CN110808378A - Preparation method of anti-pollution cathode membrane doped with metalloporphyrin - Google Patents
Preparation method of anti-pollution cathode membrane doped with metalloporphyrin Download PDFInfo
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Abstract
The invention relates to a preparation method of an anti-pollution cathode membrane doped with metalloporphyrin, which is characterized in that inorganic nano particles and one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate are dissolved in N-methylpyrrolidone solution to obtain homogeneous solution without bubbles; mixing the activated carbon, the conductive material and a porphyrin material, uniformly mixing the mixed material and the homogeneous solution with bubbles removed, and performing ultrasonic treatment for 50-60min to obtain the metalloporphyrin-doped cathode membrane. Under the condition of an external electric field, the flux attenuation rate of the doped metalloporphyrin cathode film is 14% at least and is reduced by 50% compared with that of an undoped blank film. The hydrophilicity of the filter cathode membrane was characterized by contact angle testing. The contact angle of the doped metalloporphyrin cathode film is 64.1 degrees at the minimum, and is reduced by 19 percent compared with the undoped blank film, which shows that the doping of the metalloporphyrin is beneficial to improving the hydrophilicity of the filtering cathode film.
Description
Technical Field
The invention relates to a preparation method of an anti-pollution cathode membrane doped with metalloporphyrin materials.
Background
Along with the rapid development of human society, the discharge amount of wastewater is increasing day by day, the treatment of wastewater requires the investment of a large amount of manpower and financial resources, and organic pollutants in the wastewater contain a large amount of chemical energy, so that a low-energy-consumption and high-efficiency wastewater treatment technology is urgently needed at present, the purposes of realizing wastewater treatment and energy recovery can be achieved, and the problems of water resource shortage and energy shortage can be alleviated. As a novel green wastewater recycling technology, the Microbial Fuel Cell (MFC) is a device for generating current by metabolizing organic matters by microorganisms, and brings a new hope for sustainable wastewater treatment. The MFC mainly comprises an anode chamber, a cathode chamber and a proton exchange membrane, wherein in the anode chamber, microorganisms anaerobically metabolize organic matters to generate electrons and protons, the electrons orderly move from an anode to a cathode through an external circuit to form an electric field, and the protons generated by the anode penetrate through the proton exchange membrane to diffuse to the cathode, are combined with oxygen of the cathode, and generate an oxygen reduction reaction.
Compared with the traditional single MFC air cathode membrane, the filter type air cathode membrane has double functions of electrocatalysis and filtering of the cathode, so that the MFC system has better effluent quality and power output effect. However, in the filtration process, contaminants are easy to block the surface or the pores of the membrane, and the internal structure is subjected to the membrane hydraulic action, so that serious surface adsorption, pore blockage or filter cake formation is caused. The contamination of the filtration cathode membrane inevitably results in an unfavorable change in the membrane structure and a significant deterioration in the separation performance, resulting in a significant decrease in the membrane flux. Meanwhile, a filter cake layer is formed on the surface of the membrane, so that the oxygen reduction reaction rate of a three-phase interface of the cathode membrane is reduced, and the productivity output of a system is reduced. To maintain a stable membrane flux and good cathode electrochemical performance, higher pressures and chemical reagent washes need to be applied, which will greatly reduce the membrane life time, resulting in increased membrane replacement speed. It is currently a focus of research to improve the contamination resistance of the filter cathode membrane.
It is therefore desirable to prepare a cathode membrane that is resistant to contamination, enhances the resistance of the membrane to contamination, prevents the membrane from clogging and performance degradation, maintains its good rejection performance and excellent electrochemical performance during long-term operation, enables regeneration of the cathode membrane, and reduces replacement and cleaning of the cathode membrane.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-pollution cathode membrane doped with metalloporphyrin, wherein the metalloporphyrin material improves the hydrophilic property of the membrane, a hydration layer is formed on the surface of the membrane to inhibit pollutants from directly contacting the surface of a filtering cathode membrane, so that the blockage of the pollutants on membrane pores during filtering is reduced, meanwhile, under the condition of an external electric field, the response to charges is enhanced by the cathode membrane doped with metalloporphyrin, more negative charges are enriched on the cathode membrane, and electrostatic repulsion is formed with the pollutants with the negative charges, so that the adsorption of the pollutants on the membrane is reduced, and the membrane pollution is reduced. The improvement of hydrophilicity and the double anti-pollution mechanism of an external electric field strengthen the anti-pollution performance of the filtering cathode membrane.
The technical scheme of the invention is as follows:
a preparation method of an antipollution cathode membrane doped with metalloporphyrin comprises the following steps:
(1) dissolving inorganic nano particles and one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate in an N-methylpyrrolidone solution at the temperature of 40-45 ℃, wrapping the inorganic nano particles with tinfoil, stirring the mixture for 9-11 hours in a dark place, and standing the mixture for 9-10 hours to obtain a bubble-removed homogeneous solution; the mass ratio of one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate to the inorganic nano particles is 3 (1-3), and the mass ratio of one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate to the N-methylpyrrolidone solution is 1 (12.5-14);
(2) mixing activated carbon, a conductive material and a porphyrin material according to a mass ratio of 9:1: 1-9: 1:5, uniformly mixing the mixed material and the homogeneous solution from which bubbles are removed in the step (1) according to a mass ratio of 9: 1-7: 1, and performing ultrasonic treatment for 50-60min to prepare a conductive film liquid;
(3) according to the step (2), the activated carbon powder in the conductive film liquidThe load capacity is 30-33 mg cm-2Uniformly coating the conductive film liquid prepared in the step (2) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. And soaking the stainless steel mesh coated with the conductive film liquid in a non-solvent for 25min to form the film, thus obtaining the metalloporphyrin-doped cathode film.
The inorganic nano-particles in the step 1) are one of silicon dioxide, aluminum oxide or zirconium dioxide.
The conductive material in the step 2) is one of carbon black, graphene oxide or poly diallyl dimethyl ammonium chloride.
In the step 2), the porphyrin material is one of iron porphyrin, cobalt porphyrin or magnesium porphyrin.
The non-solvent in the step 3) is one of deionized water, ethanol or acetone.
The invention has the beneficial effects that:
the invention adopts the phase inversion method to prepare the cathode film, and has simple preparation process and low cost. The preparation raw materials of the anti-pollution cathode membrane doped with metalloporphyrin comprise organic polymer membrane forming resin, inorganic nano materials, activated carbon, conductive materials, porphyrin materials and the like. The inorganic nano-particles enhance the pollution resistance of the catalytic membrane and improve the hydrophilicity of the membrane. The activated carbon is used as an excellent electrocatalytic cathode membrane carrier, and has the advantages of large specific surface area, excellent conductivity and stable mechanical property. The conductive material such as carbon black particles with smaller particle size is beneficial to improving the conductivity, and is easy to disperse in organic polymer film-forming resin to form a good conductive network. The metalloporphyrin is a material combined by transition metal and macrocyclic conjugated ligand, the whole porphyrin system is rich in electrons and has good conductivity, the response to charges is promoted under an electric field, so that the cathode membrane is enriched with more negative charges, and the pollution resistance of the filtering cathode membrane is enhanced. The cathode membrane is doped with metalloporphyrin containing hydrophilic groups, so that the hydrophilicity of the membrane can be improved, and the blockage of pollutants on membrane pores during filtration is reduced. In the process of filtering pollutants, the hydrophilic groups can be preferentially combined with water molecules, a hydration layer can be formed on the surface of the membrane, and proteins are prevented from directly contacting the surface of the membrane, so that the membrane has outstanding protein adsorption resistance.
The fouling resistance of the membrane was mainly characterized by the flux decay rate and laser scanning confocal microscopy (CLSM). Under the condition of an external electric field, the flux attenuation rate of the doped metalloporphyrin cathode film is 14% at least and is reduced by 50% compared with that of an undoped blank film. The hydrophilicity of the filter cathode membrane was characterized by contact angle testing. The contact angle of the doped metalloporphyrin cathode film is 64.1 degrees at the minimum, and is reduced by 19 percent compared with the undoped blank film, which shows that the doping of the metalloporphyrin is beneficial to improving the hydrophilicity of the filtering cathode film.
The doped metalloporphyrin cathode membrane has the advantages that the hydrophilic performance is improved, the blocking of pollutants to membrane pores during filtering is reduced, and a large amount of negative charges are gathered on the surface of the cathode membrane with high conductivity under the condition of applying an electric field on the other hand. Thus improving the anti-fouling performance of the membrane. CLSM images show that the metalloporphyrin-doped membrane surface adhesion of contaminants is significantly reduced compared to the undoped membrane, which also indicates that the metalloporphyrin-doped modified membrane has significantly improved stain resistance.
Drawings
FIG. 1 is a CLSM image of the cathode film at 100mgL-1The bovine serum albumin solution is used as a simulated pollutant to filter the cathode membrane, and after 30min of hydraulic cleaning, the bovine serum albumin content remained on the membrane surface is determined by a laser scanning confocal microscope (CLSM) to reflect the anti-pollution performance of the cathode membrane. a is the CLSM image of the blank cathode film (cathode film undoped metalloporphyrin), b is the CLSM image of the doped metalloporphyrin cathode film prepared in example one, c is the CLSM image of the doped metalloporphyrin cathode film prepared in example two, and d is the CLSM image of the doped metalloporphyrin cathode film prepared in example three.
FIG. 2 shows the flux recovery of the cathode film at 100mgL-1The bovine serum albumin solution is used as a simulated pollutant, three times of circulating filtration are carried out on the cathode membrane, the filtration flux of the cathode membrane is measured, and the cathode membrane is cleaned by water power after each filtration. When other conditions are not changed, the non-electric field condition is compared with the flux filtered by the cathode membrane when the external direct current electric field condition of 1.5V is applied, and the flux under the action of the electric field is evaluatedThe effect of doped metalloporphyrin on the membrane fouling resistance. a, c, e and g are respectively the flux attenuation rates of the blank filtering cathode film, the doped metalloporphyrin cathode film prepared in the first embodiment, the doped metalloporphyrin cathode film prepared in the second embodiment and the doped metalloporphyrin cathode film prepared in the third embodiment under the condition of no electric field, and b, d, f and h are the flux recovery rates of the blank filtering cathode film, the doped metalloporphyrin cathode film prepared in the first embodiment, the doped metalloporphyrin cathode film prepared in the second embodiment and the doped metalloporphyrin cathode film prepared in the third embodiment under the condition of an applied electric field. The Cycle1 is the first Cycle filtration of the filtering cathode film, the Cycle2 is the second Cycle filtration of the filtering cathode film, and the Cycle3 is the third Cycle filtration of the filtering cathode film.
FIG. 3 is the contact angle of the filter cathode film, a is the contact angle of the blank filter electrode, b is the contact angle of the doped metalloporphyrin cathode film of example one, c is the contact angle of the doped metalloporphyrin cathode film of example two, and d is the contact angle of the doped metalloporphyrin cathode film of example three.
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 one
This example illustrates a method for preparing and characterizing a doped metalloporphyrin cathode film provided by the present invention.
The preparation steps of the doped metalloporphyrin cathode film are as follows:
(1) dissolving polyacrylonitrile and silicon dioxide in N-methylpyrrolidone solution at 40 ℃, wrapping with tinfoil, stirring for 9h in a dark place, and standing for 9h to obtain a bubble-removed homogeneous solution; the mass ratio of the polyacrylonitrile to the silicon dioxide is 3:1, and the mass ratio of the polyacrylonitrile to the N-methyl pyrrolidone is 1: 12.5;
(2) mixing activated carbon, carbon black and ferriporphyrin according to a mass ratio of 9:1:1, uniformly mixing the mixed material and the homogeneous solution from which bubbles are removed in the step (1) according to a mass ratio of 7:1, and performing ultrasonic treatment for 50min to prepare a conductive film liquid;
(3) according to the step (2), the loading amount of the activated carbon powder in the conductive film liquid is 30mg cm-2Uniformly coating the conductive film liquid prepared in the step (2) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. And soaking the stainless steel mesh coated with the conductive film liquid in deionized water for 25min to form the film, thus obtaining the metalloporphyrin-doped cathode film.
The characterization method of the first embodiment is as follows:
characterization method 1: and doping the metalloporphyrin cathode membrane, filtering by using bovine serum albumin solution, and performing CLSM test after 30min hydraulic cleaning. As shown in FIG. 1 b, the particle size distribution of the adsorbed protein of the metalloporphyrin-doped cathode membrane prepared in the first embodiment is 450-500 um, the particle size of the protein aggregated on the cathode membrane filtered by the blank filter membrane is 600um (a in FIG. 1), and the thickness of the contaminated layer is 1-1.5 um. CLSM images show that the doped metalloporphyrin cathode film prepared in example one has significantly improved resistance to contamination over the blank film.
Characterization method 2: the cathode membrane was filtered using a doped metalloporphyrin filter membrane, and the flux decay rate test was performed using bovine serum albumin solution, and after three times of filtration, as shown in d in fig. 2, the flux decay rate of the doped metalloporphyrin cathode membrane prepared in the first example after external electric field enhancement was 21.8%, which was 24% lower than the blank flux decay rate of 28.7% (b in fig. 2) under the same conditions.
Characterization method 3: the contact angle of the filtered cathode film was measured and, as shown in b of FIG. 3, the contact angle of the doped metalloporphyrin cathode film prepared in example one was 66.7 deg., which is 16% lower than the contact angle of the undoped blank cathode film of 79.4 deg. (a of FIG. 3)
Example two
The preparation steps of the doped metalloporphyrin cathode film are as follows:
(1) dissolving polyarylethersulfone ketone and aluminum oxide in an N-methylpyrrolidone solution at the temperature of 43 ℃, wrapping with tinfoil, stirring for 10 hours in a dark place, and standing for 9.5 hours to obtain a bubble-removed homogeneous solution; the mass ratio of the polyarylethersulfone ketone to the aluminum oxide is 3:2, and the mass ratio of the polyarylethersulfone ketone to the N-methylpyrrolidone is 1: 13;
(2) mixing activated carbon, graphene oxide and magnesium porphyrin according to a mass ratio of 9:1:3, uniformly mixing the mixed material and the homogeneous solution from which bubbles are removed in the step (1) according to a mass ratio of 8:1, and performing ultrasonic treatment for 55min to prepare a conductive film liquid;
(3) according to the step (2), the loading amount of the activated carbon powder in the conductive film liquid is 32mg cm-2Uniformly coating the conductive film liquid prepared in the step (2) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. And (3) soaking the stainless steel mesh coated with the conductive film liquid into ethanol for 25min to form the film, thus obtaining the metalloporphyrin-doped cathode film.
The characterization method of example two is as follows:
characterization method 1: and doping the metalloporphyrin cathode membrane, filtering by using bovine serum albumin solution, and performing CLSM test after 30min hydraulic cleaning. As shown in fig. 1 c, the particle size of the adsorbed protein of the doped metalloporphyrin cathode membrane prepared in example two is 300-350 um, the particle size of the protein aggregated on the blank filter membrane filtration cathode membrane is 600um (a in fig. 1), and the thickness of the contaminated layer is 1-1.5 um. CLSM images show that the doped metalloporphyrin cathode film prepared in example two has greatly improved stain resistance over the blank film.
Characterization method 2: the flux decay rate test using bovine serum albumin solution was performed, and after three times of filtration, as shown in f in fig. 2, the flux decay rate of the doped metalloporphyrin cathode film prepared in example two after external electric field enhancement was 14.1%, which was 50.1% lower than the blank flux decay rate of 28.7% (b in fig. 2) under the same conditions.
Characterization method 3: the contact angle of the filtered cathode film was measured and, as shown in c of FIG. 3, the contact angle of the doped metalloporphyrin cathode film prepared in example two was 64.1 deg., which is 19% lower than the contact angle of the undoped blank cathode film of 79.4 deg. (a of FIG. 3)
EXAMPLE III
The preparation steps of the doped metalloporphyrin cathode film are as follows:
(1) dissolving sodium polyacrylate and zirconium dioxide in N-methylpyrrolidone solution at 45 ℃, wrapping with tinfoil, stirring in the dark for 11h, and standing for 10h to obtain bubble-removed homogeneous solution; the mass ratio of the sodium polyacrylate to the zirconium dioxide is 1:1, and the mass ratio of the sodium polyacrylate to the N-methyl pyrrolidone is 1: 14;
(2) mixing activated carbon, poly (diallyldimethylammonium chloride) and cobalt porphyrin according to a mass ratio of 9:1:5, uniformly mixing the mixed material and the homogeneous solution from which bubbles are removed in the step (1) according to a mass ratio of 9:1, and performing ultrasonic treatment for 60min to prepare a conductive film solution;
(3) according to the step (2), the loading amount of the activated carbon powder in the conductive film liquid is 33mg cm-2Uniformly coating the conductive film liquid prepared in the step (2) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. And soaking the stainless steel net coated with the conductive film liquid in acetone for 25min to obtain the metalloporphyrin-doped cathode film.
The characterization method of example three is as follows:
characterization method 1: and doping the metalloporphyrin cathode membrane, filtering by using bovine serum albumin solution, and performing CLSM test after 30min hydraulic cleaning. As shown in d in FIG. 1, the particle size of the adsorbed protein of the metalloporphyrin-doped cathode membrane prepared in the third example is 400-450 um, the particle size of the protein aggregated on the cathode membrane filtered by the blank filter membrane is 600um (a in FIG. 1), and the thickness of the contaminated layer is 1-1.5 um. CLSM images show that the doped metalloporphyrin cathode film prepared in example three has improved resistance to contamination over the blank film.
Characterization method 2: the cathode membrane was filtered using a doped metalloporphyrin filter membrane, and flux decay rate test was performed using bovine serum albumin solution, and after three times of filtration, as shown in h in fig. 2, the flux decay rate of the doped metalloporphyrin cathode membrane prepared in example three after external electric field enhancement was 20.6%, which was 28% lower than the blank flux decay rate of 28.7% (b in fig. 2) under the same conditions.
Characterization method 3: the contact angle of the filtered cathode film was measured and, as shown by d in FIG. 3, the contact angle of the doped metalloporphyrin cathode film prepared in example three was 73.7 deg., which was 7% lower than the contact angle of the undoped blank cathode film of 79.4 deg. (a in FIG. 3)
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 an antipollution cathode membrane doped with metalloporphyrin comprises the following steps:
(1) dissolving inorganic nano particles and one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate in an N-methylpyrrolidone solution at the temperature of 40-45 ℃, wrapping the inorganic nano particles with tinfoil, stirring the mixture for 9-11 hours in a dark place, and standing the mixture for 9-10 hours to obtain a bubble-removed homogeneous solution; the mass ratio of one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate to the inorganic nano particles is 3 (1-3), and the mass ratio of one of polyacrylonitrile, polyarylethersulfone ketone or sodium polyacrylate to the N-methylpyrrolidone solution is 1 (12.5-14);
(2) mixing activated carbon, a conductive material and a porphyrin material according to a mass ratio of 9:1: 1-9: 1:5, uniformly mixing the mixed material and the homogeneous solution from which bubbles are removed in the step (1) according to a mass ratio of 9: 1-7: 1, and performing ultrasonic treatment for 50-60min to prepare a conductive film liquid;
(3) according to the step (2), the loading amount of the activated carbon powder in the conductive film liquid is 30-33 mg cm-2Uniformly coating the conductive film liquid prepared in the step (2) on an effective area of 7cm by using a spatula2The stainless steel net has a single surface. And soaking the stainless steel mesh coated with the conductive film liquid in a non-solvent for 25min to form the film, thus obtaining the metalloporphyrin-doped cathode film.
2. The method of claim 1, wherein the inorganic nanoparticles in step 1) are one of silica, alumina or zirconia.
3. The method as set forth in claim 1, wherein the conductive material in the step 2) is one of carbon black, graphene oxide or poly diallyldimethylammonium chloride.
4. The method as set forth in claim 1, wherein the porphyrin-based material in step 2) is one of iron porphyrin, cobalt porphyrin or magnesium porphyrin.
5. The method as set forth in claim 1, wherein the non-solvent of the step 3) is one of deionized water, ethanol or acetone.
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