CN116282414A - Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Preparation method of integrated membrane electrode - Google Patents

Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Preparation method of integrated membrane electrode Download PDF

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CN116282414A
CN116282414A CN202310520268.7A CN202310520268A CN116282414A CN 116282414 A CN116282414 A CN 116282414A CN 202310520268 A CN202310520268 A CN 202310520268A CN 116282414 A CN116282414 A CN 116282414A
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phosphorus
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周利民
欧阳金波
刘延璘
敖仙倩
刘峙嵘
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East China Institute of Technology
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Abstract

The invention relates to carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps: s1, preparing phosphorus doped graded pore carbon; s2, phosphorus doped graded pore carbon/MoS 2 Preparing; s3, phosphorus doped graded pore carbon/MoS 2 Preparing an electrode; s4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 And (3) preparing an integrated membrane electrode. According to the invention, the high-phosphorus-content phytic acid is used as a phosphorus source and F127 is used as a template agent to prepare the phosphorus-doped graded pore carbon, so that the pore structure and the hydrophilicity of the carbon material can be improved, and the pseudo capacitance can be increased; grading pore carbon doped with phosphorus and MoS with high specific capacitance 2 The specific capacitance of the electrode material can be obviously improved by compounding. Grading pore carbon/MoS by potentiostatic method 2 The carboxylated polyaniline film is modified on the surface of the electrode to serve as an ion exchange film, and an integrated film electrode is constructed, so that the specific capacitance, the hydrophilicity and the selective permeability of the ion exchange film of the electrode can be remarkably improved, and the desalination performance of MCDI (micro-chemical vapor deposition) treatment of low-concentration uranium-containing wastewater is further improved.

Description

Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Preparation method of integrated membrane electrode
Technical Field
The invention relates to the field of chemical separation, in particular to carboxylated polyanilinePhosphorus doped graded pore carbon/MoS 2 A preparation method of an integrated membrane electrode.
Background
A great amount of uranium-containing wastewater is generated in the nuclear fuel circulation process, and the generated radioactive pollution seriously damages the environment and human health. In recent years, a novel separation technology of Membrane Capacitance Deionization (MCDI) is developed, wherein a reverse ion exchange membrane is placed in front of an electrode, namely a cation exchange membrane and an anion exchange membrane are respectively placed in front of a cathode and an anode, and ions in a solution are induced to selectively permeate the ion exchange membrane by using an external electric field and are enriched in holes of a porous electrode (such as a carbon electrode), so that the ions can be quickly embedded in/extracted from the porous electrode through potential regulation. The MCDI ion exchange membrane can be used as an ion permeation selective barrier, improves the distribution of absorbed ions, reduces side reactions of electrodes and improves desalination performance. The method for treating the low-concentration uranium-containing wastewater by using the MCDI has the advantages of energy conservation, high efficiency, simple and convenient operation, economy and environmental protection.
High performance electrode materials and membrane materials are key to the treatment of low-concentration uranium-containing wastewater using MCDI. Electrode material properties are primarily dependent on material specific capacitance, conductivity, hydrophilicity, and membrane permeation properties. The carbon electrode material commonly used in the prior MCDI mainly comprises micropores, and has low specific capacitance and poor hydrophilicity; in addition, the ion exchange membrane adopted by the membrane capacitance deionization device is separated from the electrode material, and the commercial ion exchange membrane is thicker, has poor membrane permeability and conductivity, and seriously affects the practical effect of treating low-concentration uranium-containing wastewater by MCDI. Therefore, how to improve the pore structure of the MCDI electrode material, improve the specific capacitance and hydrophilicity of the material, and improve the membrane permeability and conductivity is a technical problem to be solved in the treatment of low-concentration uranium-containing wastewater by using MCDI.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 A preparation method of an integrated membrane electrode.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps:
s1, preparing phosphorus doped graded pore carbon;
using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% of template agent F127 into 100 mL coal tar, uniformly mixing, adding 6 g phytic acid as a phosphorus source, uniformly mixing, performing ultrasonic treatment for 30 min, adding the mixed solution into a reaction kettle, stirring at 210 ℃ for reacting 12 h, filtering the product, and drying to obtain a phosphorus-doped carbon precursor;
the prepared phosphorus doped carbon precursor is placed in the middle of a tube furnace, and N is at 700 DEG C 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere according to a volume ratio of 1:1:1, synchronously removing a template agent F127, washing the carbonized product with water, and drying in vacuum to obtain phosphorus-doped hierarchical pore carbon;
s2, phosphorus doped graded pore carbon/MoS 2 Preparing;
firstly, 18.6. 18.6 g ammonium molybdate and 34.2 g thiourea are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon is added according to a certain proportion, the mixture is dispersed for 30 min by ultrasonic, the mixture is transferred into a reaction kettle, and the mixture is treated by 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 ；
S3, phosphorus doped graded pore carbon/MoS 2 Preparing an electrode;
the prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing the conductive additive and the polyvinyl alcohol according to the mass ratio of 8:1:1, adding a small amount of epichlorohydrin, fully and uniformly mixing, coating the mixture on a foam titanium substrate, and coating the mixture on 70 o And C, drying in vacuum.
Further, the method comprises the following steps:
s4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Preparing an integrated membrane electrode;
adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode;
wherein the reaction system contains aniline, aniline-2-carboxylic acid and 0.1M KClO with certain concentration 4 The method comprises the steps of carrying out a first treatment on the surface of the Introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 An integrated membrane electrode;
the reaction formula for generating carboxylated polyaniline through electrochemical polymerization is as follows:
Figure SMS_1
in the S1, coal tar is used as a carbon source, phytic acid is used as a phosphorus dopant, the phosphorus doped graded pore carbon is prepared, and N is used as 2 +steam+CO 2 The mixed gas is an activating agent, and the activation time is 2 h.
Further, in the step S2, the adding amount of the phosphorus doped graded pore carbon is 3-9 g.
Further, in S3, the conductive additive is conductive graphite.
In the step S4, the concentration of the aniline and the concentration of the aniline-2-carboxylic acid are the same and are 0.1-0.2M.
The beneficial effects of the invention are as follows: the invention prepares the phosphorus doped graded pore carbon by using the phytic acid with high phosphorus content as a phosphorus source and F127 as a mesoporous template agent, thereby improving the pore structure and the hydrophilicity of the carbon material and increasing the pseudo-capacitance; moS with high pseudo-capacitance and phosphorus doped hierarchical pore carbon 2 The specific capacitance of the electrode material can be obviously improved by compounding. Grading pore carbon/MoS by potentiostatic method 2 The carboxylated polyaniline film is modified on the surface of the electrode to serve as an ion exchange film, and an integrated film electrode is constructed, so that the specific capacitance, the hydrophilicity and the selective permeability of the ion exchange film of the electrode can be remarkably improved, and the desalination performance of MCDI (micro-chemical mechanical polishing) treatment of low-concentration uranium-containing wastewater is further improved;
in addition, in the step 1 of the present invention, N is used 2 +steam+CO 2 The mixed gas activates the graded pore carbon in a volume ratio of 1:1:1, which is beneficial to forming a graded pore carbon structure mainly comprising micropores/mesopores, improving the pore size distribution and avoiding the problem of the traditional chemical activation corrosion equipment;
in the step 3 of the invention, the hydrophilic PVA adhesive is used for replacing the traditional hydrophobic adhesive (such as polyvinylidene fluoride), so that the hydrophilicity of the electrode material can be effectively improved;
in step 4 of the invention, the graded pore carbon/MoS is doped in the phosphorus by a potentiostatic method 2 The carboxylated conductive polymer film formed on the surface of the electrode has good ion exchange performance and conductivity, and can obviously improve the conductivity and ion selective permeability of the film.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Description of the embodiments
Examples
As shown in figure 1, a carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps:
s1, preparing phosphorus doped hierarchical pore carbon
Using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% template agent F127 into 100 mL coal tar, mixing, and adding 6 g phytic acid (cyclohexanethol hexaphosphoric acid, molecular formula C 6 H 18 O 24 P 6 ) Mixing as phosphorus source, and ultrasonic treating for 30 min. Adding the mixed solution into a reaction kettle, stirring at 210 ℃ for reaction 12 h, filtering and drying the product to obtain the phosphorus-doped carbon precursor.
The prepared phosphorus doped carbon precursor is placed in the middle of a tube furnace at 700 ℃ and N 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere with the volume ratio of 1:1:1, synchronously removing the template agent F127, and washing and vacuum drying the obtained carbonized product to obtain the phosphorus doped graded pore carbon.
S2, phosphorus doped graded pore carbon/MoS 2 Preparation
Firstly, ammonium molybdate (18.6 g) and thiourea (34.2 g) are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon 3 g is added according to a certain proportion, the ultrasonic dispersion is carried out for 30 min, the mixture is transferred into a reaction kettle, and the mixture is stirred at 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 。
S3, phosphorus doped graded pore carbon/MoS 2 Electrode preparation
The prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing conductive graphite (conductive additive) and polyvinyl alcohol (PVA water solution, binder) according to a mass ratio of 8:1:1, adding a small amount of epichlorohydrin (ECH cross-linking agent accounting for about PVA 1 wt%), fully and uniformly mixing, coating on a titanium foam substrate (current collector), and coating on 70 parts of titanium foam substrate (current collector) o Vacuum drying under C (while crosslinking PVA).
S4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Integrated membrane electrode preparation
Adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The reaction system contains 0.15M of aniline, 0.15M of aniline-2-carboxylic acid and 0.1M of KClO 4 (increasing the conductivity of the solution); introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 An integrated membrane electrode.
For the carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The performance of the integrated membrane electrode is tested, which shows that the specific capacitance is 142F/g, and the contact angle in aqueous solution is 46 o 。
Wherein, the reaction formula for generating carboxylated polyaniline by electrochemical polymerization is as follows:
Figure SMS_2
the prepared pair of carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The integrated membrane electrode is used as a parallel electrode (electrode active material weight is 30 mg) for carrying out membrane capacitance deionization treatment on 1L uranium-containing wastewater with concentration of 15 mg/L, which shows that membrane permeation flux is 0.021 m 3 /(m 2 H), the adsorption equilibrium time is 80 min, the uranium removal rate reaches 66%, and the uranium is removedCapacity 330 mg/g.
Examples
Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps:
s1, preparing phosphorus doped hierarchical pore carbon
Using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% template agent F127 into 100 mL coal tar, mixing, and adding 6 g phytic acid (cyclohexanethol hexaphosphoric acid, molecular formula C 6 H 18 O 24 P 6 ) Mixing as phosphorus source, and ultrasonic treating for 30 min. Adding the mixed solution into a reaction kettle, stirring at 210 ℃ for reaction 12 h, filtering and drying the product to obtain the phosphorus-doped carbon precursor.
The prepared phosphorus doped carbon precursor is placed in the middle of a tube furnace at 700 ℃ and N 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere with the volume ratio of 1:1:1, synchronously removing the template agent F127, and washing and vacuum drying the obtained carbonized product to obtain the phosphorus doped graded pore carbon.
S2, phosphorus doped graded pore carbon/MoS 2 Preparation
Firstly, ammonium molybdate (18.6 g) and thiourea (34.2 g) are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon 6 g is added according to a certain proportion, the ultrasonic dispersion is carried out for 30 min, the mixture is transferred into a reaction kettle, and the mixture is stirred at 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 。
S3, phosphorus doped graded pore carbon/MoS 2 Electrode preparation
The prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing conductive graphite (conductive additive) and polyvinyl alcohol (PVA water solution, binder) according to a mass ratio of 8:1:1, adding a small amount of epichlorohydrin (ECH cross-linking agent accounting for about PVA 1 wt%), fully and uniformly mixing, coating on a titanium foam substrate (current collector), and coating on 70 parts of titanium foam substrate (current collector) o Vacuum drying under C (while crosslinking PVA).
S4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Integrated membrane electrode preparation
Adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The reaction system contains 0.15M aniline, 0.15M aniline-2-carboxylic acid and 0.1M KClO 4 (increasing the conductivity of the solution); introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 An integrated membrane electrode.
For the carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The performance of the integrated membrane electrode is tested, which shows that the specific capacitance is 178F/g, and the contact angle in aqueous solution is 31 o 。
The prepared pair of carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The integrated membrane electrode is used as a parallel electrode (electrode active material weight is 30 mg) for carrying out membrane capacitance deionization treatment on 1L uranium-containing wastewater with concentration of 15 mg/L, which shows that the membrane permeation flux is 0.023 m 3 /(m 2 H) the method comprises the following steps of. The adsorption equilibrium time is 60 min, the uranium removal rate reaches 95%, and the uranium removal capacity is 476 mg/g.
Examples
Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps:
s1, preparing phosphorus doped hierarchical pore carbon
Using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% template agent F127 into 100 mL coal tar, mixing, and adding 6 g phytic acid (cyclohexanethol hexaphosphoric acid, molecular formula C 6 H 18 O 24 P 6 ) Mixing as phosphorus source, and ultrasonic treating for 30 min. Adding the mixed solution into a reaction kettle, stirring at 210 ℃ for reaction 12 h, filtering and drying the product to obtain the phosphorus-doped carbon precursor.
The prepared phosphorus doped carbon precursor is placed in the middle of a tube furnace at 700 ℃ and N 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere with the volume ratio of 1:1:1, and synchronously removingRemoving the template agent F127, and washing and vacuum drying the obtained carbonized product to obtain the phosphorus doped graded pore carbon.
S2, phosphorus doped graded pore carbon/MoS 2 Preparation
Firstly, ammonium molybdate (18.6 g) and thiourea (34.2 g) are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon 9 g is added according to a certain proportion, the ultrasonic dispersion is carried out for 30 min, the mixture is transferred into a reaction kettle, and the mixture is stirred at 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 。
S3, phosphorus doped graded pore carbon/MoS 2 Electrode preparation
The prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing conductive graphite (conductive additive) and polyvinyl alcohol (PVA water solution, binder) according to a mass ratio of 8:1:1, adding a small amount of epichlorohydrin (ECH cross-linking agent accounting for about PVA 1 wt%), fully and uniformly mixing, coating on a titanium foam substrate (current collector), and coating on 70 parts of titanium foam substrate (current collector) o Vacuum drying under C (while crosslinking PVA).
S4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Integrated membrane electrode preparation
Adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The reaction system contains 0.15M aniline, 0.15M aniline-2-carboxylic acid and 0.1M KClO 4 (increasing the conductivity of the solution); introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 An integrated membrane electrode.
For the carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The performance of the integrated membrane electrode is tested, which shows that the specific capacitance is 125F/g, and the contact angle in aqueous solution is 48 o 。
The pair of carboxylated polyaniline/phosphorus doped hierarchical pore carbon prepared in the above wayMoS 2 The integrated membrane electrode is used as a parallel electrode (electrode active material weight is 30 mg) for carrying out membrane capacitance deionization treatment on 1L uranium-containing wastewater with concentration of 15 mg/L, which shows that membrane permeation flux is 0.017 m 3 /(m 2 H) the method comprises the following steps of. The adsorption equilibrium time is 90 min, the uranium removal rate reaches 69%, and the uranium removal capacity is 345mg/g.
Examples
Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps:
s1, preparing phosphorus doped hierarchical pore carbon
Using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% template agent F127 into 100 mL coal tar, mixing, and adding 6 g phytic acid (cyclohexanethol hexaphosphoric acid, molecular formula C 6 H 18 O 24 P 6 ) Mixing as phosphorus source, and ultrasonic treating for 30 min. Adding the mixed solution into a reaction kettle, stirring at 210 ℃ for reaction 12 h, filtering and drying the product to obtain the phosphorus-doped carbon precursor.
The prepared phosphorus doped carbon precursor is placed in the middle of a tube furnace at 700 ℃ and N 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere with the volume ratio of 1:1:1, synchronously removing the template agent F127, and washing and vacuum drying the obtained carbonized product to obtain the phosphorus doped graded pore carbon.
S2, phosphorus doped graded pore carbon/MoS 2 Preparation
Firstly, ammonium molybdate (18.6 g) and thiourea (34.2 g) are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon 6 g is added according to a certain proportion, the ultrasonic dispersion is carried out for 30 min, the mixture is transferred into a reaction kettle, and the mixture is stirred at 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 。
S3, phosphorus doped graded pore carbon/MoS 2 Electrode preparation
The prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing conductive graphite (conductive additive) and polyvinyl alcohol (PVA water solution and adhesive) according to a mass ratio of 8:1:1, adding a small amount of epichlorohydrin (ECH cross-linking agent,about 1 wt% of PVA) is fully mixed and coated on a foam titanium substrate (current collector) at 70% o Vacuum drying under C (while crosslinking PVA).
S4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Integrated membrane electrode preparation
Adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The reaction system contains 0.10M aniline, 0.10M aniline-2-carboxylic acid and 0.1M KClO 4 (increasing the conductivity of the solution); introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 An integrated membrane electrode.
For the carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The performance of the integrated membrane electrode is tested, which shows that the specific capacitance is 115F/g, and the contact angle in aqueous solution is 49 o 。
The prepared pair of carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The integrated membrane electrode is used as a parallel electrode (electrode active material weight is 30 mg) for carrying out membrane capacitance deionization treatment on 1L uranium-containing wastewater with concentration of 15 mg/L, which shows that the membrane permeation flux is 0.018 m 3 /(m 2 H) the method comprises the following steps of. The adsorption equilibrium time is 90 min, the uranium removal rate reaches 62%, and the uranium removal capacity is 310 mg/g.
Examples
Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode comprises the following steps:
s1, preparing phosphorus doped hierarchical pore carbon
Using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% template agent F127 into 100 mL coal tar, mixing, and adding 6 g phytic acid (cyclohexanethol hexaphosphoric acid, molecular formula C 6 H 18 O 24 P 6 ) Mixing as phosphorus source, and ultrasonic treating for 30 min. Adding the mixed solution into a reaction kettle, and stirring for reaction at 210 DEG C12 And h, filtering and drying the product to obtain the phosphorus doped carbon precursor.
The prepared phosphorus doped carbon precursor is placed in the middle of a tube furnace at 700 ℃ and N 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere with the volume ratio of 1:1:1, synchronously removing the template agent F127, and washing and vacuum drying the obtained carbonized product to obtain the phosphorus doped graded pore carbon.
S2, phosphorus doped graded pore carbon/MoS 2 Preparation
Firstly, ammonium molybdate (18.6 g) and thiourea (34.2 g) are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon 6 g is added according to a certain proportion, the ultrasonic dispersion is carried out for 30 min, the mixture is transferred into a reaction kettle, and the mixture is stirred at 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 。
S3, phosphorus doped graded pore carbon/MoS 2 Electrode preparation
The prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing conductive graphite (conductive additive) and polyvinyl alcohol (PVA water solution, binder) according to a mass ratio of 8:1:1, adding a small amount of epichlorohydrin (ECH cross-linking agent accounting for about PVA 1 wt%), fully and uniformly mixing, coating on a titanium foam substrate (current collector), and coating on 70 parts of titanium foam substrate (current collector) o Vacuum drying under C (while crosslinking PVA).
S4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Integrated membrane electrode preparation
Adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The reaction system contains 0.20M aniline, 0.20M aniline-2-carboxylic acid and 0.1M KClO 4 (increasing the conductivity of the solution); introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 An integrated membrane electrode.
For the aboveCarboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The performance of the integrated membrane electrode is tested, which shows that the specific capacitance is 131F/g, and the contact angle in aqueous solution is 38 o 。
The prepared pair of carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The integrated membrane electrode is used as a parallel electrode (electrode active material weight is 30 mg) for deionizing 1L of uranium-containing wastewater with concentration of 15 mg/L by using a membrane capacitor, which shows that the membrane permeation flux is 0.016 m 3 /(m 2 H) the method comprises the following steps of. The adsorption equilibrium time is 70 min, the uranium removal rate reaches 78%, and the uranium removal capacity is 392 mg/g.
As is clear from the experimental results of examples 1 to 5 for treating 1L of uranium-containing wastewater having a concentration of 15 mg/L by Membrane Capacitive Deionization (MCDI), example 2 (according to the present invention, the addition of phosphorus-doped hierarchical pore carbon was 6 g in step 2, and the concentration of aniline was 0.15M and the concentration of aniline-2-carboxylic acid was 0.15M in step 4) was the best in treating wastewater, and at this time, the membrane permeation flux was 0.023, 0.023 m 3 /(m 2 H) the method comprises the following steps of. The adsorption equilibrium time is 60 min, the uranium removal rate reaches 95%, and the uranium removal capacity is 476 mg/g. As the monomer concentration increases, the loading of carboxylated polyaniline increases, which increases the specific capacitance of the electrode, but excessive loading can clog the electrode pore structure, rather degrading MCDI. The carboxylic polyaniline/phosphorus-doped graded pore carbon/MoS can be optimized by adjusting the adding amount of the phosphorus-doped graded pore carbon and the concentration of polymerized monomer aniline and aniline-2-carboxylic acid 2 The phosphorus doped graded pore carbon content and the carboxylic polyaniline loading capacity in the integrated membrane electrode enable the phosphorus doped graded Kong Tankong structure to be matched with pseudocapacitance provided by the carboxylic polyaniline, and the synergistic effect of the phosphorus doped graded pore carbon content and the carboxylic polyaniline loading capacity is exerted, so that the MCDI desalination performance is optimal.
According to the invention, the high-phosphorus-content phytic acid is used as a phosphorus source and F127 is used as a template agent to prepare the phosphorus-doped graded pore carbon, so that the pore structure and the hydrophilicity of the carbon material can be improved, and the pseudo capacitance can be increased; moS with high pseudo-capacitance and phosphorus doped hierarchical pore carbon 2 The specific capacitance of the electrode material can be obviously improved by compounding. Grading pore carbon/MoS by potentiostatic method 2 The carboxylated polyaniline film modified on the surface of the electrode is used as an ion exchange film to construct an integrated film electrode, which can obviously improve the electricityThe extremely specific capacitance, the hydrophilicity and the ion exchange membrane selective permeability are adopted, so that the desalination performance of the MCDI treatment of the low-concentration uranium-containing wastewater is improved;
in addition, in the step 1 of the present invention, N is used 2 +steam+CO 2 The mixed gas activates the graded pore carbon in a volume ratio of 1:1:1, which is beneficial to forming a graded pore carbon structure mainly comprising micropores/mesopores, improving the pore size distribution and avoiding the problem of the traditional chemical activation corrosion equipment;
in the step 3 of the invention, the hydrophilic PVA adhesive is used for replacing the traditional hydrophobic adhesive (such as polyvinylidene fluoride), so that the hydrophilicity of the electrode material can be effectively improved;
in step 4 of the invention, the graded pore carbon/MoS is doped in the phosphorus by a potentiostatic method 2 The carboxylated conductive polymer film formed on the surface of the electrode has good ion exchange performance and conductivity, and can obviously improve the conductivity and ion selective permeability of the film.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 The preparation method of the integrated membrane electrode is characterized by comprising the following steps of:
s1, preparing phosphorus doped hierarchical pore carbon
Using coal tar as a carbon source, and synthesizing mesoporous carbon by using a template method: adding 5% of template agent F127 into 100 mL coal tar, uniformly mixing, adding 6 g phytic acid as a phosphorus source, uniformly mixing, performing ultrasonic treatment for 30 min, adding the mixed solution into a reaction kettle, stirring at 210 ℃ for reacting 12 h, filtering the product, and drying to obtain a phosphorus-doped carbon precursor;
preparing the above materialsThe phosphorus-doped carbon precursor is arranged in the middle of a tube furnace, and N is at 700 DEG C 2 +steam+CO 2 Heating and carbonizing 2 h in a mixed atmosphere according to a volume ratio of 1:1:1, synchronously removing a template agent F127, washing the carbonized product with water, and drying in vacuum to obtain phosphorus-doped hierarchical pore carbon;
s2, phosphorus doped graded pore carbon/MoS 2 Preparation
Firstly, 18.6. 18.6 g ammonium molybdate and 34.2 g thiourea are dissolved in 1000 mL deionized water, the prepared phosphorus doped graded pore carbon is added according to a certain proportion, the mixture is dispersed for 30 min by ultrasonic, the mixture is transferred into a reaction kettle, and the mixture is treated by 180 DEG C o Heating under C for 24-h, washing the obtained product with deionized water and ethanol, and vacuum drying to obtain phosphorus doped hierarchical porous carbon/MoS 2 ；
S3, phosphorus doped graded pore carbon/MoS 2 Preparing an electrode;
the prepared phosphorus doped graded pore carbon/MoS is subjected to 2 Mixing the conductive additive and the polyvinyl alcohol according to the mass ratio of 8:1:1, adding a small amount of epichlorohydrin, fully and uniformly mixing, coating the mixture on a foam titanium substrate, and coating the mixture on 70 o And C, drying in vacuum.
2. Carboxylated polyaniline/phosphorus-doped graded pore carbon/MoS according to claim 1 2 The preparation method of the integrated membrane electrode is characterized by further comprising the following steps:
s4, carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Preparing an integrated membrane electrode;
adopts a three-electrode system to dope graded pore carbon/MoS with phosphorus respectively 2 The electrode is a working electrode, pt is a counter electrode, and the Ag/AgCl electrode is a reference electrode;
wherein the reaction system contains aniline, aniline-2-carboxylic acid and 0.1M KClO with certain concentration 4 The method comprises the steps of carrying out a first treatment on the surface of the Introducing nitrogen into the reaction system for 30 min to remove oxygen before the reaction, controlling the polymerization potential to be 1.0V and the polymerization time to be 250 s, and doping the graded pore carbon/MoS after the reaction is completed 2 Forming carboxylated conductive polymer film on the surface of the electrode to prepare carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Integrated membrane electrode。
3. Carboxylated polyaniline/phosphorus-doped graded pore carbon/MoS according to claim 1 2 The preparation method of the integrated membrane electrode is characterized in that in S1, coal tar is used as a carbon source, phytic acid is used as a phosphorus doping agent, phosphorus doped graded pore carbon is prepared, and N is used as 2 +steam+CO 2 The mixed gas is an activating agent, and the activation time is 2 h.
4. Carboxylated polyaniline/phosphorus-doped graded pore carbon/MoS according to claim 2 2 The preparation method of the integrated membrane electrode is characterized in that in the S2, the adding amount of the phosphorus doped graded pore carbon is 3-9 g.
5. Carboxylated polyaniline/phosphorus-doped graded pore carbon/MoS according to claim 2 2 The preparation method of the integrated membrane electrode is characterized in that in the step S3, the conductive additive is conductive graphite.
6. Carboxylated polyaniline/phosphorus-doped graded pore carbon/MoS according to claim 2 2 The preparation method of the integrated membrane electrode is characterized in that in the S4, the concentration of the aniline and the concentration of the aniline-2-carboxylic acid are the same and are 0.1-0.2M.
CN202310520268.7A 2023-05-10 2023-05-10 Carboxylated polyaniline/phosphorus doped graded pore carbon/MoS 2 Preparation method of integrated membrane electrode Pending CN116282414A (en)

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