CN108383098B - Hollow porous carbon material co-doped with various heteroatoms, and preparation method and application thereof - Google Patents
Hollow porous carbon material co-doped with various heteroatoms, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hollow porous carbon material codoped with multiple heteroatoms, and a preparation method and application thereof. The method comprises the steps of firstly taking a metal organic framework as a structural template and a nitrogen source, then adding two reactants containing nitrogen, phosphorus and sulfur heteroatoms, carrying out in-situ polymerization reaction on the surfaces of the two reactants on the metal organic framework, and simultaneously doping the nitrogen, phosphorus and sulfur heteroatoms. The complex has a geometric shape similar to that of a pure metal organic framework compound crystal, and metal oxides are removed through high-temperature calcination and hydrochloric acid aqueous solution reaction to obtain a plurality of heteroatom co-doped hollow porous carbon materials; and uniformly mixing the composite material, acetylene black and polytetrafluoroethylene emulsion, coating the mixture on graphite paper, and drying to obtain the capacitive desalting electrode. The method has the advantages of simple operation, easily controlled conditions, large-scale synthesis, high specific surface area of the obtained electrode, good conductivity and wettability, and potential application prospect in the aspect of capacitive desalination.
Description
Technical Field
The invention relates to a hollow porous carbon material codoped with multiple heteroatoms, and a preparation method and application thereof.
Background
The shortage of fresh water resources is one of the biggest resource crises facing the whole world in this century, and the desalination and desalination technology of seawater and brackish water has attracted extensive social attention as an important way to effectively solve the crisis. The existing desalination methods mainly include a distillation method and a membrane method. The distillation method has high operation temperature, large energy consumption and serious boiler scale damage and corrosion; the membrane process has stringent requirements for membrane performance, high membrane damage rate and high cost. In addition, the desalination methods have the defect of high energy consumption, and even the reverse osmosis membrane method with the lowest energy consumption has the energy consumption about ten times of the theoretical value. Therefore, the development of desalination technology with low energy consumption and low cost is the demand of the times. Capacitive desalination is a brand new desalination technology based on the remote electric double layer capacitance. The method has low energy consumption and high desalting efficiency, and is environment-friendly. Can be applied to the desalination of seawater and brackish water, the softening of industrial and agricultural production and domestic water and the like, and has wide development space and application prospect.
Based on the principle of capacitive desalination, an electrode material with large specific surface area, developed gaps and good conductivity becomes the key for obtaining high capacitive desalination performance. The porous carbon material is always the first choice of the electrode material of the capacitive desalting device due to the characteristics of high specific surface area, good conductivity, unique chemical stability, easy control of pore structure, good conductivity and the like. Metal-organic frameworks (MOFs) compounds have high specific surface area, large pore volume and tunable pore structure, and have recently been demonstrated to be useful as carbon precursors or templates for the preparation of porous carbon materials (Chaikitisil W, Hu M, Wang H, Huang H S, Fujita T, Wu K C W, Chen L C, Yamauchi Y, Ariga K, Nanopous carbon through direct carbon synthesis of a zeolitic adsorbent framework for supercritical electrolytes, M. Commun. 2012, 48(58): 7259) 7261). The porous carbon material has the characteristics of simple preparation method, excellent electrochemical performance and the like. For the capacitive desalination technology, in addition to the high specific surface area and high order structure of the electrode material, the electrical conductivity of the electrode material is also very critical. A great deal of research shows that hetero atoms, such as boron, nitrogen, phosphorus, sulfur or oxygen, are introduced into the porous carbon material to remarkably increase the surface functional groups of the carbon material and improve the mechanical, conductive or electrochemical properties (Iyyamperual E, Wang S Y, Dai L M, Vertically Aligned BCN Nanotubes with High performance, ACS Nano 2012, 6(6): 5259-5265), so that the material is endowed with unique properties such as mechanical, electronic, optical, semiconductor, energy storage and the like, and is widely applied to the fields of electrode materials, adsorbents, hydrogen storage, catalysts and the like of supercapacitors. Obviously, more heteroatoms are doped in the carbon material to provide a multifunctional or polyatomic synergistic effect, so that the conductivity and wettability of the carbon material are improved. However, the capacitance desalting electrode material is mainly nitrogen-doped carbon material, and a small amount of nitrogen and phosphorus co-doped carbon material, and few reports about ternary element-doped carbon material exist.
Zeolitic Imidazolate framework materials (ZIFs) are three-dimensional tetrahedral Frameworks that form a structure similar to a zeolite from transition metals and imidazole ligands. The high thermal stability and chemical stability of ZIFs and the rich nitrogen source in the imidazole ligand make the ZIFs an ideal precursor for preparing nitrogen-doped porous carbon with excellent performance.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a hollow porous carbon material co-doped with multiple kinds of heteroatoms for use in desalination of sea water by electric double layer capacitance desalination.
The second object of the present invention is to provide a method for producing the hollow porous carbon material.
The invention also aims to provide application of the hollow porous carbon material in preparation of a hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms.
In order to overcome the performance defect of a single element doped porous carbon material serving as a capacitive desalination electrode, ZIF-8 is used as a structural template and a nitrogen doping source, hexachlorocyclotriphosphazene serving as a nitrogen source and a phosphorus source and 4,4 '-sulfonyl diphenol serving as a sulfur source are polymerized in situ on the surface of ZIF-8 to form poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol), and the hollow porous carbon material codoped with various heteroatoms and codoped with nitrogen, phosphorus and sulfur is formed after high-temperature carbonization.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a hollow porous carbon material of multiple heteroatom codope which characterized in that this hollow porous carbon material is: the nitrogen, phosphorus and sulfur co-doped hollow carbon polyhedron comprises the following components in percentage by mass: 79.65: 5.29: 1.55: 0.63.
the method for preparing the hollow porous carbon material codoped with various heteroatoms is characterized by comprising the following specific steps:
a. preparing a methanol solution of ZIF-8 with the mass percent concentration of 0.8-0.9% by using a metal organic framework ZIF-8;
b. dropwise adding methanol solutions of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the methanol solution of ZIF-8 obtained in the step a under the condition of stirring at a molar ratio of 1:3: 1-1: 4:3 at a speed of: 40-60 mL/min, adding 1-2 mL of triethylamine (serving as an initiator of polymerization reaction of hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol) under the stirring condition, stirring at 310-350 rpm/min for 24-26 h, centrifuging, and drying to obtain poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8;
c. b, carbonizing the poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8 obtained in the step b in an inert atmosphere, adding a hydrochloric acid aqueous solution to react to remove metal oxides, and fully washing and drying to obtain a plurality of heteroatom co-doped hollow porous carbon materials; the carbonization process comprises the following steps: controlling the heating rate to be 1-2 ℃/min, heating to 800-900 ℃, preserving the heat for 1-3 hours, and then cooling to room temperature, wherein the flow rate of the inert gas is 80-140 mL/min.
The preparation method of the metal organic framework ZIF-8 comprises the following steps: dissolving zinc nitrate hexahydrate and 2-methylimidazole in a methanol solution according to a molar ratio of 1: 7-1: 8, stirring at 310-350 rpm/min for 24-26 h, uniformly stirring and mixing, centrifuging, washing with the methanol solution, and drying to obtain the metal organic framework ZIF-8.
A preparation method of a hollow porous carbon-based capacitive desalination electrode adopts the hollow porous carbon material co-doped with various heteroatoms as a raw material, and is characterized by comprising the following process steps: uniformly stirring and mixing a plurality of heteroatom-codoped hollow porous carbon materials, acetylene black and polytetrafluoroethylene emulsion according to a mass ratio of 80:10: 10-90: 5:5, coating the mixture on conductive substrate graphite paper, and drying at 100-120 ℃; finally, the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms is prepared.
In the preparation process of the ZIF-8, the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1: 7-1: 8; the obtained ZIF-8 has a uniform size and a uniform diameter of 0.05-0.1 μm, and if the molar ratio is less than the range, the ZIF-8 with a larger diameter can be obtained, and the particles with larger sizes can reduce the specific surface area, so that the improvement of the capacitive desalting performance is not facilitated.
In the preparation process of the ZIF-8, the violent stirring speed is kept at 310-350 rpm/min, and the stirring time is 24-26 h. If the stirring speed is too high, the formation of the MOF structure is not facilitated; if the stirring time is too short, the MOF growth process is insufficient, which may reduce the yield.
In the preparation process of the hollow carbon-based capacitive desalination electrode codoped with multiple heteroatoms, the preparation method is characterized in that in the preparation process, the molar ratio of hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and ZIF-8 is 1:3: 1-1: 4: 3. If the molar ratio is less than this range, complete coating of the poly (cyclotriphosphazene-co-4, 4' -sulfonyldiphenol) with ZIF-8 cannot be achieved.
In the preparation process of the hollow carbon-based capacitive desalination electrode codoped with multiple heteroatoms, the preparation method is characterized in that in the preparation process, the dripping speed of a methanol solution of hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol is moderate, otherwise, the dispersibility of poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) on the surface of ZIF-8 is not ideal, so that the formation of a hollow structure of a final product is influenced.
In the preparation process of the hollow carbon-based capacitive desalination electrode codoped with multiple heteroatoms, the carbonization process in the inert atmosphere needs to be realized through temperature-controlled calcination, the temperature rise rate is controlled to be 1-2 ℃/min, the temperature is firstly raised to 800-900 ℃, the temperature is kept for 1-3 hours at the temperature, and then the temperature is reduced to the room temperature; the inert protective gas comprises nitrogen and argon, and the gas flow rate is 80-140 mL/min. The carbonization process is carried out under the protection of inert gas, which is beneficial to maintaining the structure of the carbon skeleton, and if the carbonization process is carried out under the condition of oxygen, the collapse of the carbon skeleton and the loss of carbon can be caused. The temperature rise rate, the carbonization temperature and the heat preservation time cannot be too high or too low, so that the loss of heteroatoms can be caused when the temperature rise rate, the carbonization temperature and the heat preservation time are too high, and the graphitization degree of the carbon material can be reduced when the temperature rise rate, the carbonization temperature and the heat preservation time are too low, so that the desalting performance of the capacitance desalting electrode carbon material is influenced.
The preparation method of the hollow carbon-based capacitive desalination electrode co-doped with various heteroatoms, which is prepared by the method, is characterized in that the composite material prepared by the method takes a metal organic framework ZIF-8 as a structural template and a nitrogen doping source, the in-situ polymerization of poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) realizes the doping of three hetero elements containing nitrogen, phosphorus and sulfur at the same time, and the ZIF-8 is decomposed to release gas in the high-temperature carbonization process, so that the hollow porous carbon material co-doped with nitrogen, phosphorus and sulfur is formed. The characteristics of high surface area, high conductivity, excellent wettability, developed gaps and the like are applied to desalination, and the novel carbon material is believed to have a good application prospect in the field of desalination.
The novel hollow carbon material co-doped with various heteroatoms has higher conductivity, excellent wettability, developed gaps and higher surface utilization rate as a desalting electrode material, and provides a new way for desalting with high performance, high efficiency and low energy consumption.
The desalting electrode prepared by the invention has high efficiency and low energy consumption desalting performance. Belongs to the technical field of manufacturing process of electric desalting electrodes. The invention can be applied to desalination of seawater and brackish water, and provides a new way for low-energy consumption, low-cost and high-performance desalination.
Drawings
FIG. 1 is a transmission electron micrograph of a plurality of heteroatom-codoped hollow carbon-based capacitive desalination electrodes obtained in example II of the present invention;
FIG. 2 is a photograph of elemental mapping of a plurality of heteroatom-codoped hollow carbon-based capacitive desalination electrodes obtained in example II of the present invention;
FIG. 3 is a diagram illustrating the desalination performance of a hollow carbon-based capacitive desalination electrode co-doped with multiple heteroatoms obtained in example II of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the following examples are given, but the present invention is not limited to the scope of the examples.
The first embodiment is as follows:
dissolving zinc nitrate hexahydrate and 2-methylimidazole in a molar ratio of 1:7 in 100 ml of methanol solution, mechanically stirring for 24 hours at a stirring speed of 310rpm/min to fully react, centrifuging, washing with the methanol solution for 2-3 times, and drying to obtain a metal organic framework ZIF-8;
preparing a methanol solution with the mass concentration of 0.8wt% of ZIF-8 from the obtained metal organic framework ZIF-8, and mixing hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and ZIF-8 according to the weight ratio of 1:3:1, dropwise adding a methanol solution of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the above ZIF-8 methanol solution at a stirring speed of 310rpm/min, dropwise adding 1mL of triethylamine, continuously and violently and mechanically stirring for 18h, centrifuging, washing for 2-3 times with methanol, drying at 80 ℃, placing in a tube furnace, controlling the heating rate to be 2 ℃/min under the protection of nitrogen gas with a gas flow rate of 90 mL/min, heating to 800 ℃, preserving heat for 2 h at 800 ℃, cooling to room temperature, adding a 2M-3M hydrochloric acid solution, stirring overnight to remove metal oxides, fully washing and drying to obtain the nitrogen, phosphorus and sulfur co-doped hollow graded porous carbon material. The obtained nitrogen, phosphorus and sulfur co-doped hollow porous carbon material is uniformly mixed with acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10:10, then the mixture is coated on conductive substrate graphite paper, and then the conductive substrate graphite paper is dried at 100-120 ℃; finally, the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms is prepared.
And testing the specific capacitance of the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms. Using a CHI-660D type electrochemical workstation, wherein the electrolyte is 0.5M sodium chloride solution, the scanning speed is 1mV/s, and the voltage range is-0.5V; the specific capacitance of the electrode was measured to be greater than 200F/g. The electrode prepared above was tested for desalting performance, and the desalting efficiency was more than 80% in 50ppm of saline.
Example two:
dissolving zinc nitrate hexahydrate and 2-methylimidazole in a molar ratio of 1:75 in 200ml of methanol solution, mechanically stirring for 24 hours at a stirring speed of 330 rpm/min to fully react, centrifuging, washing with the methanol solution for 2-3 times, and drying to obtain a metal organic framework ZIF-8;
preparing a methanol solution with the mass concentration of 0.9wt% of ZIF-8 from the obtained metal organic framework ZIF-8, and mixing hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and ZIF-8 according to the weight ratio of 1:3: 2, under the stirring speed of 330 rpm/min, dropwise adding methanol solution of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the methanol solution of the ZIF-8 at the speed of 60mL/min, dropwise adding 1mL triethylamine, continuously and violently and mechanically stirring for 18h, centrifuging, washing for 2-3 times by using methanol, drying at 80 ℃, placing in a tubular furnace, controlling the heating rate to be 2 ℃/min under the protection of nitrogen gas with the gas flow rate of 90 mL/min, heating to 850 ℃, preserving heat for 2 h at 850 ℃, adding 2M-3M hydrochloric acid solution after cooling to room temperature, stirring overnight to remove metal oxides, fully washing and drying to obtain the nitrogen, phosphorus and sulfur co-doped hollow hierarchical porous carbon material. The obtained nitrogen, phosphorus and sulfur co-doped hollow porous carbon material is uniformly mixed with acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10:10, then the mixture is coated on conductive substrate graphite paper, and then the conductive substrate graphite paper is dried at 100-120 ℃; finally, the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms is prepared.
And testing the specific capacitance of the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms. Using a CHI-660D type electrochemical workstation, wherein the electrolyte is 0.5M sodium chloride solution, the scanning speed is 1mV/s, and the voltage range is-0.5V; the specific capacitance of the electrode was measured to be greater than 250F/g. The electrode prepared above was tested for desalting performance, and the desalting efficiency was greater than 85% in 50ppm of brine.
Example three:
dissolving zinc nitrate hexahydrate and 2-methylimidazole in a molar ratio of 1:8 in 160ml of methanol solution, mechanically stirring for 24 hours at a stirring speed of 320 rpm/min to fully react, centrifuging, washing with the methanol solution for 2-3 times, and drying to obtain a metal organic framework ZIF-8;
preparing a methanol solution with the mass concentration of 0.86wt% of ZIF-8 from the obtained metal organic framework ZIF-8, and mixing hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and ZIF-8 according to the weight ratio of 1:4:3, dropwise adding a methanol solution of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the above ZIF-8 methanol solution at a stirring speed of 320 rpm/min, dropwise adding 1mL of triethylamine, continuously and violently and mechanically stirring for 18h, centrifuging, washing for 2-3 times with methanol, drying at 80 ℃, placing in a tube furnace, controlling the heating rate to be 2 ℃/min under the protection of nitrogen gas with a gas flow rate of 90 mL/min, heating to 900 ℃, preserving heat for 2 h at 900 ℃, cooling to room temperature, adding a 2M-3M hydrochloric acid solution, stirring overnight to remove metal oxides, fully washing and drying to obtain the nitrogen, phosphorus and sulfur co-doped hollow graded porous carbon material. The obtained nitrogen, phosphorus and sulfur co-doped hollow porous carbon material is uniformly mixed with acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10:10, then the mixture is coated on conductive substrate graphite paper, and then the conductive substrate graphite paper is dried at 100-120 ℃; finally, the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms is prepared.
And testing the specific capacitance of the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms. Using a CHI-660D type electrochemical workstation, wherein the electrolyte is 0.5M sodium chloride solution, the scanning speed is 1mV/s, and the voltage range is-0.5V; the specific capacitance of the electrode was measured to be greater than 300F/g. The electrode prepared above was tested for desalting performance, and the desalting efficiency was greater than 90% in 50ppm of saline.
The foregoing description of the exemplary embodiment should not be construed as limiting the present invention. Although exemplary embodiments have been disclosed, any changes or substitutions that may be easily made by one skilled in the art within the technical scope of the disclosure should be covered by the protection scope of the present invention. Therefore, the method for preparing other hollow carbon-based capacitive desalination electrode co-doped with various heteroatoms by adopting the same or similar steps and structures as those of the above embodiment of the invention and the capacitive desalination electrode prepared by implementing the method are within the protection scope of the invention.
Claims (4)
1. The utility model provides a hollow porous carbon material of multiple heteroatom codope which characterized in that this hollow porous carbon material is: the nitrogen, phosphorus and sulfur co-doped hollow carbon polyhedron comprises the following components in percentage by mass: 79.65: 5.29: 1.55: 0.63, the hollow porous carbon material co-doped with various heteroatoms is prepared by the following steps:
a. preparing a methanol solution of ZIF-8 with the mass percent concentration of 0.8-0.9% by using a metal organic framework ZIF-8;
b. dropwise adding methanol solutions of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the methanol solution of ZIF-8 obtained in the step a under the condition of stirring at a molar ratio of 1:3: 1-1: 4:3 at a speed of: 40-60 mL/min, adding 1-2 mL of triethylamine (used as an initiator for polymerization reaction of hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol) under the stirring condition, stirring at 310-350 rpm/min for 24-26 h, centrifuging, and drying to obtain poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8;
c. carbonizing the poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8 obtained in the step b in an inert atmosphere, adding a hydrochloric acid aqueous solution to react to remove metal oxides, and fully washing and drying to obtain a hollow porous carbon material co-doped with various heteroatoms; the carbonization process comprises the following steps: controlling the heating rate to be 1-2 ℃/min, heating to 800-900 ℃, preserving the heat for 1-3 hours, and then cooling to room temperature, wherein the flow rate of the inert gas is 80-140 mL/min.
2. A method for preparing a plurality of heteroatom-codoped hollow porous carbon materials according to claim 1, which is characterized by comprising the following specific steps:
a. preparing a methanol solution of ZIF-8 with the mass percent concentration of 0.8-0.9% by using a metal organic framework ZIF-8;
b. dropwise adding methanol solutions of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the methanol solution of ZIF-8 obtained in the step a under the condition of stirring at a molar ratio of 1:3: 1-1: 4:3 at a speed of: 40-60 mL/min, adding 1-2 mL of triethylamine (used as an initiator for polymerization reaction of hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol) under the stirring condition, stirring at 310-350 rpm/min for 24-26 h, centrifuging, and drying to obtain poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8;
c. carbonizing the poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8 obtained in the step b in an inert atmosphere, adding a hydrochloric acid aqueous solution to react to remove metal oxides, and fully washing and drying to obtain a hollow porous carbon material co-doped with various heteroatoms; the carbonization process comprises the following steps: controlling the heating rate to be 1-2 ℃/min, heating to 800-900 ℃, preserving the heat for 1-3 hours, and then cooling to room temperature, wherein the flow rate of the inert gas is 80-140 mL/min.
3. The method for preparing multiple kinds of heteroatom-codoped hollow porous carbon materials according to claim 2, wherein the method for preparing the poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazolate framework-8 comprises the following steps: dropwise adding methanol solutions of hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol into the obtained methanol solution of ZIF-8 under the stirring condition, wherein the molar ratio is 1:3: 1-1: 4:3, and the dropwise adding speed is as follows: 40-60 mL/min, adding 1-2 mL of triethylamine (used as an initiator for polymerization reaction of hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol) under the stirring condition, stirring for 24-26 h at 310-350 rpm/min, fully reacting, centrifuging, and drying to obtain the poly (cyclotriphosphazene-co-4, 4' -sulfonyl diphenol) @ zeolite imidazole ester skeleton-8.
4. A preparation method of a hollow porous carbon-based capacitive desalination electrode, which adopts the hollow porous carbon material co-doped with various heteroatoms as claimed in claim 1 as a raw material, and is characterized by comprising the following process steps: uniformly stirring and mixing a plurality of heteroatom-codoped hollow porous carbon materials, acetylene black and polytetrafluoroethylene emulsion according to a mass ratio of 80:10: 10-90: 5:5, coating the mixture on conductive substrate graphite paper, and drying at 100-120 ℃; finally, the hollow carbon-based capacitive desalting electrode co-doped with various heteroatoms is prepared.
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