed, then continuing to stir and react for 80min, filtering and separating the obtained solid phase product, washing with deionized water and ethanol, and vacuum drying at 60 ℃ for 12h to obtain the porous polyimidazole nano-film loaded with nano zero-valent iron.
The SEM image, the iron element distribution map and the infrared spectrogram of the porous polyimidazole nano-film loaded with nano zero-valent iron prepared in the embodiment are the same as those in the embodiment 1, and the drawings are not repeated.
Comparative example
The difference from example 1 is that only the porous polyimidazole nanofilm of example 1 was prepared, and no nano zero-valent iron loading treatment was performed on the porous polyimidazole nanofilm.
The porous polyimidazole nano-film loaded with nano zero-valent iron prepared in the examples 1-3 and the porous polyimidazole nano-film in the comparative example are applied to the remediation of heavy metal contaminated soil, and are used as heavy metal contaminated soil remediation agents, and the test performance is shown in the following table 1:
TABLE 1 detection results of heavy metal content of soil samples before and after remediation
Wherein, the soil sample is taken from the surrounding polluted soil of the Wuhan steel industrial port in Hubei province as the sample, the pH value of the soil before restoration is 6.8+/-0.3, and the pH value after adding the restoration agent is 7.1+/-0.3. The porous polyimidazole nano-film loaded with nano zero-valent iron prepared in the examples 1-3 and the porous polyimidazole nano-film in the comparative example are used as heavy metal contaminated soil restoration agents, and are applied at 25kg per mu, then deeply turned for 20cm and restored for 2 weeks.
From table 1, it can be seen that the porous polyimidazole nano film loaded with nano zero-valent iron of the invention is used as a heavy metal contaminated soil restoration agent, and has good restoration effect on heavy metal contaminated treatment.
The preparation method of the porous polyimidazole nano-film loaded with nano zero-valent iron has the following beneficial effects:
(1) The porous polyimidazole nano-film is prepared by combining electrochemical polymerization and chemical oxidation method, and compared with the polyimidazole film prepared by adopting electrochemical polymerization in the prior art, the porous polyimidazole nano-film is prepared by fully utilizing the most common chemical oxidation method, and oxidizing agent (such as MnO 2 ) The imidazole monomer is oxidized to obtain a chemically doped polyimidazole compound film on one hand, and on the other hand, the pore-forming process of the polymer surface is realized through polymerization reaction under proper oxidation conditions, so that the specific surface area of the material is enlarged, and the overall soil restoration performance of the material is improved.
(2) Compared with nano zero-valent iron loaded by a porous polyimidazole nano film, the nano zero-valent iron loaded by the porous polyimidazole nano film can reduce the environmental oxidation degree of pure nano zero-valent iron, prevent the pure nano zero-valent iron from being oxidized by moisture and other substances in the environment in the early application period and prolong the application period of the pure nano zero-valent iron; on the other hand, through the load of the oxidized polyimidazole film, the aggregation of the zero-valent iron nano particles can be effectively prevented, the monodispersity and the subsequent adsorption performance of the zero-valent iron nano particles are improved, and the aim of enhancing the soil restoration performance of the zero-valent iron nano particles is fulfilled.
(3) The porous polyimidazole nano film loaded with nano zero-valent iron has better removal capability for heavy metal ion pollutants in soil.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (6)

1. The preparation method of the porous polyimidazole nano-film loaded with nano zero-valent iron is characterized by comprising the following steps of:
(1) Preparing a porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation;
(2) Preparing a porous polyimidazole nano film loaded with nano zero-valent iron by adopting a liquid phase reduction method;
the process of preparing the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation method is as follows:
preparing polyimidazole by adopting cyclic voltammetry electrochemical polymerization, and adding an oxidant during the process to carry out chemical doping and pore-forming;
in the preparation of the porous polyimidazole 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 under a three-electrode system, an electrolyte is a mixed solution of imidazole monomer and dilute sulfuric acid, the concentration of the dilute sulfuric acid is 0.2-1.2 mol/L, and an oxidant is MnO 2 ；
The electrochemical polymerization electrical parameters were 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 are controlled as follows: 2-20 mL of imidazole monomer is added into 400mL of dilute sulfuric acid, and then 0.02-1.80 g of MnO is added 2 An oxidizing agent;
the preparation process of the porous nanometer polyimidazole film loaded with nanometer zero-valent iron by adopting the liquid phase reduction method comprises the following steps:
in FeSO 4 Adding a porous polyimidazole nano film into the solution, adding a reducing agent, filtering after the reaction is finished, washing and drying a solid phase product to obtain the porous polyimidazole nano film loaded with nano zero-valent iron.
2. The method for preparing a nano zero-valent iron loaded porous polyimidazole nano-film according to claim 1, wherein after the preparation of the porous polyimidazole nano-film by combining electrochemical polymerization and chemical oxidation is completed, the method further comprises the steps of sequentially washing a working electrode with dilute hydrochloric acid, ethanol and distilled water, gently removing a product from the working electrode, and drying for later use.
3. The method for preparing the nano zero-valent iron-loaded porous polyimidazole nano film according to claim 1, wherein the reducing agent is NaBH of 0.75mol/L 4 Solution, feSO 4 The concentration of the solution is 0.25-1 mol/L.
4. The method for preparing the nano zero-valent iron-loaded porous polyimidazole nano film according to claim 3, wherein the method for preparing the nano zero-valent iron-loaded porous polyimidazole nano film by adopting a liquid phase reduction method comprises the following steps of:
taking 100mL of FeSO 4 Placing the solution into a three-neck flask, then adding 0.5-2.4 g of porous polyimidazole nano film, stirring and dripping 0.2-0.5 mL of NaBH at uniform speed under the protection of nitrogen 4 And (3) continuously 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 vacuum drying at 60 ℃ for 5-12 h to obtain the porous polyimidazole nano-film loaded with nano zero-valent iron.
5. A nano zero-valent iron loaded porous polyimidazole nano-film prepared by the preparation method of any one of claims 1-4.
6. The application of the porous polyimidazole nano-film loaded with nano-zero-valent iron according to claim 5, which is characterized in that the porous polyimidazole nano-film is used as a heavy metal contaminated soil restoration agent.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687187A (en) * 2005-05-12 2005-10-26 上海交通大学 Poly imidazole and preparation method thereof
CN102993454A (en) * 2011-09-08 2013-03-27 睿元奈米环境科技股份有限公司 Zero-valent metal-containing polymer composite carrier and manufacturing method thereof
CN105732982A (en) * 2014-12-10 2016-07-06 中国科学院大连化学物理研究所 Method for synthesizing porous polyimidazoline high-polymer material
CN106825013A (en) * 2017-02-27 2017-06-13 环境保护部南京环境科学研究所 Using the method for modified Nano Zero-valent Iron heavy metal contaminated soil stabilization processes
CN106967217A (en) * 2016-01-14 2017-07-21 华南理工大学 Polyimidazole class compound and its in-situ preparation method and application
CN109092265A (en) * 2018-09-10 2018-12-28 陕西科技大学 A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687187A (en) * 2005-05-12 2005-10-26 上海交通大学 Poly imidazole and preparation method thereof
CN102993454A (en) * 2011-09-08 2013-03-27 睿元奈米环境科技股份有限公司 Zero-valent metal-containing polymer composite carrier and manufacturing method thereof
CN105732982A (en) * 2014-12-10 2016-07-06 中国科学院大连化学物理研究所 Method for synthesizing porous polyimidazoline high-polymer material
CN106967217A (en) * 2016-01-14 2017-07-21 华南理工大学 Polyimidazole class compound and its in-situ preparation method and application
CN106825013A (en) * 2017-02-27 2017-06-13 环境保护部南京环境科学研究所 Using the method for modified Nano Zero-valent Iron heavy metal contaminated soil stabilization processes
CN109092265A (en) * 2018-09-10 2018-12-28 陕西科技大学 A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified

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