CN110937663B - Preparation method of filter type cathode membrane doped with zinc phthalocyanine - Google Patents

Preparation method of filter type cathode membrane doped with zinc phthalocyanine Download PDF

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CN110937663B
CN110937663B CN201910975385.6A CN201910975385A CN110937663B CN 110937663 B CN110937663 B CN 110937663B CN 201910975385 A CN201910975385 A CN 201910975385A CN 110937663 B CN110937663 B CN 110937663B
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zinc phthalocyanine
membrane
type cathode
doped
cathode membrane
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CN110937663A (en
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刘佳
郁美莹
陈雪鹏
李楠
何伟华
冯玉杰
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Tianjin University
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material

Abstract

The invention relates to a preparation method of a filter type cathode membrane doped with zinc phthalocyanine. Dissolving one of polypropylene, polytetrafluoroethylene or polysulfonamide and one of acrylic acid, polyvinyl alcohol or polyethylene glycol methacrylate in an organic solvent; wrapping and stirring the tinfoil, and standing to obtain a bubble-removed homogeneous solution; mixing activated carbon, carbon black and zinc phthalocyanine, uniformly mixing the mixed material and the bubble-removed homogeneous solution, and performing ultrasonic treatment for 20-30min to obtain a conductive film solution; and preparing the filter type cathode membrane doped with zinc phthalocyanine by coating the conductive membrane liquid. Zinc phthalocyanine is used as a doping agent of the filter type cathode membrane, so that the interception effect of the membrane is improved. After the filtering type cathode membrane is formed, a high molecular filter layer formed by high molecular resin exists on the surface of the electrode, and the aperture of the ultrafiltration membrane is smaller than 10nm so as to separate particles with the molecular weight larger than 500 daltons and the particle size larger than 10 nm. Therefore, the ultrafiltration conductive membrane has the functions of filtration and interception and improves the quality of the effluent.

Description

Preparation method of filter type cathode membrane doped with zinc phthalocyanine
Technical Field
The invention relates to a preparation method of a filter type cathode membrane doped with zinc phthalocyanine.
Background
The Microbial Fuel Cell (MFC) is a device which takes microbes as a catalyst and directly converts chemical energy in organic matters into electric energy, provides a wide prospect for the utilization of wastewater resources, a cathode material is an important place for electrochemical reaction and electron transmission, and a cathode receives electrons transmitted from an anode to complete the electrochemical process of the system.
The cathode of the conventional microbial fuel cell is generally prepared by a rolling method or a coating method and generally consists of a stainless steel mesh, a catalytic layer and a diffusion layer. In the preparation process, a catalyst layer and a diffusion layer are required to be prepared respectively and fixed respectivelyThe manufacturing process of the stainless steel net is relatively complex. Therefore, there is a need to develop new and integrated cathodes by innovating existing process technologies. The traditional cathode membrane has single performance and poor pollutant degradation effect, and the COD of the effluent in MFC is 100mgL-1The above. The filtration type cathode membrane is improved on the basis of the traditional cathode membrane, and can have the functions of filtration and cathode catalysis. The pollutant removing effect is improved through the interception effect of the filtering type cathode membrane, so that the effluent quality is improved. Therefore, the preparation and development of the high-performance filter type cathode membrane are key factors for improving the performance of the microbial electrochemical system.
The phthalocyanine metal complex is a macrocyclic complex with a conjugated pi electron system and has unique physicochemical properties. The phthalocyanine metal complex has good catalytic activity in oxygen reduction reaction as a cathode catalyst, and simultaneously, the phthalocyanine metal complex can be synthesized in a large amount due to low cost and good chemical properties and thermal stability of the phthalocyanine metal complex, so that the cathode film taking the phthalocyanine metal complex as the catalyst has the characteristics of high output power, low cost, low activation voltage, excellent conductivity and the like.
The invention aims to solve the problem of poor removal effect of the pollutants in the MFC system due to single performance and low performance of the cathode in the traditional cathode membrane. The zinc phthalocyanine doped filtration type cathode membrane prepared by the invention has both cathode catalytic performance and the interception effect of an ultrafiltration membrane, and a thin filtration layer is formed on the surface of the filtration type cathode membrane, so that the filtration effect of the membrane is improved. Therefore, the pollutants are catalytically degraded by the MFC and are filtered and intercepted by the filter type cathode membrane, and the pollutant removal effect of the MFC system is deeply improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a filter type cathode membrane doped with zinc phthalocyanine. The surface of filtration type negative pole membrane has the thin filtering layer of one deck, and the aperture is at 0.1 ~ 10um, can separate the granule that the molecular weight is greater than 500 dalton (atomic mass unit), particle diameter are at 0.1 ~ 1um, on the single negative pole membrane basis of traditional performance, the interception effect of degree of depth promotion pollutant. The specific technical scheme is as follows:
a preparation method of a filter type cathode membrane doped with zinc phthalocyanine comprises the following steps:
(1) dissolving one of polypropylene, polytetrafluoroethylene or polysulfonamide and one of acrylic acid, polyvinyl alcohol or polyethylene glycol methacrylate in an organic solvent according to a certain mass ratio at the temperature of 25-30 ℃; wrapping and stirring the tinfoil for 3-5h, and standing for 4-5h to obtain a bubble-removed homogeneous solution; mixing activated carbon, carbon black and zinc phthalocyanine, uniformly mixing the mixed material and the bubble-removed homogeneous solution, and performing ultrasonic treatment for 20-30min to obtain a conductive film solution;
(2) uniformly coating the conductive film liquid prepared in the step (1) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface; controlling the thickness of the film to be 3-5mm, and standing the stainless steel mesh coated with the conductive film liquid in air for 10-30 s;
(3) and (3) soaking the stainless steel mesh coated with the conductive film liquid in the step (2) into deionized water for 10-20min to obtain the filter type cathode film doped with zinc phthalocyanine.
The organic solvent in the step (1) is one of N, N-dimethylacetamide solution, N-dimethylformamide solution or dimethyl sulfoxide solution.
In the step (1), the mass ratio of one of polypropylene, polytetrafluoroethylene or polysulfonamide to the organic solvent is 1 (7-10).
In the step (1), the mass ratio of one of polypropylene, polytetrafluoroethylene or polysulfonamide to one of acrylic acid, polyvinyl alcohol or polyethylene glycol methacrylate is 4 (1-3).
The activated carbon, the carbon black and the zinc phthalocyanine in the step (1) are mixed according to a mass ratio of 10:1: 1-10: 1: 3.
The mixed material in the step (1) and the homogeneous solution are mixed according to the following weight ratio of (0.25-0.35 g):1ml of the mixture is mixed.
The invention has the beneficial effects that:
the invention provides a preparation method of a filter type cathode membrane doped with zinc phthalocyanine. The invention adopts a phase inversion method as a preparation method of the filter type cathode film doped with zinc phthalocyanine, and the preparation method is simple and easy to implement. The zinc phthalocyanine is used as a doping agent of the filtering type cathode membrane, so that the interception effect of the cathode membrane is improved, a high-molecular filter layer formed by high-molecular resin exists on the surface of the electrode after the filtering type cathode membrane is formed, and the aperture of the ultrafiltration membrane is smaller than 10nm so as to separate particles with the molecular weight larger than 500 daltons (atomic mass unit) and the particle size larger than 10 nm. Therefore, the cathode membrane has the functions of filtration and interception and improves the quality of the effluent.
Bovine Serum Albumin (BSA) solution is used as a simulated pollutant, and after three times of circulating filtration, the filtering type cathode membrane is tested for the BSA interception and removal effect. The results show that the BSA rejection of the filter-type cathode membrane doped with zinc phthalocyanine is up to 82.8%, which is 27% higher than the BSA rejection (65.1%) of the undoped blank filter membrane. This indicates that the rejection performance of the filter type cathode membrane after doping with zinc phthalocyanine is improved.
Meanwhile, the retention effect of the filter type cathode membrane on the COD of the effluent of the MFC reactor is tested, and the result shows that the highest retention rate of the COD of the filter type cathode membrane doped with the zinc phthalocyanine is 67%, and the retention rate of the COD is improved by 34% compared with the retention rate (50%) of the COD of a blank filter membrane not doped with the zinc phthalocyanine. This shows that the pollutant interception effect of the zinc phthalocyanine doped filter type cathode membrane is obviously improved, which can effectively improve the effluent quality of the MFC system.
Drawings
Fig. 1 is a structural view of a membrane electrode of the present invention.
Fig. 2 is a structural view of a filter type cathode membrane applied to an MFC system.
FIG. 3 shows the BSA retention rate of the filter type cathode membrane at 100mgL-1And (2) taking Bovine Serum Albumin (BSA) solution as a simulated pollutant, carrying out three times of circulating filtration on the cathode membrane, cleaning the cathode membrane for 30min after each filtration, measuring the BSA concentration of the filtered effluent, and further calculating the retention rate of the filter type cathode membrane to the BSA. The retention rates of a, b, c and d are respectively blank cathode membranes, example-one filtration type cathode membrane doped with zinc phthalocyanine, example-two filtration type cathode membrane doped with zinc phthalocyanine and example-three filtration type cathode membrane doped with zinc phthalocyanine, 1 is first filtration, 2 is second filtration and 3 is third filtration.
Fig. 4 shows the COD rejection of the cathode filter membrane, and a, b, c, and d are the COD rejection of the blank cathode membrane, the example-first filter cathode membrane doped with zinc phthalocyanine, the example-second filter cathode membrane doped with zinc phthalocyanine, and the example-third filter cathode membrane doped with zinc phthalocyanine, respectively.
Detailed Description
The present invention is further described by the following embodiments with reference to the drawings, but it should be noted that the embodiments are not to be construed as limiting the scope of the present invention.
Example 1
This example illustrates the preparation and characterization of zinc phthalocyanine doped filter cathode membranes provided by the present invention. The steps of the filter type cathode membrane doped with zinc phthalocyanine are as follows:
(1) mixing polypropylene and acrylic acid according to a mass ratio of 4:1 at the temperature of 25 ℃, dissolving in an N, N-dimethylacetamide solution, wrapping with tinfoil, stirring in the dark for 3 hours, and standing for 4 hours to obtain a bubble-removed homogeneous solution. The mass ratio of the polypropylene to the N, N-dimethylacetamide is 1: 7. Mixing activated carbon, carbon black and zinc phthalocyanine according to a mass ratio of 10:1:1, and mixing the mixed material with the bubble-removed homogeneous solution according to the following ratio (0.25 g):1ml of the mixture is evenly mixed and is subjected to ultrasonic treatment for 20min to prepare conductive film liquid;
(2) uniformly coating the conductive film liquid prepared in the step (1) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. Controlling the thickness of the film to be 3mm, and standing the stainless steel mesh coated with the conductive film liquid in air for 10 s;
(3) and (3) soaking the stainless steel mesh with the conductive film liquid in the step (2) in deionized water for 10min to obtain the filter type cathode film doped with zinc phthalocyanine.
(4) Characterization method and results
The structure of the zinc phthalocyanine doped filter cathode membrane of example one, as shown in figure 1; the structure of the filter type cathode membrane doped with zinc phthalocyanine in the MFC system application of example one is shown in fig. 2.
The BSA (bovine serum albumin) retention of the filter-type cathode membrane was measured. As shown in fig. 3 b, the BSA retention of example one zinc phthalocyanine doped filter cathode membrane was 68.3%, which is a 5% increase compared to 65.1% BSA retention of the blank filter cathode membrane, fig. 3 a;
the COD rejection of the filtration type cathode membrane was measured. As shown in b in FIG. 4, the COD retention of the example-zinc phthalocyanine doped filter type cathode membrane is 59%, which is 18% higher than the COD retention of the blank membrane 50% and a in FIG. 4
Example 2
The steps of the filter type cathode membrane doped with zinc phthalocyanine are as follows:
(1) mixing polytetrafluoroethylene and polyvinyl alcohol at the temperature of 27 ℃ according to the mass ratio of 4:2, dissolving in an organic solvent N, N-dimethylformamide solution, wrapping with tinfoil, stirring in the dark for 4h, and standing for 4.5h to obtain a bubble-removed homogeneous solution; the mass ratio of the polytetrafluoroethylene to the N, N-dimethylformamide is 1: 8. Mixing the activated carbon, the carbon black and the zinc phthalocyanine according to a mass ratio of 10:1:2, uniformly mixing the mixed material and the uniform solution (0.3g) from which bubbles are removed for 25min by ultrasonic waves according to a volume ratio of 1ml to obtain the conductive film liquid.
(2) Uniformly coating the conductive film liquid prepared in the step (1) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. The thickness of the membrane is controlled to be 4mm, and the stainless steel mesh coated with the conductive membrane liquid is placed in the air and stands for 20 s.
(3) And (3) soaking the stainless steel mesh with the conductive film liquid in the step (2) in deionized water for 15min to obtain the filter type cathode film doped with zinc phthalocyanine.
(4) Characterization method and results
The structure of the zinc phthalocyanine doped filter cathode membrane of example two, as shown in figure 1; the structure of the filter type cathode membrane doped with zinc phthalocyanine of example two in the application of MFC system is shown in fig. 2.
BSA retention of the filtered cathode membranes was measured. As shown in fig. 3 c, the BSA retention of example di-doped zinc phthalocyanine filter cathode membranes was 77.5%, which is a 16% increase over the blank filter cathode membrane BSA retention of 65.1% in fig. 3 a;
the COD rejection of the filtration type cathode membrane was measured. As shown in c in FIG. 4, the COD retention of the example filter type cathode membrane doped with zinc phthalocyanine is 63%, which is increased by 26% compared with the blank membrane COD retention of 50% and a in FIG. 4
Example 3
The steps of the filter type cathode membrane doped with zinc phthalocyanine are as follows:
(1) at the temperature of 30 ℃, the polysulfone amide and the polyethylene glycol methacrylate are mixed according to the mass ratio of 4: 3, mixing, dissolving in dimethyl sulfoxide solution, wrapping with tinfoil, stirring for 5h in a dark place, and standing for 5h to obtain a homogeneous solution without bubbles. The mass ratio of the polysulfonamide to the dimethyl sulfoxide is 1: 10; mixing the activated carbon, the carbon black and the zinc phthalocyanine according to a mass ratio of 10:1:3, and mixing the mixed material with the homogeneous solution from which bubbles are removed in the step (1) according to a ratio of (0.35 g):1ml of the mixture is evenly mixed and is subjected to ultrasonic treatment for 30min to prepare conductive film liquid;
(2) uniformly coating the conductive film liquid prepared in the step (1) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. Controlling the thickness of the film to be 5mm, and standing the stainless steel mesh coated with the conductive film liquid in air for 30 s;
(3) and (3) soaking the stainless steel mesh with the conductive film liquid in the step (2) in deionized water for 20min to obtain the filter type cathode film doped with zinc phthalocyanine.
(4) Characterization method and results
Example structure of a filter type cathode membrane doped with zinc phthalocyanine, as shown in figure 1; example a block diagram of a filter type cathode membrane triple doped with zinc phthalocyanine in an MFC system application is shown in fig. 2.
BSA retention of the filtered cathode membranes was measured. As shown in d of fig. 3, the BSA rejection of the example tri-doped zinc phthalocyanine filter cathode membrane was 82.8%, which is a 27% increase compared to 65.1% BSA rejection of the blank filter cathode membrane, a of fig. 3;
the COD rejection of the filtration type cathode membrane was measured. As shown in d of fig. 4, the example triple-doped zinc phthalocyanine filter type cathode membrane has a COD retention of 67% which is 34% higher than the COD retention of the blank membrane 50% in a of fig. 4.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (5)

1. A preparation method of a filter type cathode membrane doped with zinc phthalocyanine is characterized by comprising the following steps:
(1) dissolving one of polypropylene, polytetrafluoroethylene or polysulfonamide and one of acrylic acid, polyvinyl alcohol or polyethylene glycol methacrylate in an organic solvent according to a certain mass ratio at the temperature of 25-30 ℃; wrapping and stirring the tinfoil for 3-5h, and standing for 4-5h to obtain a bubble-removed homogeneous solution; mixing activated carbon, carbon black and zinc phthalocyanine, and uniformly mixing the mixed material and the bubble-removed homogeneous solution to prepare a conductive film solution by ultrasonic waves;
(2) uniformly coating the conductive film liquid prepared in the step (1) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface; the thickness of the film is controlled to be 3-5 mm;
(3) and (3) soaking the stainless steel mesh coated with the conductive film liquid in the step (2) into deionized water for 10-20min to obtain the filter type cathode film doped with zinc phthalocyanine.
2. The method as set forth in claim 1, characterized in that the mass ratio of one of polypropylene, polytetrafluoroethylene or polysulfonamide to the organic solvent in the step (1) is 1 (7-10).
3. The method as set forth in claim 1, wherein the mass ratio of one of polypropylene, polytetrafluoroethylene or polysulfone amide to one of acrylic acid, polyvinyl alcohol or polyethylene glycol methacrylate in the step (1) is 4 (1-3).
4. The method as set forth in claim 1, wherein the activated carbon, the carbon black and the zinc phthalocyanine are mixed in a mass ratio of 10:1:1 to 10:1:3 in the step (1).
5. The method as set forth in claim 1, wherein the mixed material of the step (1) is mixed with the homogeneous solution in an amount of (0.25 to 0.35 g):1ml of the mixture is mixed.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS618543B2 (en) * 1979-08-17 1986-03-14 Matsushita Electric Ind Co Ltd
CN101507930A (en) * 2009-03-27 2009-08-19 华南师范大学 Metal phthalocyanine/carbon nano tube composite catalyst and its preparation method and lithium/thinly chloride battery using the catalyst
CN108511765A (en) * 2018-04-19 2018-09-07 哈尔滨工业大学 A kind of graphene doping filtering membrane electrode and preparation method thereof suitable for microbiological fuel cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS618543B2 (en) * 1979-08-17 1986-03-14 Matsushita Electric Ind Co Ltd
CN101507930A (en) * 2009-03-27 2009-08-19 华南师范大学 Metal phthalocyanine/carbon nano tube composite catalyst and its preparation method and lithium/thinly chloride battery using the catalyst
CN108511765A (en) * 2018-04-19 2018-09-07 哈尔滨工业大学 A kind of graphene doping filtering membrane electrode and preparation method thereof suitable for microbiological fuel cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
铁酞菁改性PVDF催化膜的制备及其对染料水溶液的分离特性研究;陈锋涛;《中国优秀博士学位论文全文数据库 工程科技Ⅰ辑》;20190131;第53、57-58、83页 *

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