A method for simultaneous synthesis and carbonization application of polypyrrole-thiophene

Abstract

The invention discloses a method for synthesizing polypyrrole-thiophene simultaneously, firstly prepolymerizing thiophene monomer, surfactant, ferric chloride and hydrogen peroxide in aqueous solution; then adding pyrrole monomer solution containing surfactant, uniformly mixing for 24h to obtain polypyrrole-thiophene. The present invention also provides a method for polypyrrole-thiophene to catalyze persulfate degradation of aniline, carbonizing polypyrrole-thiophene to obtain carbonized polypyrrole-thiophene, applying carbonized polypyrrole-thiophene to catalyze persulfate, and for degrading aniline solution, realizing aniline degradation. The present invention realizes the one-step synthesis of polypyrrole-thiophene in aqueous solution using surfactant, greatly reduces the use of organic solvent and ferric chloride, the material preparation process is simple, efficient and safe, the obtained polypyrrole-thiophene is used to catalyze persulfate degradation of aniline, the aniline degradation rate is high, and the carbonized polypyrrole-thiophene also has a certain adsorption effect on aniline, further improving the processing efficiency.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, and in particular to a method for simultaneous synthesis and carbonization application of polypyrrole-thiophene. Background Art

[0002] With the continuous progress and development of industrial production technology and the continuous updating and reform of wastewater deep treatment technology, in order to solve the difficulties of physical treatment methods such as high energy consumption, high operating costs, and strict equipment requirements; chemical treatment methods (such as transition metal ions and metal oxides catalyzed persulfate) metal leaching, metal sludge sedimentation, etc., the development and preparation of green and environmentally friendly catalysts with no metal leaching toxicity and high persulfate utilization rate is a problem that needs to be solved at this stage.

[0003] At present, the existing non-metallic carbon-based catalyst materials (such as biochar, activated carbon and carbon fiber) have complex surface structures and uncontrollable types of active functional groups, and are not the best carbon-based catalyst materials. In addition, by adding sulfur or nitrogen-containing raw materials to carbon-based materials, sulfur and nitrogen are doped. In this process, a large amount of heteroatom elements are inevitably lost, the doping elements are unevenly distributed, and multi-step synthesis is required. Therefore, in the selection of heteroatom doping methods, it is still necessary to further explore more efficient and simple doping methods.

[0004] Currently, polypyrrole or polythiophene is synthesized in an organic medium, an ethanol-water medium, or an aqueous medium using pyrrole monomers, thiophene monomers, ferric chloride, ferrous chloride, hydrogen peroxide, and a surfactant. For example, Chinese patent document No. CN104785223A discloses a polypyrrole / nickel ferrite nanocomposite material and its preparation and application. The patent uses an ethanol-water mixed solution as a medium to prepare a polypyrrole composite material under the action of ferric chloride and ultrasound. For example, Chinese patent document No. CN102766250A discloses a polythiophene microsphere and its preparation method. The patent uses an aqueous solution as a medium to prepare a polythiophene microsphere under the action of ferrous chloride and hydrogen peroxide. Aysegul A., Omastová, M., & Yavuz, AG (2007). Synthesis and characterization of polythiophenes prepared in the presence of surfactants. Synthetic metals, 157 (1), 23-29.) et al. used anionic surfactants (sodium dodecylbenzenesulfonate), cationic surfactants (tetradecyltrimethylammonium bromide) or nonionic surfactants (polyethylene oxide) to synthesize polythiophenes in chloroform medium and ferric chloride. In order to achieve in-situ doping of sulfur and nitrogen elements in carbon materials, reduce the amount of ferric chloride and organic solvents, and simplify the preparation process, it is necessary to find a method for efficient and simultaneous synthesis of polypyrrole-thiophene in aqueous solution, and to carbonize and apply it. Summary of the invention

[0005] The purpose of the present invention is to provide a method for simultaneously synthesizing polypyrrole-thiophene to solve the deficiency of separately synthesizing polypyrrole and polythiophene in the prior art.

[0006] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0007] A method for simultaneously synthesizing polypyrrole-thiophene, the method comprising the following steps:

[0008] Step 1, adding thiophene monomer, surfactant, ferric chloride and hydrogen peroxide into an aqueous solution for prepolymerization;

[0009] Step 2, adding a pyrrole monomer solution containing a surfactant to the aqueous solution in step 1, uniformly mixing, filtering, rinsing, and drying to obtain polypyrrole-thiophene.

[0010] In the above steps, a surfactant is used to dissolve the thiophene monomer and the pyrrole monomer in an aqueous solution, and hydrogen peroxide is used to reduce the amount of ferric chloride, and the polypyrrole-thiophene material is synthesized under the action of ferric chloride. Since the synthesis time of polythiophene is long, a part of polythiophene is synthesized first, and then the pyrrole monomer is added.

[0011] Furthermore, in step 1, the surfactant includes: a cationic surfactant or a non-ionic surfactant.

[0012] Preferably, the surfactant includes one or more of hexadecyltrimethylammonium bromide and triblock copolymer.

[0013] Preferably, the mass ratio of thiophene monomer, surfactant, ferric chloride and 30% hydrogen peroxide is 3.16-6.30:0.50:0.09:22.20-133.20.

[0014] Preferably, the amount of thiophene monomer used is 6.30 g / L.

[0015] Preferably, the amount of 30% hydrogen peroxide used is 20 mL / L.

[0016] Furthermore, in step 2, the mass ratio of the surfactant to the pyrrole monomer is 0.50:5.00-7.55.

[0017] The surfactant includes: one or more of hexadecyltrimethylammonium bromide and triblock copolymer.

[0018] Preferably, the pyrrole monomer is used in an amount of 5.00 g / L.

[0019] Preferably, the filtering and rinsing step comprises filtering the aqueous solution, and rinsing the filter residue with hydrochloric acid solution, ultrapure water and ethanol in sequence.

[0020] Preferably, the drying condition is 60° C. and the drying time is 12 to 36 hours.

[0021] Furthermore, the present invention also includes a method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate, the method comprising the steps of:

[0022] Step 3, carbonizing polypyrrole-thiophene to obtain carbonized polypyrrole-thiophene;

[0023] Step 4: carbonized polypyrrole-thiophene is used to catalyze persulfate and to degrade aniline solution.

[0024] Polypyrrole-thiophene is carbonized to obtain a carbon material containing an aromatic ring structure. The nitrogen elements in the carbonized polypyrrole-thiophene are mainly graphitic nitrogen and pyridinic nitrogen, which are beneficial to the catalytic degradation of persulfate and oxidative degradation of aniline, and the catalytic degradation time is 1-30 minutes.

[0025] Furthermore, in step 3, polypyrrole-thiophene is calcined in a heat-resistant sealed container in a nitrogen atmosphere, the calcination temperature is set at 900-1200° C., the calcination time is set at 2 h, and nitrogen is introduced for cooling after calcination to obtain carbonized polypyrrole-thiophene.

[0026] Preferably, the calcination temperature is 1000°C.

[0027] Preferably, in step 4, the cooled carbonized polypyrrole-thiophene is ground.

[0028] Preferably, in step 4, the carbonized polypyrrole-thiophene is ground to -0.14 mm (100 mesh).

[0029] Furthermore, in step 4, the carbonized polypyrrole-thiophene cooled in step 3.2 is ground, and the ground carbonized polypyrrole-thiophene is used to catalyze 0.5 g of persulfate, and then used to degrade the aniline solution.

[0030] Preferably, step 4 may also be: adding the ground carbonized polypyrrole-thiophene to an aniline solution to prepare a first solution, and adding persulfate to the first solution to degrade the aniline.

[0031] Preferably, in step 4, the concentration of the aniline solution is 30 mg / L, and the persulfate is one or more of potassium permonosulfate, sodium persulfate or potassium persulfate.

[0032] Preferably, the mass ratio of carbonized polypyrrole-thiophene to aniline is 2:1.

[0033] Preferably, the mass ratio of carbonized polypyrrole-thiophene to sodium persulfate is 1:5.

[0034] Preferably, the ratio of the carbonized polypyrrole-thiophene, persulfate and aniline solution is 0.05-0.40 g: 0.25-2.00 g: 1 L.

[0035] Preferably, all undefined variables in the present invention, if not clearly defined, can be manually set thresholds.

[0036] Compared with the prior art, the present invention has the following beneficial technical effects:

[0037] The use of surfactants to synthesize polypyrrole-thiophene in an aqueous solution in one step greatly reduces the use of organic solvents and ferric chloride. The material preparation process is simple, efficient and safe, and solves the current problems of uneven distribution of heteroatoms, element loss, and complex procedures in the doping process. The prepared polypyrrole-thiophene is used to catalyze the degradation of aniline with persulfate, and the aniline degradation rate is high. At the same time, the carbonized polypyrrole-thiophene also has a certain adsorption effect on aniline, further improving the treatment efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 A flow chart of the simultaneous synthesis of polypyrrole-thiophene and catalytic degradation of aniline by persulfate provided by the present invention;

[0039] Figure 2 This is the full XPS spectrum of the polypyrrole-thiophene material obtained in Example 1 of the present invention;

[0040] Figure 3 This is the full XPS spectrum of the carbonized polypyrrole-thiophene material obtained in Example 11 of the present invention;

[0041] Figure 4This is the XPS nitrogen element fine spectrum of the carbonized polypyrrole-thiophene material obtained in Example 11 of the present invention. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. The specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0043] It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values ​​​​exemplified below.

[0044] The following is an exemplary description of a method for simultaneously synthesizing polypyrrole-thiophene provided by the present invention.

[0045] like Figure 1 The flowchart of a method for simultaneous synthesis and carbonization of polypyrrole-thiophene is shown, and the method comprises the following steps:

[0046] Step 1, adding thiophene monomer, surfactant, ferric chloride and hydrogen peroxide into an aqueous solution for prepolymerization;

[0047] Step 2, adding a pyrrole monomer solution containing a surfactant to the aqueous solution in step 1, uniformly mixing, filtering, rinsing, and drying to obtain polypyrrole-thiophene;

[0048] Step 3, carbonizing polypyrrole-thiophene to obtain carbonized polypyrrole-thiophene;

[0049] Step 4, carbonized polypyrrole-thiophene is applied to catalyze persulfate and used to degrade aniline solution.

[0050] In the above steps, a surfactant is used to dissolve the thiophene monomer and the pyrrole monomer in an aqueous solution, and hydrogen peroxide is used to reduce the amount of ferric chloride, and the polypyrrole-thiophene material is synthesized under the action of ferric chloride. Since the synthesis time of polythiophene is long, a part of polythiophene is synthesized first, and then the pyrrole monomer is added.

[0051] Furthermore, in step 1, the surfactant includes: a cationic surfactant or a non-ionic surfactant.

[0052] Preferably, the surfactant includes one or more of hexadecyltrimethylammonium bromide and triblock copolymer.

[0053] Preferably, the mass ratio of thiophene monomer, surfactant, ferric chloride and 30% hydrogen peroxide is 3.16-6.30:0.50:0.09:22.20-133.20.

[0054] Preferably, the amount of thiophene monomer used is 6.30 g / L.

[0055] Preferably, the amount of 30% hydrogen peroxide used is 20 mL / L.

[0056] Furthermore, in step 2, the mass ratio of the surfactant to the pyrrole monomer is 0.50:5.00-7.55.

[0057] The surfactant includes: one or more of hexadecyltrimethylammonium bromide and triblock copolymer.

[0058] Preferably, the pyrrole monomer is used in an amount of 5.00 g / L.

[0059] Preferably, the filtering and rinsing step comprises filtering the aqueous solution, and rinsing the filter residue with hydrochloric acid solution, ultrapure water and ethanol in sequence.

[0060] Preferably, the drying condition is 60° C. and the drying time is 12 to 36 hours.

[0061] In step 3 and step 4, the obtained polypyrrole-thiophene is carbonized and then used to degrade aniline.

[0062] Carbonization of polypyrrole-thiophene can obtain a carbon material containing an aromatic ring structure. The nitrogen elements in the carbonized polypyrrole-thiophene are mainly graphitic nitrogen and pyridinic nitrogen, which are beneficial to the catalytic degradation of persulfate and oxidative degradation of aniline, and the catalytic degradation time is 1 to 30 minutes.

[0063] Furthermore, in step 3, polypyrrole-thiophene is calcined in a heat-resistant sealed container in a nitrogen atmosphere, the calcination temperature is set at 900-1200° C., the calcination time is set at 2 h, and nitrogen is introduced for cooling after calcination to obtain carbonized polypyrrole-thiophene.

[0064] Preferably, the calcination temperature is 1000°C.

[0065] Preferably, in step 4, the cooled carbonized polypyrrole-thiophene is ground.

[0066] Preferably, in step 4, the carbonized polypyrrole-thiophene is ground to -0.14 mm (100 mesh).

[0067] Furthermore, in step 4, the carbonized polypyrrole-thiophene cooled in step 3.2 is ground, and the ground carbonized polypyrrole-thiophene is used to catalyze 0.5 g of persulfate, and then used to degrade the aniline solution.

[0068] Preferably, step 4 may also be: adding the ground carbonized polypyrrole-thiophene to an aniline solution to prepare a first solution, and adding persulfate to the first solution to degrade the aniline.

[0069] Preferably, in step 4, the concentration of the aniline solution is 30 mg / L, and the persulfate is one or more of potassium permonosulfate, sodium persulfate or potassium persulfate.

[0070] Preferably, the mass ratio of carbonized polypyrrole-thiophene to aniline is 2:1.

[0071] Preferably, the mass ratio of carbonized polypyrrole-thiophene to sodium persulfate is 1:5.

[0072] Preferably, the ratio of the carbonized polypyrrole-thiophene, persulfate and aniline solution is 0.05-0.40 g: 0.25-2.00 g: 1 L.

[0073] Preferably, all undefined variables in the present invention, if not clearly defined, can be manually set thresholds.

[0074] Example 1

[0075] 4.21 g of thiophene monomer, 0.50 g of hexadecyltrimethylammonium bromide and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 550 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 20 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0076] 6.71 g of pyrrole monomer and 0.50 g of hexadecyltrimethylammonium bromide were weighed and dissolved in 430 mL of ultrapure water, added to the mixed solution, and stirred evenly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0077] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0078] like Figure 2 Shown is the full XPS spectrum of the prepared polypyrrole-thiophene.

[0079] Example 2

[0080] 4.21 g of thiophene monomer, 0.50 g of hexadecyltrimethylammonium bromide and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 510 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 60 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0081] 6.71 g of pyrrole monomer and 0.50 g of hexadecyltrimethylammonium bromide were weighed and dissolved in 430 mL of ultrapure water, and added to the mixed solution obtained in step S1, and stirred uniformly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0082] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0083] Example 3

[0084] 4.21 g of thiophene monomer, 0.50 g of hexadecyltrimethylammonium bromide and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 450 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 120 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0085] 6.71 g of pyrrole monomer and 0.50 g of hexadecyltrimethylammonium bromide were weighed and dissolved in 430 mL of ultrapure water, added to the mixed solution, and stirred evenly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0086] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0087] Example 4

[0088] 4.21 g of thiophene monomer, 0.50 g of triblock copolymer and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 550 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 20 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0089] 6.71 g of pyrrole monomer and 0.50 g of triblock copolymer were weighed and dissolved in 430 mL of ultrapure water, and then added to the obtained mixed solution, and stirred uniformly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0090] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0091] Example 5

[0092] 6.30 g of thiophene monomer, 0.50 g of hexadecyltrimethylammonium bromide and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 550 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 20 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0093] 5.00 g of pyrrole monomer and 0.50 g of hexadecyltrimethylammonium bromide were weighed and dissolved in 430 mL of ultrapure water, added to the mixed solution, and stirred evenly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0094] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0095] Example 6

[0096] 3.16 g of thiophene monomer, 0.50 g of hexadecyltrimethylammonium bromide and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 550 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 20 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0097] 7.55 g of pyrrole monomer and 0.50 g of hexadecyltrimethylammonium bromide were weighed and dissolved in 430 mL of ultrapure water, added to the mixed solution, and stirred evenly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0098] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0099] Example 7

[0100] 10 g of the polypyrrole-thiophene from Example 1 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0101] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0102] Example 8

[0103] 10 g of the polypyrrole-thiophene from Example 1 was weighed and placed in a tube furnace, and kept at 900° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0104] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0105] Example 9

[0106] 10 g of the polypyrrole-thiophene from Example 1 was weighed and placed in a tube furnace, and kept at 1200° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0107] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0108] Example 10

[0109] 10 g of the polypyrrole-thiophene from Example 1 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0110] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of potassium permonosulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0111] Embodiment 11

[0112] 10 g of the polypyrrole-thiophene from Example 5 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0113] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0114] like Figure 3 The XPS full spectrum of the carbonized polypyrrole-thiophene is shown as follows: Figure 4 Shown is the XPS nitrogen element fine spectrum of the carbonized polypyrrole-thiophene.

[0115] Example 12

[0116] 10 g of the polypyrrole-thiophene from Example 6 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0117] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0118] Example 13

[0119] 10 g of the polypyrrole-thiophene from Example 5 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0120] 0.05 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0121] Embodiment 14

[0122] 10 g of the polypyrrole-thiophene from Example 5 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0123] 0.40 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0124] Embodiment 15

[0125] 10 g of the polypyrrole-thiophene from Example 5 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0126] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.25 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0127] Example 16

[0128] 10 g of the polypyrrole-thiophene from Example 5 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0129] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 2.00 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0130] Comparative Example 1

[0131] 4.21 g of thiophene monomer, 0.50 g of dodecyl sulfate (anionic surfactant) and 0.09 g of anhydrous ferric chloride were weighed and dissolved in 550 mL of ultrapure water to obtain a mixed solution. After uniform mixing, 20 mL of 30% hydrogen peroxide was added to the mixed solution and stirred at 25° C. and 200 rpm for 200 min.

[0132] 6.71 g of pyrrole monomer and 0.50 g of dodecyl sulfate (anionic surfactant) were weighed and dissolved in 430 mL of ultrapure water, added to the mixed solution, and stirred evenly at 25° C. and 200 rpm under magnetic stirring for 24 h.

[0133] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0134] Comparative Example 2

[0135] 4.21 g of thiophene monomer and 95.18 g of anhydrous ferric chloride were weighed and dissolved in 550 mL of acetonitrile, and stirred at 25° C. and 200 rpm for 200 min to obtain a mixed solution.

[0136] 6.71 g of pyrrole monomer was weighed into 450 mL of acetonitrile, added to the mixed solution, and stirred at 25° C. and 200 rpm for 24 h.

[0137] The mixed solution was filtered, and the residue was rinsed with 100 mL of 1 M hydrochloric acid solution, 100 mL of ultrapure water, and 100 mL of ethanol in sequence. Finally, the residue was dried at 60° C. for 24 h to obtain polypyrrole-thiophene.

[0138] Comparative Example 3

[0139] 0.5 g of sodium persulfate was weighed and dissolved in 1 L of an aqueous solution containing 30 mg / L aniline.

[0140] Comparative Example 4

[0141] Weigh 0.5 g of potassium permonosulfate and dissolve it in 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0142] Comparative Example 5

[0143] 10 g of the polypyrrole-thiophene from Example 5 was weighed and placed in a tube furnace, and kept at 1000° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0144] 0.10 g of carbonized polypyrrole-thiophene was weighed and used to degrade 1 L of aqueous solution with a concentration of 30 mg / L aniline.

[0145] Comparative Example 6

[0146] 10 g of the polypyrrole-thiophene from Example 1 was weighed and placed in a tube furnace, and kept at 800° C. for 2 h under a nitrogen atmosphere. The tube furnace was cooled to room temperature under a nitrogen atmosphere, and the calcined solid was ground evenly and passed through a 100-mesh sieve to obtain carbonized polypyrrole-thiophene.

[0147] 0.10 g of carbonized polypyrrole-thiophene was weighed to catalyze 0.5 g of sodium persulfate and applied to degrade 1 L of an aqueous solution with an aniline concentration of 30 mg / L.

[0148] The polypyrrole-thiophene materials obtained in Examples 1 to 4 were subjected to synthesis rate and XPS full spectrum analysis, wherein the synthesis rate of the polypyrrole-thiophene material was calculated based on the amount of pyrrole monomer and thiophene monomer added and the solid amount of the polypyrrole-thiophene material. The synthesis rate and surface element content of the polypyrrole-thiophene material are shown in the following table.

[0149]

[0150] Synthesis rate and surface element content (carbon, oxygen, sulfur, nitrogen) of polypyrrole-thiophene materials

[0151] As shown in the table above, in Examples 1, 2, and 3, the synthesis rate reached more than 70% under the action of hexadecyltrimethylammonium bromide and 30% hydrogen peroxide, and the materials all contained carbon, nitrogen, and sulfur elements. As the amount of 30% hydrogen peroxide decreased, the synthesis rate increased, and the oxygen content decreased and the sulfur content increased. In Examples 1 and 4, the synthesis rate reached more than 70% under the action of hexadecyltrimethylammonium bromide and triblock copolymers, and the materials all contained carbon, nitrogen, and sulfur elements. It can be seen that Examples 1 to 4 all successfully prepared polypyrrole-thiophene materials. Comparative Example 1 uses dodecyl sulfate instead of hexadecyltrimethylammonium bromide, and the recovery rate of polypyrrole-thiophene is only 8.02%, indicating that anionic surfactants cannot be used for the simultaneous synthesis of polypyrrole-thiophene in an aqueous medium. In Comparative Example 2, the synthesis rate and nitrogen doping amount of polypyrrole-thiophene are much lower than those of Examples 1 to 4. It can be seen that, compared with the simultaneous synthesis of polypyrrole-thiophene in an organic solvent, Examples 1 to 4 can prepare polypyrrole-thiophene with a high synthesis rate and a large amount of nitrogen doping.

[0152] In Examples 7 to 16, carbonized polypyrrole-thiophene was added to an aniline solution, and after magnetic stirring for 60 minutes, the concentration of aniline in the filtered solution was determined by high performance liquid chromatography (HPLC), thereby obtaining the adsorption rate of carbonized polypyrrole-thiophene to aniline. Persulfate was then added, reacted for 30 minutes, and the concentration of aniline in the filtered solution was determined by HPLC. The amount of aniline removed was subtracted from the amount of aniline adsorbed by carbonized polypyrrole-thiophene to finally obtain the oxidation removal rate of aniline catalyzed by carbonized polypyrrole-thiophene to persulfate, as shown in the following table.

[0153] Oxidation removal rate of aniline (%) Example 7 71.26 Example 8 52.10 Example 9 65.33 Example 10 50.21 Embodiment 11 83.88 Example 12 76.83 Example 13 53.91 Embodiment 14 74.35 Embodiment 15 73.52 Example 16 80.22 Comparative Example 3 7.52 Comparative Example 4 28.43 Comparative Example 5 0 (adsorption removal rate 2.81%) Comparative Example 6 20.12

[0154] Oxidative removal efficiency of aniline by persulfate oxidation catalyzed by carbonized polypyrrole-thiophene

[0155] As shown in the table above, in Examples 7 to 16, carbonized polypyrrole-thiophene catalyzes the removal of aniline by persulfate with obvious effects. Excluding the adsorption effect of carbonized polypyrrole-thiophene (Comparative Example 5), the oxidation removal rate of aniline by catalyzing persulfate reaches 50.21 to 83.88%. The oxidation removal rate of aniline in Comparative Examples 3 to 4 is only 7.52 to 28.43%, which confirms the catalytic and degradation effect of carbonized polypyrrole-thiophene on persulfate and aniline in Examples 7 to 16. Combined with Example 11 and Comparative Example 5 (oxidation and adsorption), the optimal total removal rate of aniline degradation by carbonized polypyrrole-thiophene catalyzing persulfate is 86.69%. It can be seen from Comparative Example 6 that a calcination temperature below 900°C cannot produce carbonized polypyrrole-thiophene with obvious catalytic activity.

[0156] In summary, the present invention uses hexadecyltrimethylammonium bromide or triblock copolymer, ferric chloride, 30% hydrogen peroxide, pyrrole monomer, and thiophene monomer in an aqueous solution to prepare a polypyrrole-thiophene material, thereby reducing the use of a large amount of organic solvents and ferric chloride. The prepared polypyrrole-thiophene is carbonized and applied to catalyze the degradation of aniline by persulfate, and has a significant ability to activate persulfate and degrade organic pollutants.

[0157] Although the description of the present invention has been quite detailed and has been described in particular with respect to several described embodiments, it is not intended to be limited to any of these details or embodiments or any particular embodiment, so as to effectively cover the intended scope of the present invention. In addition, the present invention is described above with the embodiments foreseeable by the inventors, and its purpose is to provide a useful description, and those non-substantial changes to the present invention that are not currently foreseen may still represent equivalent changes of the present invention.

[0158] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0159] Although the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that many changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention.

Claims

1. A method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate, characterized in that: The method comprises: Polypyrrole-thiophene is prepared in advance, and the preparation method of polypyrrole-thiophene comprises the following steps: Step 1, adding thiophene monomer, surfactant, ferric chloride and 30% hydrogen peroxide into water for prepolymerization; Step 2, adding a pyrrole monomer solution containing a surfactant to the aqueous solution in step 1, uniformly mixing, filtering, rinsing, and drying to obtain polypyrrole-thiophene; In step 1, the surfactant includes: one or more of hexadecyltrimethylammonium bromide and triblock copolymer; In step 1, the mass ratio of thiophene monomer, surfactant, ferric chloride, and 30% hydrogen peroxide is 3.16-6.30:0.50:0.09:22.20-133.20; In step 2, the mass ratio of the surfactant to the pyrrole monomer is 0.50:5.00-7.55, and the surfactant includes one or more of hexadecyltrimethylammonium bromide and a triblock copolymer; The method for degrading aniline by persulfate catalyzed by polypyrrole-thiophene comprises the following steps: Step 3, carbonizing the pre-prepared polypyrrole-thiophene to obtain carbonized polypyrrole-thiophene; Step 4: carbonized polypyrrole-thiophene is used to catalyze persulfate and to degrade aniline solution.

2. The method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate according to claim 1, characterized in that: The sub-steps of step 3 are: Step 3.1, calcining the polypyrrole-thiophene prepared in claim 1 in a heat-resistant sealed container in a nitrogen atmosphere, and setting the calcination temperature to 900-1200° C.; Step 3.2, after calcination, nitrogen is introduced for cooling to obtain carbonized polypyrrole-thiophene.

3. The method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate according to claim 2, characterized in that: The sub-steps of step 4 are: The carbonized polypyrrole-thiophene cooled in step 3.2 was ground, and the ground carbonized polypyrrole-thiophene was used to catalyze 0.5 g of persulfate, and then used to degrade the aniline solution.

4. The method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate according to claim 1, characterized in that: In step 4, the concentration of the aniline solution is 30 mg / L.

5. The method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate according to claim 1, characterized in that: In step 4, the persulfate is one or more of potassium peroxymonosulfate, sodium persulfate or potassium persulfate.

6. The method for degrading aniline by using polypyrrole-thiophene to catalyze persulfate according to claim 1, characterized in that: In step 4, the ratio of the carbonized polypyrrole-thiophene, persulfate and aniline solution is 0.05-0.40 g:0.25-2.00 g:1 L.

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