CN111039388A - Polyimide-based catalytic cathode carbon membrane loaded with monoatomic catalyst and application thereof - Google Patents
Polyimide-based catalytic cathode carbon membrane loaded with monoatomic catalyst and application thereof Download PDFInfo
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Abstract
The invention provides a polyimide-based catalytic cathode carbon film loaded with a single-atom catalyst and application thereof, which utilize the principle of MOF-based in-situ derived single-atom catalyst, take polyimide as a carbon film precursor, mix and disperse the prepared MOF precursor and conductive nano-materials into an organic solvent, then add the solution into a polyamic acid solution, and blade-coat the solution on a glass plate to form an MOF polyamic acid hybrid film; and finally, carbonizing in an inert gas atmosphere by using a programmed heating method, wherein metal ions in the MOF are pyrolyzed and reduced into a single atom catalyst in situ in the carbonizing process, and the polyamic acid is firstly converted into polyimide and then further forms a carbon film. The invention prepares the conductive cathode catalytic membrane with high mechanical property, chemical corrosion resistance, high stability and high ORR activity. The method is used in an EMBR system, a microbial fuel cell system and an electro-catalytic system, and is suitable for the water membrane treatment of high-concentration refractory organic industrial wastewater.
Description
Technical Field
The invention belongs to the field of high molecular polymer/monatomic catalyst functional composite material construction and application and the technical field of sewage purification and wastewater resource utilization, and particularly relates to a monoatomic catalyst-loaded polyimide-based catalytic cathode carbon membrane suitable for high-concentration refractory organic industrial wastewater membrane treatment, and provides a membrane electrode for improving the catalytic activity of a carbon-based microbial fuel cell and a preparation method thereof.
Background
Water is a source of all lives and is also an indispensable important resource for developing national economy. With the rapid development of the industrial process in China, more and more organic compounds are widely applied to the production or life of human beings, and a large amount of toxic and harmful organic pollutants enter a water body, and especially a large amount of organic wastewater which is difficult to degrade is discharged in the industrial production of printing and dyeing, chemical industry, pharmacy, organic synthesis and the like. The pollution of high-concentration refractory organic wastewater is upgraded into a serious environmental problem, and is also a hotspot and difficulty of the research in the current environmental field. The main characteristics of the waste water are complex components, high pollutant concentration, high chroma, high toxicity and poor biodegradability. The conventional biochemical method is adopted for treatment, so that the satisfactory treatment effect is difficult to achieve, especially the removal effect on refractory organic matters is poor, the COD content is still high after treatment, and the effluent quality is poor; in addition, the simple physical and chemical method is used as a pretreatment and subsequent treatment process, the required conditions are harsh, and the problems of medicament addition, high operation cost and secondary pollution exist at the same time; in addition, a series of high-tech treatment experimental equipment researched at present has high requirements and high cost, is not suitable for industrial production and is not suitable for treating bulk wastewater. Therefore, in order to solve the problem of water pollution, the development of new materials and new technologies for treating the organic wastewater which is economic and effective and is difficult to degrade is imperative.
At present, the problem of organic industrial wastewater difficult to degrade is solved by mainly improving the original mode of wastewater treatment from the aspects of improving the biodegradability of wastewater and reducing the cost. On the other hand, organic matters in the sewage contain a large amount of chemical energy, and analysis from the perspective of energy shows that how to realize resource utilization in the sewage purification process is a new direction for environmental technology development.
The bioelectrochemical system is a novel sewage treatment and energy recovery technology as a reactor for oxidizing and decomposing pollutants by using electrochemically active microorganisms and generating electric energy. The chemical energy of organic matters in the sewage can be directly converted into electric energy, the loss caused by energy multi-stage transmission is avoided, the potential is huge in the fields of water treatment and energy recovery, and the chemical energy is also widely concerned by numerous scholars in the fields of environment and energy in recent years.
The membrane separation technology has been developed rapidly and widely used in recent decades, and has become an important means for solving the problems of environmental pollution and energy. The method has the advantages of high efficiency, energy conservation, compact equipment, easily controlled process, convenient operation, safe environment, convenient amplification, easy integration with other technologies and the like. A Membrane Bioreactor (MBR) is an advanced wastewater treatment method combining membrane technology and biotechnology, and mainly removes biodegradable organic pollutants in water by utilizing the biotechnology, and then filters suspended matters and water-soluble macromolecular substances by utilizing the membrane technology to reduce water turbidity and play double roles of biochemical treatment and reverse osmosis treatment. The MBR has the advantages of high treatment efficiency, small occupied area, high automation degree and the like, and is a sewage treatment and reclaimed water recycling technology with the greatest development prospect in the 21 st century.
In order to enhance the removal of organic matter from wastewater by MBRs, researchers have attempted to couple membrane separation techniques to bio-electrochemical systems. An electrically assisted membrane bioreactor (EMBR) couples a Microbial Fuel Cell (MFC) and a membrane bioreactor together, can generate electricity while treating wastewater, can degrade organic pollutants by using the metabolism of microorganisms, can decompose carbon dioxide, electrons and protons by using the anaerobic respiration of the microorganisms, and the electrons are transferred to a cathode by an external circuit to generate a potential difference to form current so as to enable the cathode and activated sludge, colloid and the like with negative electricity to generate near electrostatic repulsion force, thereby controlling membrane pollution; in addition, the mode of recycling and utilizing the chemical energy of the organic matters in the form of electric energy by utilizing the microorganisms in the mild environment has huge potential, and has important practical significance for sustainable energy sources and environmental problem treatment in the future. Currently, researchers have studied on the coupling technology, for example, patent document No. 201210081071.X discloses a "reactor and wastewater treatment method for directly coupling a bioreactor and a microbial fuel cell", in which a conductive material is used as a filter medium of a membrane bioreactor and simultaneously as a cathode of a microbial fuel cell to realize direct coupling of the MBR and the MFC, so that good effluent quality and membrane pollution control can be realized, and the coupling technology has a good development prospect.
The most central component in the whole coupled system is the membrane electrode, which plays a decisive role in the catalytic activity of organic reactions, the output power and the service life of microbial fuel cells. The electrocatalytic Oxygen Reduction Reaction (ORR) is a half-reaction that occurs at the cathode, which is always aerated during the operation of the reactor, and the higher the oxygen mass transfer efficiency of the cathode, the higher the cell potential obtained and the higher the electricity production efficiency. However, the kinetic rate of the oxygen reduction reaction is much slower than the anode reaction rate, which is a major factor that limits the performance of microbial fuel cells; therefore, increasing the oxygen reduction reaction rate becomes one of the key issues driving the development process of fuel cells. The catalyst mainly plays a role in increasing the reaction rate, efficiency and selectivity in the chemical conversion process, so the catalyst plays a crucial role in electrode reaction, and how to prepare the cathode catalytic membrane with high activity and high stability becomes the core for improving the efficiency of the EMBR reaction system.
Single-atom catalysts (SACs) are a new catalytic material emerging in recent years, and are novel catalysts with a size smaller than that of nanoparticles and sub-nanoclusters, the particle dispersion degree of the catalysts can reach the level of Single atom, and the maximum atom utilization rate and the excellent catalytic performance can be obtained. The supported metal catalyst only contains isolated single metal atoms as a main active center, and the single atoms have no interaction and spatial ordering, and the structure of the atomic scale can generate unsaturated environment of metal active sites, quantum size effect, metal-carrier interaction and the like, so that the single atom catalyst has very excellent catalytic performance. However, the method also has a troublesome problem that when the metal particles are reduced to a monoatomic level, the monoatomic catalyst is easily agglomerated during the synthesis process due to the sharp increase of the free energy of the metal surface. Therefore, the stability and loading of the monatomic catalyst remain two major challenges to be solved in the development of monatomic catalysts. In addition, the literature reports of loading the monatomic catalyst on the separation membrane are few, most researches are basically focused on the preparation of the monatomic catalyst material, and the powdery catalyst is very easy to have the problems of poor stability, easy loss, difficult collection, difficult realization of long-term cyclic utilization and the like in the water treatment process.
Disclosure of Invention
The invention provides a polyimide-based catalytic cathode carbon film loaded with a single-atom catalyst and suitable for high-concentration refractory organic industrial wastewater film treatment and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyimide-based catalytic cathode carbon film loaded with a monatomic catalyst adopts the principle of MOF-based in-situ derivation of the monatomic catalyst to prepare a functional carbon film from a polyimide precursor.
The aperture of the catalytic cathode carbon membrane is 1.5-30nm, the porosity is 30% -80%, and the conductivity is 10-300S/cm; the tensile strength of the catalytic cathode carbon membrane is 5-100MPa, and the maximum bearable pressure is 3-5 MPa.
A preparation method of a polyimide-based catalytic cathode carbon membrane loaded with a monoatomic catalyst comprises the steps of mixing and dispersing a prepared MOF precursor and a conductive nano material into an organic solvent, adding a polyamic acid solution into the solution, and blade-coating the solution on a glass plate to form an MOF polyamic acid hybrid membrane; and finally, carbonizing in an inert gas atmosphere by using a programmed heating method, wherein metal ions in the MOF are pyrolyzed and reduced into a single atom catalyst in situ in the carbonizing process, and the polyamic acid is firstly converted into polyimide and then further forms a carbon film.
The preparation method comprises the following steps:
1) preparation of ZnM-BMOFs: the target metal M salt methanol solution and Zn2+Mixing a salt methanol solution and a 2-methylimidazole organic ligand methanol solution, regulating the pH value, ultrasonically mixing, dissolving and stirring, drying for 4 hours, washing a precipitate by using the methanol solution, and drying at 70-80 ℃;
2) preparation of ZnM-BMOFs/carbon nano tube/polyamic acid hybrid membrane: ultrasonically dispersing ZnM-BMOFs powder and carbon nanotube powder prepared in the step 1) into an N, N-dimethylacetamide solvent to prepare a solution A for later use; dissolving 4,4 '-diaminodiphenyl ether in an N, N-dimethylacetamide solvent, stirring until the 4, 4' -diaminodiphenyl ether is completely dissolved, and then adding pyromellitic dianhydride into the solution for multiple times to completely dissolve the pyromellitic dianhydride to prepare a performed polymer polyamic acid solution B; uniformly mixing the solution A and the solution B, strongly stirring for 12-14h and carrying out ultrasonic treatment for 1-2 h; pouring the solution on a horizontal glass plate with a heater, blade-coating the solution to form a film, and drying the film at 35-40 ℃;
3) preparing a target metal M monatomic catalyst/carbon nanotube/polyimide-based catalytic carbon membrane: putting the ZnM-BMOFs/carbon nano tube/polyamide acid hybrid membrane prepared in the step 2) into a vacuum tube furnace, carbonizing in an inert gas atmosphere, controlling the gas flow rate at 60-100mL/min, and adopting a temperature programming mode, wherein the temperature programming is as follows: heating to 100 +/-5 ℃, 200 +/-5 ℃ and 350 +/-5 ℃ at the heating speed of 2-5 ℃/min, and respectively staying for 1-1.5h, thus forming the ZnM-BMOFs/carbon nanotube/polyimide film; and continuously heating until the temperature is 800-900 ℃, staying for 2-3h, then generating the M metal monoatomic catalyst by the MOF in situ, further carbonizing the polyimide film into a polyimide-based carbon film, and finally naturally cooling to obtain the target metal M monoatomic catalyst/carbon nanotube/polyimide-based catalytic carbon film.
The target metal M is one or two of Fe, Co, Ni and Cu.
The target metal M salt and Zn in the step 1) above2+The salt is one or more of nitrate, chloride and acetate.
The molar concentration of the target metal M salt methanol solution in the step 1) is 0.01-0.15mol/L, Zn2+The molar concentration of the salt methanol solution is 0.02-0.3mol/L, the molar concentration of the 2-methylimidazole organic ligand methanol solution is 0.1-3mol/L, Zn2+The mixing molar ratio with the target metal M salt is 1:1 to 2:1, and the preferable range is 1.25:1 to 1.5: 1.
The mass fraction of the solution A in the step 2) is 10 wt% -25 wt%, the mass ratio of ZnM-BMOFs to the carbon nano tubes is 1:1-2:1, the mass fraction of the prepolymer polyamic acid solution B is 12 wt% -30 wt%, and the molar ratio of 4, 4' -diaminodiphenyl ether to pyromellitic dianhydride in the prepolymer polyamic acid solution B is 1:1-1: 1.5.
The inert gas in the step 3) is nitrogen or argon.
The polyimide-based catalytic cathode carbon membrane loaded with the monatomic catalyst is used in an EMBR system, a microbial fuel cell system and an electrocatalysis system, and is used for purifying high-concentration organic wastewater difficult to degrade.
The invention utilizes coordination chemistry to prepare metal organic framework material, metal ions and 2-methylimidazole form a complex, and Zn is introduced to increase the distance between target metal atoms2+Ion protection, avoidThe target metal atoms are bonded with each other to form large metal atom nano particles, and under the protection of the fence effect of Zn, the phenomena of metal atom aggregation and uneven microstructure are prevented. In the high-temperature pyrolysis process, due to the characteristic of low boiling point of Zn, the Zn is directly volatilized, and the target metal M is pyrolyzed and reduced to metal single atoms from an ion state in situ, so that the catalytic activity of the membrane electrode is greatly improved. Meanwhile, in the process of high-temperature heat treatment, the organic ligand 2-methylimidazole is carbonized, and a nitrogen source is gradually decomposed to generate ammonia gas to be doped on carbon to form pyridine nitrogen and pyrrole nitrogen which are used as anchoring sites of monoatomic metal, so that the physicochemical structure is stable; and the heteroatom-doped carbon material can further improve the ORR catalytic activity, so that the ORR active sites are more exposed, and the optimization of the material transmission performance is facilitated.
The carbon molecular sieve membrane is prepared by adopting polyimide which is most researched and has the best performance at present as a precursor of the functional carbon membrane, so that the carbon molecular sieve membrane can obtain incomparable good permeability, corrosion resistance, dimensional stability and mechanical performance of the traditional polymer, the tensile strength range of the catalytic cathode carbon membrane is 5-100MPa, the maximum bearable pressure is 3-5MPa, and the carbon molecular sieve membrane is particularly suitable for treating high-concentration refractory organic wastewater and prolongs the service life of the catalytic cathode carbon membrane. Meanwhile, the carbon nano tube nano material is introduced to improve the conductivity of the membrane electrode, and the range of the conductivity is 10-300S/cm.
The MOF precursor material and the carbon nano tube conductive material are introduced into the polyamic acid solution at the earlier stage of preparation, and are further carbonized to form the polyimide-based catalytic carbon film after the polyamic acid hybrid film is prepared.
Compared with the prior art, the invention has the beneficial effects that:
1) the preparation method of the polyimide-based catalytic cathode carbon film loaded with the monatomic catalyst is simple and easy for practical production, and by utilizing the principle of MOF in-situ derivation of the monatomic catalyst, under the synergistic protection of the metal organic framework and the 'fence' action of Zn, the phenomena of metal atom aggregation and uneven microstructure in the high-temperature pyrolysis process are avoided, the problem of low metal atom utilization rate is effectively solved, the ORR activity of the film electrode is greatly improved, the progress of the cathode oxygen reduction reaction is promoted, the cathode potential is increased, and the electricity generation efficiency of the reactor is improved.
2) According to the polyimide-based catalytic cathode carbon film loaded with the monatomic catalyst, polyimide is used as a precursor of a carbon molecular sieve film, and a functional carbon film with good mechanical property, stability, corrosion resistance and permeability can be obtained by controlling the processes of precursor synthesis and carbonization temperature rise; meanwhile, the carbon nano tube nano material is introduced, so that the electron transfer resistance is reduced, the ohmic loss is reduced, the continuous electron transmission can be realized, the conductivity of the cathode film is increased, and the current efficiency of the fuel cell is improved.
3) Compared with the traditional cathode membrane material preparation process, the polyimide-based catalytic cathode carbon membrane loaded with the monatomic catalyst adopts the idea of synchronous conversion preparation of the metal monatomic catalyst and the base membrane, the whole functional carbon membrane network is combined with each other through chemical bond interaction, the acting force between catalytic particles and the base membrane is stronger, the stability of the membrane electrode and the catalyst is higher, the problems of falling off and loss of the catalyst in the water treatment process are effectively solved, the polyimide-based catalytic cathode carbon membrane is suitable for high-concentration organic wastewater treatment, the anti-pollution performance can be improved, the cleaning frequency is reduced, and the service life is prolonged.
Drawings
Fig. 1 is a schematic diagram of the design concept of a polyimide-based catalytic cathode carbon membrane loaded with a monatomic catalyst.
In the figure: 1-MOFs, 2-carbon nanotubes, 3-target metal M single-atom catalyst, 4-ZnM-BMOFs/carbon nanotube/polyamic acid hybrid membrane and 5-target metal M single-atom catalyst/carbon nanotube/polyimide-based catalytic carbon membrane.
Detailed Description
The following embodiments are further illustrated by reference to the following specific examples:
as shown in fig. 1, a polyimide-based catalytic cathode carbon film loaded with a monatomic catalyst adopts the principle of MOF-based in-situ derivation of the monatomic catalyst to prepare a functional carbon film from a polyimide precursor.
The aperture of the catalytic cathode carbon membrane is 1.5-30nm, the porosity is 30% -80%, and the conductivity is 10-300S/cm; the tensile strength of the catalytic cathode carbon membrane is 5-100MPa, and the maximum bearable pressure is 3-5 MPa.
A preparation method of a polyimide-based catalytic cathode carbon membrane loaded with a monoatomic catalyst comprises the steps of mixing and dispersing a prepared MOF precursor and a conductive nano material into an organic solvent, adding a polyamic acid solution into the solution, and blade-coating the solution on a glass plate to form an MOF polyamic acid hybrid membrane; and finally, carbonizing in an inert gas atmosphere by using a programmed heating method, wherein metal ions in the MOF are pyrolyzed and reduced into a single atom catalyst in situ in the carbonizing process, and the polyamic acid is firstly converted into polyimide and then further forms a carbon film.
The preparation method comprises the following steps:
1) preparation of ZnM-BMOFs: the target metal M salt methanol solution and Zn2+Mixing a salt methanol solution and a 2-methylimidazole organic ligand methanol solution, regulating the pH value, ultrasonically mixing, dissolving and stirring, drying for 4 hours, washing a precipitate by using the methanol solution, and drying at 70-80 ℃;
2) preparation of ZnM-BMOFs/carbon nano tube/polyamic acid hybrid membrane: ultrasonically dispersing ZnM-BMOFs powder and carbon nanotube powder prepared in the step 1) into an N, N-dimethylacetamide solvent to prepare a solution A for later use; dissolving 4,4 '-diaminodiphenyl ether in an N, N-dimethylacetamide solvent, stirring until the 4, 4' -diaminodiphenyl ether is completely dissolved, and then adding pyromellitic dianhydride into the solution for multiple times to completely dissolve the pyromellitic dianhydride to prepare a performed polymer polyamic acid solution B; uniformly mixing the solution A and the solution B, strongly stirring for 12-14h and carrying out ultrasonic treatment for 1-2 h; pouring the solution on a horizontal glass plate with a heater, blade-coating the solution to form a film, and drying the film at 35-40 ℃;
3) preparing a target metal M monatomic catalyst/carbon nanotube/polyimide-based catalytic carbon membrane: putting the ZnM-BMOFs/carbon nano tube/polyamide acid hybrid membrane prepared in the step 2) into a vacuum tube furnace, carbonizing in an inert gas atmosphere, controlling the gas flow rate at 60-100mL/min, and adopting a temperature programming mode, wherein the temperature programming is as follows: heating to 100 +/-5 ℃, 200 +/-5 ℃ and 350 +/-5 ℃ at the heating speed of 2-5 ℃/min, and respectively staying for 1-1.5h, thus forming the ZnM-BMOFs/carbon nanotube/polyimide film; and continuously heating until the temperature is 800-900 ℃, staying for 2-3h, then generating the M metal monoatomic catalyst by the MOF in situ, further carbonizing the polyimide film into a polyimide-based carbon film, and finally naturally cooling to obtain the target metal M monoatomic catalyst/carbon nanotube/polyimide-based catalytic carbon film.
The target metal M is one or two of Fe, Co, Ni and Cu.
The target metal M salt and Zn in the step 1) above2+The salt is one or more of nitrate, chloride and acetate.
The molar concentration of the target metal M salt methanol solution in the step 1) is 0.01-0.15mol/L, Zn2+The molar concentration of the salt methanol solution is 0.02-0.3mol/L, the molar concentration of the 2-methylimidazole organic ligand methanol solution is 0.1-3mol/L, Zn2+The mixing molar ratio with the target metal M salt is 1:1 to 2:1, and the preferable range is 1.25:1 to 1.5: 1.
The mass fraction of the solution A in the step 2) is 10 wt% -25 wt%, the mass ratio of ZnM-BMOFs to the carbon nano tubes is 1:1-2:1, the mass fraction of the prepolymer polyamic acid solution B is 12 wt% -30 wt%, and the molar ratio of 4, 4' -diaminodiphenyl ether to pyromellitic dianhydride in the prepolymer polyamic acid solution B is 1:1-1: 1.5.
The inert gas in the step 3) is nitrogen or argon.
The polyimide-based catalytic cathode carbon membrane loaded with the monatomic catalyst is used in an EMBR system, a microbial fuel cell system and an electrocatalysis system, and is used for purifying high-concentration organic wastewater difficult to degrade.
Example 1:
1. preparing a target metal Co monatomic catalyst/carbon nanotube/polyimide-based catalytic carbon film:
1) 1.86g of Zn (NO) was taken3)2·6H2O and 1.455g of Co (NO)3)2·6H2Dissolving O in 50mL of methanol solution, and oscillating for dissolution; 2.05g of 2-methylimidazole were dissolved in 50mL of methanol solution, dissolved and mixed well. Then adding the prepared metal salt mixed solution into an organic ligand methanol solution, ultrasonically dissolving for 15min, and stirring for 12 h; and placing the obtained mixed solution in an oven at 120 ℃ for 4h, centrifuging the precipitate cooled to room temperature, washing the precipitate for 3 to 5 times by using methanol, and finally drying the precipitate at 70 ℃ for 8h to obtain the ZnCo-BMOFs material.
2) Respectively taking 1g of ZnCo-BMOFs powder and 1g of carbon nanotube powder, dispersing into 10mL of N, N-dimethylacetamide solvent, magnetically stirring for 2h, and ultrasonically dispersing for 2h to prepare a solution A for later use; dissolving 5.4g of 4,4 '-diaminodiphenyl ether in 50mL of N, N-dimethylacetamide solvent, stirring until the 4, 4' -diaminodiphenyl ether is completely dissolved, then adding 5.886g of pyromellitic dianhydride into the solution in three batches, and stirring for 2 hours to prepare a polyamic acid solution B; and uniformly mixing the solution A and the solution B, strongly stirring for 12 hours and carrying out ultrasonic treatment for 2 hours. And pouring the mixed solution on a horizontal glass plate with a heater, blade-coating the mixed solution to form a film, and drying the film for 24 hours at 40 ℃ in an environment with the humidity not higher than 40% to obtain the ZnCo-BMOFs/carbon nano tube/polyamide acid hybrid film.
3) Putting the ZnCo-BMOFs/carbon nano tube/polyamic acid hybrid membrane into a vacuum tube furnace, and reacting in a reaction vessel under the vacuum condition2Carbonizing in a gas atmosphere, controlling the nitrogen flow rate at 60-100mL/min, and adopting a temperature programming mode, wherein the temperature programming is as follows: the heating speed is 2 ℃/min, the temperature is raised to 100 ℃, 200 ℃ and 350 ℃ and stays for 1h respectively, and then ZnCo-BMOFs/carbon nano tube/polyimide film is formed; and continuously heating the mixture until the temperature is 800 ℃, staying for 2-3h, generating Co metal single-atom catalysts (Co-SACs) by the MOF in situ, and finally naturally cooling the mixture to obtain the Co-SACs/carbon nano tubes/polyimide group catalytic carbon film.
2. Application of Co-SACs/carbon nanotube/polyimide-based catalytic carbon membrane in EMBR (emulsion enhanced biological reactor) system
In this example, the raw coking wastewater was treated with an EMBR system.
The raw water quality of wastewater from a certain coke plant is shown in Table 1.
TABLE 1 raw Water quality of wastewater from certain coking plant
High-concentration coking wastewater of a coking plant is taken as inlet water, a self-made Co-SACs/carbon nano tube/polyimide-based catalytic carbon membrane is taken as a cathode membrane electrode, and aeration is carried out on the surface of the cathode. The wastewater is firstly treated by the microorganisms in the anode chamber and then enters the cathode chamber for the catalytic filtration treatment of the cathode membrane. The peristaltic pump is used for controlling the flow rate of inlet and outlet water, the hydraulic retention time is 48h, the COD and the ammonia nitrogen concentration in the water are measured periodically, the COD of the outlet water is lower than 100mg/L after stable operation for one week, the removal rate of the COD can reach more than 98%, and the ammonia nitrogen concentration is lower than 15 mg/L.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The polyimide-based catalytic cathode carbon film loaded with the monatomic catalyst is characterized in that the functional carbon film is prepared from a polyimide precursor by adopting the MOF-based in-situ derivation monatomic catalyst principle.
2. The monatomic catalyst-supported polyimide-based catalytic cathode carbon membrane according to claim 1, wherein the catalytic cathode carbon membrane has a pore diameter of 1.5 to 30nm, a porosity of 30 to 80%, and an electrical conductivity of 10 to 300S/cm; the tensile strength of the catalytic cathode carbon membrane is 5-100MPa, and the maximum bearable pressure is 3-5 MPa.
3. The preparation method of the single-atom catalyst supported polyimide-based catalytic cathode carbon membrane as claimed in claim 1 or 2, characterized in that the prepared MOF precursor and the conductive nano-material are mixed and dispersed in an organic solvent, then the solution is added into a polyamic acid solution, and a MOF polyamic acid hybrid membrane is formed by blade coating on a glass plate; and finally, carbonizing in an inert gas atmosphere by using a programmed heating method, wherein metal ions in the MOF are pyrolyzed and reduced into a single atom catalyst in situ in the carbonizing process, and the polyamic acid is firstly converted into polyimide and then further forms a carbon film.
4. The preparation method of the monatomic catalyst-supported polyimide-based catalytic cathode carbon film according to claim 3, which is characterized by comprising the following steps:
1) preparation of ZnM-BMOFs: the target metal M salt methanol solution and Zn2+Mixing a salt methanol solution and a 2-methylimidazole organic ligand methanol solution, regulating the pH value, ultrasonically mixing, dissolving and stirring, drying for 4 hours, washing a precipitate by using the methanol solution, and drying at 70-80 ℃;
2) preparation of ZnM-BMOFs/carbon nano tube/polyamic acid hybrid membrane: ultrasonically dispersing ZnM-BMOFs powder and carbon nanotube powder prepared in the step 1) into an N, N-dimethylacetamide solvent to prepare a solution A for later use; dissolving 4,4 '-diaminodiphenyl ether in an N, N-dimethylacetamide solvent, stirring until the 4, 4' -diaminodiphenyl ether is completely dissolved, and then adding pyromellitic dianhydride into the solution for multiple times to completely dissolve the pyromellitic dianhydride to prepare a performed polymer polyamic acid solution B; uniformly mixing the solution A and the solution B, strongly stirring for 12-14h and carrying out ultrasonic treatment for 1-2 h; pouring the solution on a horizontal glass plate with a heater, blade-coating the solution to form a film, and drying the film at 35-40 ℃;
3) preparing a target metal M monatomic catalyst/carbon nanotube/polyimide-based catalytic carbon membrane: putting the ZnM-BMOFs/carbon nano tube/polyamide acid hybrid membrane prepared in the step 2) into a vacuum tube furnace, carbonizing in an inert gas atmosphere, controlling the gas flow rate at 60-100mL/min, and adopting a temperature programming mode, wherein the temperature programming is as follows: heating to 100 +/-5 ℃, 200 +/-5 ℃ and 350 +/-5 ℃ at the heating speed of 2-5 ℃/min, and respectively staying for 1-1.5h, thus forming the ZnM-BMOFs/carbon nanotube/polyimide film; and continuously heating until the temperature is 800-900 ℃, staying for 2-3h, then generating the M metal monoatomic catalyst by the MOF in situ, further carbonizing the polyimide film into a polyimide-based carbon film, and finally naturally cooling to obtain the target metal M monoatomic catalyst/carbon nanotube/polyimide-based catalytic carbon film.
5. The method for preparing the monatomic catalyst-supported polyimide-based catalytic cathode carbon film according to claim 4, wherein the target metal M is one or two of Fe, Co, Ni and Cu.
6. The method for preparing a monoatomic catalyst-supporting polyimide-based catalytic cathode carbon membrane according to claim 4, wherein the target metal M salt and Zn in the step 1) are2+The salt is one or more of nitrate, chloride and acetate.
7. The method for preparing a monoatomic catalyst-supporting polyimide-based catalytic cathode carbon membrane according to claim 4, wherein the molar concentration of the target metal M salt in methanol in the step 1) is 0.01 to 0.15mol/L, and Zn is added2+The molar concentration of the salt methanol solution is 0.02-0.3mol/L, the molar concentration of the 2-methylimidazole organic ligand methanol solution is 0.1-3mol/L, Zn2+The mixing molar ratio of the target metal M salt to the target metal M salt is 1:1-2: 1.
8. The method for preparing the monoatomic catalyst-supported polyimide-based catalytic cathode carbon film according to claim 4, wherein the mass fraction of the solution A in the step 2) is 10 wt% to 25 wt%, the mass ratio of ZnM-BMOFs to carbon nanotubes is 1:1 to 2:1, the mass fraction of the prepolymer polyamic acid solution B is 12 wt% to 30 wt%, and the molar ratio of 4, 4' -diaminodiphenyl ether to pyromellitic dianhydride in the prepolymer polyamic acid solution B is 1:1 to 1: 1.5.
9. The method for preparing a monatomic catalyst-supported polyimide-based catalytic cathode carbon film according to claim 4, wherein the inert gas in the step 3) is nitrogen or argon.
10. The use of the monoatomic catalyst-supported polyimide-based catalytic cathode carbon membrane according to claim 1, wherein the membrane is used in an EMBR system, a microbial fuel cell system, and an electrocatalysis system to purify high-concentration refractory organic wastewater.
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