CN117585792B - Preparation of functionalized biochar quantum dot doped conductive fiber electrode and application of functionalized biochar quantum dot doped conductive fiber electrode in electrically enhanced microbial load - Google Patents

Preparation of functionalized biochar quantum dot doped conductive fiber electrode and application of functionalized biochar quantum dot doped conductive fiber electrode in electrically enhanced microbial load Download PDF

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CN117585792B
CN117585792B CN202311544461.0A CN202311544461A CN117585792B CN 117585792 B CN117585792 B CN 117585792B CN 202311544461 A CN202311544461 A CN 202311544461A CN 117585792 B CN117585792 B CN 117585792B
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biochar
quantum dot
conductive fiber
doped conductive
fiber electrode
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CN117585792A (en
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于明川
牛军峰
周玉菲
张小霞
童延斌
鲁建江
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North China Electric Power University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/005Combined electrochemical biological processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • C02F3/105Characterized by the chemical composition
    • C02F3/106Carbonaceous materials
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • C02F3/105Characterized by the chemical composition
    • C02F3/108Immobilising gels, polymers or the like
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • C02F3/109Characterized by the shape
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • C02F3/2806Anaerobic processes using solid supports for microorganisms
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/09Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides

Abstract

The application of the functionalized biochar quantum dot doped conductive fiber electrode in preparation and electric enhancement of microbial load is provided. Introducing BCQDs into PA66, amine groups formed by surface functionalization of BCQDs can increase compatibility with PA 66; the nano-grade BCQDs is beneficial to uniformly dispersing on the surface of the PA-BC fiber yarn and improves the conductivity of the fiber yarn; the BCQDs which are uniformly dispersed is used as effective sites for microorganism loading, and the good electric conduction performance of the BCQDs can also effectively strengthen the microorganism electron transfer process and promote the microorganism metabolism. Preparing the PA-BC fiber yarn into a fiber electrode serving as a functional microorganism carrier, and constructing a directional electric strengthening functional flora efficient proliferation system by changing the operation conditions. Under the action of an externally applied electric field, the microbial electron transfer process in the flora can be strengthened, the selectivity of the process on degrading the characteristic pollutants is promoted, and the high-efficiency, low-consumption degradation and mineralization of the characteristic pollutants by the electric strengthening system are realized.

Description

Preparation of functionalized biochar quantum dot doped conductive fiber electrode and application of functionalized biochar quantum dot doped conductive fiber electrode in electrically enhanced microbial load
Technical Field
The invention belongs to the technical field of environmental engineering, relates to a preparation method of a functionalized biochar quantum dot doped nylon 66 material, and in particular relates to innovation of a method for domesticating conductive fiber electrodes serving as microbial carriers to strengthen flora.
Background
Polyhexamethylene adipamide (alias: nylon-66, PA66) is a thermoplastic resin, and the reaction precursors are adipic acid and hexamethylenediamine, which are prepared by a polycondensation method. It has high mechanical strength and hardness, high rigidity and high chemical and thermal stability. Can be used as engineering plastics, mechanical accessories and the like, and also can be used for manufacturing synthetic fibers. PA66 has potential application value in the field of microorganism loading, but the application of the PA66 in the field is restricted due to the problems of poor conductivity, insufficient material surface loading sites and the like.
The doping of the conductive carbon material can effectively improve the conductivity of the organic polymer material, such as CN218115102U, an electrobiological filler component and anaerobic electrobiological denitrification device, CN218146021U, and the conductive fiber materials mentioned in patents such as electrobiological filler component and anaerobic electrobiological denitrification device for sewage treatment are doped with the conductive carbon material such as carbon fiber and carbon black and the organic polymer material, so as to form the fiber material with certain conductivity. However, the conductive carbon materials used in the materials are all materials which are commercially produced, and after doping, the conductive performance can be only increased, the function is single, and the requirement of the microbial carrier material on biocompatibility cannot be met. In addition, the carbon material without functional modification and the high polymer organic material cannot realize effective mutual dissolution in the blending doping process, so that gaps are formed between the carbon material and the high polymer organic material after the carbon material and the high polymer organic material are doped, the mechanical property and the structural stability of the material are reduced, and the long-term stable use of the material is not facilitated.
The functionalized biochar material is introduced into a PA66 system, the functionalized and high-specific-surface-area biochar quantum dot (BCQDs) material is prepared by a quick calcination and ball milling method by using Joule heat, and is mixed and doped with PA66 to form a PA-BC fiber material, and the compatibility of the PA66 and the amine group formed by the surface functionalization of BCQDs can be increased; the BCQDs nanometer-level particle size is also beneficial to uniformly dispersing the particles on the surface of the PA-BC fiber yarn and improving the conductivity of the fiber yarn. In addition, BCQDs which are uniformly dispersed can be used as effective sites for microorganism loading, and the good electric conduction performance of BCQDs can also effectively strengthen the microorganism electron transfer process and promote microorganism metabolism. After preparing the PA-BC fiber into a fiber electrode, the fiber electrode is used as a functional microorganism carrier, and a directional electric strengthening functional flora efficient proliferation system is constructed by changing operating conditions such as voltage and the like. Meanwhile, under the action of an externally applied electric field, the microbial electron transfer process inside the flora can be effectively strengthened, the selective removal of degradation characteristic pollutants in the process is promoted, and the degradation and removal of the characteristic pollutants are efficiently and low-consumption by utilizing the electric strengthening system.
Disclosure of Invention
The invention provides a preparation method of a functionalized conductive nylon fiber, which is applied to strengthening microorganism load and fixation under the condition of a micro electric field. Biomass with low cost is used as a precursor material of a conductive component, and the biochar is prepared by a quick calcination mode of Joule heat, so that the loading capacity of surface functional groups can be effectively increased, and the porosity, micropores and medium Kong Zhanbi of the material are improved; the functional carbon quantum dots (BCQDs) prepared by the method are doped into a PA66 material (PA-BC), can be used as effective sites for microorganism loading, and can effectively strengthen the electron transfer function of microorganisms and promote the metabolic activity and proliferation process of flora due to good electric conductivity; after preparing the PA-BC fiber into a fiber electrode, the fiber electrode is used as a functional microorganism carrier, and a directional electric strengthening functional flora efficient proliferation system can be constructed by changing operating conditions such as voltage and the like.
The technical scheme of the invention is as follows:
the preparation method of the functionalized biochar quantum dot doped conductive fiber electrode and the application of the electrically enhanced microorganism load comprise the following steps:
Step 1: the nylon 66 (PA 66) material required for this patent is prepared by the method described in the article "THE SYNTHESIS of oligomers related to nylon, 4, 6and nylon 6".
Step 2: selecting dried bamboo as a biochar precursor, crushing the bamboo into blocks with the horizontal size ranging from 20mm to 30mm, and then adding the blocks into a KOH aqueous solution to obtain a reaction solution, wherein the mass ratio of the bamboo to KOH is controlled to be 3:1-2:1, and the concentration of KOH is controlled to be 0.5-0.8mol/L; heating the reaction solution to 40 ℃, and stirring for reaction for 24 hours; filtering the reaction solution, alternately cleaning the bamboo with deionized water and ethanol to remove KOH and matured and decomposed macromolecular organic matters, and drying the bamboo through a blast oven (60 ℃) to obtain matured bamboo;
Step 3: and (3) putting the cured bamboo dried in the step (2) into a graphite tube, and simultaneously adding a proper amount of a mixture of NH 4 Cl and KCl (mass ratio is 1:2), wherein the mass ratio of the cured bamboo to the mixture of NH 4 Cl and KCl is 2:1-1:1. Placing a graphite tube into a Joule ultra-fast heating device, maintaining the reaction temperature at 1000 ℃ for 100ms under vacuum condition, maintaining the reaction temperature for 10s, maintaining the temperature for 10s, repeating the heating-maintaining-cooling process once, taking out the biochar material after the reaction is finished, placing the biochar material into 0.1mol/L KOH aqueous solution, stirring for 12h, carrying out suction filtration, placing the biochar material into 0.1mol/L HCl aqueous solution, stirring for 12h, carrying out suction filtration, and flushing the biochar material by using deionized water until the pH value of effluent is=5. And taking out the biochar material, and putting the biochar material into an ancient air oven for drying at 60 ℃ to obtain the biochar material.
Step 4: putting the biochar material in the step 3 into a ball mill, adopting a wet grinding mode, wherein the adding mass ratio of the biochar to water is 3:2-1:1, ball milling for 30-60min, rotating at 4000rpm, taking out the biochar material, carrying out ultrasonic dispersion (ultrasonic for 10 min) by using deionized water, filtering the dispersion liquid, taking out black filtrate, and adopting a freeze drying mode to obtain the biochar quantum dot (BCQDs) material. Heating the PA66 material in the step 1 to 250 ℃, adding BCQDs material in a molten state, stirring for 30min in the molten state at a mass ratio of 7:3-9:1, processing by an extruder to form PA-BC fiber yarns, fixing the PA-BC fiber yarns on two stainless steel metal pipes with proper intervals by a spinning machine to form a fixed fiber curtain capable of being used for loading microorganisms, wherein the fiber length range is as follows: 50-2000mm to obtain the functionalized biochar quantum dot doped conductive fiber electrode.
The application of the functionalized biochar quantum dot doped conductive fiber electrode obtained by the preparation method in the electrically enhanced microbial load is that the functionalized biochar quantum dot doped conductive fiber electrode is taken as a microbial carrier and is put into an aerobic or anaerobic microbial reaction device, and the interval between the functionalized biochar quantum dot doped conductive fiber electrodes is 200-500mm; the functionalized biochar quantum dot doped conductive fiber electrode is respectively used as an anode and a cathode, a constant voltage of 0.01-1V is applied to operate, activated sludge is added to culture, a large number of functional microorganisms are loaded on the surface of the functionalized biochar quantum dot doped conductive fiber electrode in a short time, and along with the stability of a system, the current is maintained at the following level: 0.5-10mA. Under the same running condition and culture time, the microbial load on the fiber electrode carrier under the energizing condition is 1.2-1.7 times and 1.8-2.6 times of the microbial load of the conventional filler under the non-energizing condition. In addition, the abundance of acid-producing microorganisms on the surface of the carrier under the condition of electrification is increased by 1.3-1.8 times compared with that under the condition of no electrification.
The invention has the beneficial effects that: the functionalized conductive fiber material in the method can be used as a microbial carrier, so that the stability of the loaded microbial micelle is improved under the condition of power-up, and the metabolic activity and proliferation process of the material are promoted. In the step 1, the PA66 material is prepared by adopting a traditional method. Step 2, taking the fastest growing biomass material, namely bamboo, as a raw material, mixing the fastest growing biomass material with a proper amount of KOH solution, heating and stirring the mixture, strengthening the curing hydrolysis process, hydrolyzing and removing polysaccharide substances such as lignin, pectin and the like in the bamboo, regulating and controlling biomass components, retaining cellulose and hemicellulose (main components of a framework structure), and prefabricating a pore structure before calcining so as to regulate and control pore size distribution and pore structure of the biochar material in a calcining stage. In the step 3, the instantaneous heating equipment is selected, so that the loading capacity of the functional groups on the surface of the material can be effectively improved, and the decomposition loss of the amine groups in the carbonization rearrangement process is reduced. Combining molten salt and in-situ amination calcination, and carrying out thermal decomposition on ammonium chloride to generate ammonia gas which is condensed with carboxyl on the surface of the biomass material to realize surface functionalization; the molten salt can lead the carbonization process of the biomass material to be heated more uniformly, is favorable for the formation of a microporous structure, and meanwhile, cl < - > can also undergo substitution reaction with a carbon substrate to form a chlorine-containing functional group structure in the high-temperature carbonization rearrangement process, and the introduction of chlorine and amine functional groups can effectively regulate and control charge arrangement in a system, construct an effective charge directional migration channel and improve the charge migration capacity of the surface of the material. On the basis, the average particle size of the produced biochar quantum dot (BCQDs) material can be effectively controlled through the ball milling process. The PA66 and BCQDs are fused and blended and extruded to form the PA-BC fiber, and amine groups formed by surface functionalization of BCQDs can effectively form electrostatic attraction with carboxyl groups on the PA66 polymer chain segment, so that compatibility of the PA66 and the carboxyl groups can be improved, and the proper BCQDs particle size is also favorable for uniform dispersion of the PA-BC fiber on the surface of the fiber, so that the conductivity of the fiber is further improved. In addition, the BCQDs which is uniformly dispersed can be used as an effective site for microorganism loading, and the good electric conduction performance of the BCQDs can also effectively strengthen the electron transfer process of microorganisms and strengthen the microorganism interaction metabolism. Under the action of an external electric field, the metabolism and proliferation processes of microorganism groups with electron donors and electron acceptors are promoted, and the purposes of increasing the microorganism load on the surface of the fiber carrier, strengthening the degradation process of organic pollutants and accelerating the selective domestication of the functional microorganism groups are realized. After preparing the PA-BC fiber into a fiber electrode, the fiber electrode is used as a functional microorganism carrier, and a directional electric strengthening functional flora efficient proliferation system is constructed by changing operating conditions such as voltage and the like. In addition, under the action of an externally applied electric field, the microbial electron transfer process inside the flora can be effectively strengthened, the selectivity of the process on degradation of characteristic pollutants is promoted, and the high-efficiency, low-consumption degradation and mineralization of the characteristic pollutants by the electric strengthening system are realized.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Example 1
Preparing a functionalized biochar quantum dot material:
The dried bamboo is selected as a biochar precursor, crushed into a bulk material with the horizontal dimension of 20mm, added into KOH aqueous solution, the mass ratio of the bamboo to the KOH is 2:1, the KOH concentration is 0.5mol/L, and the reaction solution is heated to 40 ℃ and stirred for reaction for 24 hours. And filtering the reaction solution, alternately cleaning the bamboo with deionized water and ethanol to remove KOH and matured and decomposed macromolecular organic matters in the biomass material, and drying the bamboo in a forced air oven (60 ℃) to obtain the matured bamboo.
And (3) putting the dried cured bamboo into a graphite tube, and simultaneously adding a proper amount of mixture of NH 4 Cl and KCl (the mass ratio is 1:2), wherein the mass ratio of the cured bamboo to the mixture of NH 4 Cl and KCl is 2:1. Placing a graphite tube into a Joule ultra-fast heating device, maintaining the reaction temperature at 1000 ℃ for 100ms under vacuum condition, maintaining the reaction temperature for 10s, maintaining the temperature for 10s, repeating the heating-maintaining-cooling process once, taking out the biochar material after the reaction is finished, placing the biochar material into 0.1mol/L KOH aqueous solution, stirring for 12h, carrying out suction filtration, placing the biochar material into 0.1mol/L HCl aqueous solution, stirring for 12h, carrying out suction filtration, and flushing the biochar material by using deionized water until the pH value of effluent is=5. And taking out the biochar material, and putting the biochar material into an ancient air oven for drying at 60 ℃ to obtain the biochar material.
Putting the dried biochar material into a ball mill, adopting a wet grinding mode, wherein the adding mass ratio of the biochar to water is 3:2, ball milling for 60min, and the rotating speed is 4000rpm, taking out the biochar material, carrying out ultrasonic dispersion (ultrasonic for 10 min) by using deionized water, filtering the dispersion liquid, taking out black filtrate, and adopting a freeze drying mode at the temperature of minus 60 ℃ to obtain the biochar quantum dot (BCQDs) material.
Example 2
Preparing functional conductive fibers:
preparing PA66 material according to the reference in the step 1, heating the PA66 material to 250 ℃, adding BCQDs material in a molten state, stirring for 30min in the molten state, processing the PA-BC fiber yarn by an extruder, fixing the PA-BC3 fiber yarn on two stainless steel metal pipes with proper intervals by a spinning machine, and forming a fixed fiber curtain capable of being used for loading microorganisms, wherein the fiber length is 500mm.
Reference group: different BCQDs adding ratios are selected by adopting the same preparation method, different PA-BC fiber filaments are prepared, the adding mass ratio of PA66 to BCQDs is 8:2, 9:1 and 10:0 respectively, the fiber filament numbers are PA-BC2, PA-BC1 and PA-BC0 respectively, and the corresponding fixed fiber electrode is prepared by a textile machine.
Example 3
Physical and chemical performance test of PA-BC fiber yarn:
The specific surface areas of the PA-BC3, the PA-BC2, the PA-BC1 and the PA-BC0 are respectively 19.5, 12.6, 6.7 and 1.9m 2/g through an N 2 adsorption and desorption experiment. Along with the surface of the biochar doped PA-BC fiber, a large number of porous biochar quantum dots appear, so that the specific surface area of the biochar doped PA-BC fiber is gradually increased, which is helpful for enriching microorganisms on the surface of the material, and meanwhile, the microorganism electron transfer process can be promoted.
The resistances of the PA-BC3, the PA-BC2 and the PA-BC1, which are 24, 370 and 1360Ω respectively, are tested by a four-probe method, and the non-conduction of the PA-BC0 can not be tested. The conductivity of the biochar doped PA-BC fiber is gradually increased, so that the effect of an electric field generated by an external power supply on activating microorganisms on the surface of the fiber is facilitated.
The tensile strength and the elongation at break of the PA-BC3, the PA-BC2, the PA-BC1 and the PA-BC0 are respectively 180, 160, 115, 90Mpa and 5, 7, 9.5 and 12 percent by mechanical property test. With the increase of the doping of the biochar, the tensile strength of the PA-BC fiber yarn is gradually increased, which shows that the doping of the biochar can obviously improve the mechanical strength of the fiber yarn material. Meanwhile, the elongation at break gradually decreases, probably due to the fact that the rigidity and hardness of the material are improved by doping of biochar. This is advantageous in maintaining the stability of the use of the filament.
Example 4
Microbial load comparison test:
Placing the PA-BC3 fiber electrode serving as a microorganism carrier into an aerobic microorganism reaction device, wherein the interval between the fiber electrodes is 200mm; the fiber electrode is used as an anode and a cathode respectively, 0.5V constant voltage is applied to operate, activated sludge is added to culture, a large amount of microorganisms can be loaded on the surface of the fiber in a short time, and along with the stability of a system, the current is maintained at the following level: 2-3mA. Under the same operating conditions and culture time, the microbial loadings on the PA-BC3 fiber electrode under the energized condition were 1.2 and 1.8 times that of the non-energized condition and the conventional filler (polyethylene porous spherical filler), respectively.
The PA-BC3 fiber electrode is put into an anaerobic microorganism reaction device, other operation conditions are the same as those of the aerobic microorganism reaction device, and the microorganism load of the fiber electrode under the power-on condition in the anaerobic microorganism reaction device is 1.5 and 2.3 times of that of the traditional filler (polyethylene porous spherical filler) under the power-off condition.
Comparative example 1: pure PA66 and commercially available conductive nylon fibers were selected to replace PA-BC3 to prepare fiber electrodes under the same conditions as in example 2, and the obtained fiber electrodes were numbered Blank-PA and C-PA. The C-PA fiber electrode was placed in an aerobic microbial reaction apparatus, and the amount of microorganisms on the surface of the C-PA was only 2/3 of that on the surface of the PA-BC3 under the same conditions and for the same cultivation time as in example 4.
Because the Blank-PA is not conductive and can not be powered on, under the condition that other operation conditions and culture time are kept as same as those of the example 4, the surface load microorganism amount of the Blank-PA is only 1/2 of that of the PA-BC3 under the condition of no power on, and is 3/4 of that under the condition of no power on.
Comparative example 2: the same preparation conditions as in example 2 were adopted to obtain a fiber electrode, sample number B-PA, by selecting a commercially produced plain coconut shell charcoal instead of BCQDs material. The B-PA fiber electrode was placed in an aerobic microbial reaction apparatus, and the surface-supported microbial load of B-PA was only 3/5 of that of PA-BC3 under the same conditions and culture time as in example 4.
Example 5
Degradation test of chlorinated flame retardant:
The anaerobic reaction device with the PA-BC fiber electrode carrier is used for degradation test of the chlorinated flame retardant, the operation conditions are respectively two types of power-on and power-off, the degradation performance is compared with that of the liquid chromatography and the ion chromatography to respectively test the content of the tetrachlorobisphenol A and the chloride ion in the water, and the result shows that the degradation rate of the tetrachlorobisphenol A under the power-on condition is 1.2 times that under the power-off condition, and the dechlorination performance is 2 times that under the power-off condition. Under normal conditions, the ratio of dechlorinated microorganisms in anaerobic microorganism flora is generally low, functional microorganisms can be effectively enriched through an electric strengthening process, and the electron transfer effect is promoted, so that the degradation and dechlorination processes of a system on chlorine-containing pollutants are accelerated.

Claims (2)

1. The preparation method of the functionalized biochar quantum dot doped conductive fiber electrode is characterized by comprising the following steps of:
step 1: preparing a nylon 66 material;
Step 2: selecting dried bamboo as a biochar precursor, crushing the bamboo into blocks with the horizontal size ranging from 20 mm to 30mm, and then adding the blocks into a KOH aqueous solution to obtain a reaction solution, wherein the mass ratio of the bamboo to KOH is controlled to be 3:1-2:1, and the concentration of KOH is controlled to be 0.5-0.8mol/L; heating the reaction solution to 40 ℃, and stirring for reaction for 24 hours; filtering the reaction solution, alternately cleaning the bamboo with deionized water and ethanol, removing KOH and matured and decomposed macromolecular organic matters, and drying to obtain matured bamboo;
Step 3: placing the dried cured bamboo in the step 2 into a graphite tube, and simultaneously adding a mixture of NH 4 Cl and KCl in a mass ratio of 1:2, wherein the mass ratio of the cured bamboo to the mixture of NH 4 Cl and KCl is 2:1-1:1; placing a graphite tube into a Joule ultra-fast heating device, heating to a reaction temperature of 1000 ℃ for 100ms under vacuum condition, maintaining the reaction temperature for 10s, cooling for 10s, repeating the heating-maintaining-cooling process once, taking out the biochar material after the reaction is finished, placing the biochar material into a KOH aqueous solution with the concentration of 0.1mol/L, stirring for 12h, carrying out suction filtration, placing the biochar material into an HCl aqueous solution with the concentration of 0.1mol/L, stirring for 12h, carrying out suction filtration, and flushing the biochar material by using deionized water until the pH value of effluent is=5; taking out the biochar material and drying the biochar material at the temperature of 60 ℃ to obtain the biochar material;
Step 4: putting the biochar material in the step 3 into a ball mill, adopting a wet grinding mode, wherein the adding mass ratio of the biochar material to water is 3:2-1:1, ball milling is carried out for 30-60min, the rotating speed is 4000rpm, taking out the biochar material, carrying out ultrasonic dispersion by using deionized water, carrying out suction filtration on the dispersion liquid, taking out black filtrate, and adopting a freeze drying mode to obtain the biochar quantum dot BCQDs material; heating the PA66 material in the step 1 to 250 ℃, adding BCQDs material in a molten state, stirring for 30min in the molten state at a mass ratio of 7:3-9:1, processing by an extruder to form PA-BC fiber yarns, fixing the PA-BC fiber yarns on two stainless steel metal pipes with proper intervals by a spinning machine to form a fixed fiber curtain capable of being used for loading microorganisms, wherein the fiber length range is as follows: 50-2000mm to obtain the functionalized biochar quantum dot doped conductive fiber electrode.
2. The application of the functionalized biochar quantum dot doped conductive fiber electrode obtained by the preparation method in the electrically enhanced microbial load is characterized in that the functionalized biochar quantum dot doped conductive fiber electrode is taken as a microbial carrier, and is placed into an aerobic or anaerobic microbial reaction device, wherein the interval between the functionalized biochar quantum dot doped conductive fiber electrodes is 200-500mm; the functionalized biochar quantum dot doped conductive fiber electrode is respectively used as an anode and a cathode, a constant voltage of 0.01-1V is applied to operate, activated sludge is added to culture, a large number of functional microorganisms are loaded on the surface of the functionalized biochar quantum dot doped conductive fiber electrode in a short time, and along with the stability of a system, the current is maintained at the following level: 0.5-10mA.
CN202311544461.0A 2023-11-20 2023-11-20 Preparation of functionalized biochar quantum dot doped conductive fiber electrode and application of functionalized biochar quantum dot doped conductive fiber electrode in electrically enhanced microbial load Active CN117585792B (en)

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CN110550743A (en) * 2019-08-12 2019-12-10 天津大学 Regulation and control method for enhancing pollutant degradation based on microbial electrochemical principle
CN111377533A (en) * 2020-04-21 2020-07-07 无锡原旭机电科技有限公司 Sewage treatment microbial carrier and preparation method thereof

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