CN115490307B - Sodium ion removing material CoMoO 4 @CQDs-NCNTs and preparation method and application thereof - Google Patents
Sodium ion removing material CoMoO 4 @CQDs-NCNTs and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides aSodium ion removal material CoMoO 4 The preparation method and application of the @ CQDs-NCNTs comprise the following steps: heating anhydrous citric acid, cooling, adjusting to neutrality, filtering carbon particles, dialyzing, and drying at low temperature to obtain carbon quantum dot solid; adding methyl orange into water, ice-bath, stirring, adding anhydrous ferric chloride, ice-bath, stirring, adding pyrrole monomer, ice-bath, stirring, filtering, cleaning, soaking, centrifuging, cleaning, and suction-filtering to obtain polypyrrole film; weighing cobalt nitrate, adding the cobalt nitrate into deionized water, stirring, adding sodium molybdate and carbon quantum dot solids, stirring, putting a polypyrrole film into the mixture, cleaning the mixture, and drying the mixture in vacuum; heating and heating; the surface of the carbon quantum dot obtained by high-temperature pyrolysis of citric acid contains a large number of oxygen-containing functional groups, can be used as a structure guiding agent for nucleation growth, can effectively adsorb cobalt ions, and can successfully grow supported cobalt molybdate on the surface of polypyrrole under a hydrothermal condition.
Description
Technical Field
The invention belongs to the technical field of environmental material synthesis, and in particular relates to a sodium ion removal material CoMoO 4 @CQDs-NCNTs, and a preparation method and application thereof.
Background
With the continuous development of industry and agriculture and the increase of population, the problem of water resource shortage is increasingly prominent. The sea water resources on the earth are rich, and if the sea water is desalinated, sufficient water resources can be provided for human beings. Seawater mainly contains a large amount of salt, wherein NaCl is the main component of the seawater. At present, the sea water desalting technology mainly comprises thermal evaporation, electrodialysis, multistage flash evaporation, reverse osmosis, electrochemical oxidation and the like, but the technology has the defects of high energy consumption, heavy pollution, high cost and the like at different degrees, and the large-scale application of the technology is hindered. As a novel seawater desalination technology, the capacitive deionization technology (CDI) has the characteristics of high energy efficiency, high cycle performance, simplicity and convenience in operation and the like, and attracts attention of a large number of researchers worldwide. At present, the capacitive deionization sodium removal electrode has the defects of poor stability, low desalination capacity, low desalination rate and the like. Therefore, development of a novel sodium removal electrode with high desalination capacity, high desalination rate and good cycle performance is needed.
Disclosure of Invention
In view of the shortcomings in the prior art, a primary object of the present invention is to provide a sodium ion removal material CoMoO 4 Preparation method of @ CQDs-NCNTs.
A second object of the present invention is to provide the sodium ion removing material CoMoO 4 @CQDs-NCNTs。
A third object of the present invention is to provide the sodium ion removing material CoMoO 4 Use of @ CQDs-NCNTs.
To achieve the above object, the solution of the present invention is:
sodium ion removal material CoMoO 4 The preparation method of the @ CQDs-NCNTs comprises the following steps:
(1) Placing anhydrous citric acid with certain mass into a ceramic crucible, heating for a certain time at a certain temperature, and cooling to room temperature to obtain a tan solid;
(2) Regulating pH to neutrality with sodium hydroxide of certain concentration, filtering out large carbon particles with polysulfone ether filter membrane, dialyzing for certain time with dialysis bag to obtain carbon quantum dot solution, and oven drying at low temperature to obtain carbon quantum dot solid;
(3) Weighing methyl orange, adding the methyl orange into deionized water, and stirring for a certain time under the ice bath condition to obtain a first mixed solution;
(4) Adding anhydrous ferric chloride with certain mass into the first mixed solution, and stirring for a certain time under the ice bath condition to obtain a second mixed solution;
(5) Adding a certain amount of pyrrole monomer into the obtained second mixed solution, and stirring and reacting for a certain time under the ice bath condition to obtain a third mixed solution;
(6) Filtering the third mixed solution to obtain polypyrrole solid, washing the polypyrrole solid with ethanol water solution until the polypyrrole solid is colorless, and soaking the polypyrrole solid in hydrochloric acid water solution with a certain concentration for a certain time to obtain fourth mixed solution;
(7) Centrifugally separating the fourth mixed solution, washing the fourth mixed solution with deionized water for several times to prepare polypyrrole ethanol water solution with certain concentration and certain volume, and carrying out suction filtration to obtain a polypyrrole film;
(8) A certain amount of cobalt nitrate (Co (NO) 3 ） 2 ) Adding the mixture into deionized water with a certain volume, and stirring until the mixture is completely dissolved to obtain a fifth mixed solution;
(9) Adding a certain amount of sodium molybdate (Na 2 MoO 4 ) Stirring until the mixture is completely dissolved to obtain the CoMoO-containing product 4 Adding CQDs-NCNTs of carbon quantum dot solid with certain mass, and stirring until the CQDs-NCNTs are completely dissolved to obtain a sixth mixed solution;
(10) Adding the sixth mixed solution into a high-pressure reaction kettle, then putting the polypyrrole film into the solution at a certain angle, reacting for a certain time at a certain temperature, washing with deionized water and ethanol for several times after the reaction is finished, and vacuum drying;
(11) Heating at a certain temperature for a certain time at a certain temperature rising rate in an inert gas atmosphere to obtain a sodium ion removal material CoMoO 4 @CQDs-NCNTs。
Further, in the step (1), the addition amount of the anhydrous citric acid is 10-50g, and the volume of the ceramic crucible can hold 10-50g of the anhydrous citric acid; the heating temperature is 160-190 ℃, and the heating time is 36-45h.
Further, in the step (2), the concentration of the sodium hydroxide is 9-12mol/L, the pore diameter of the polysulfone ether filter membrane is 0.18-0.25 mu m, the dialysis time is 48-50h, and the low-temperature drying temperature is 36-45 ℃.
Further, in the step (3), the volume of the deionized water is 90-110mL, the molar concentration of the methyl orange is 0.002-0.005 mol/L, the temperature of the ice bath condition is (-2) -0 ℃, and the stirring time is 30-35min.
Further, in the step (4), the molar concentration of the anhydrous ferric chloride is 0.01-0.06mol/L, the molar concentration ratio of the anhydrous ferric chloride to the methyl orange in the first mixed solution is 10:1-30:1, and the stirring time is 1-3h.
Further, in the step (5), the addition amount of the pyrrole monomer is 0.22-0.30mL, and the stirring time is 20-28h.
Further, in the step (6), the volume ratio of the ethanol to the deionized water in the ethanol aqueous solution is 1:2, the concentration of the hydrochloric acid aqueous solution is 0.2-0.9mol/L, and the soaking time is 10-18h.
Further, in the step (7), the rotating speed of centrifugal separation is 3500-4000rpm, the concentration of the polypyrrole ethanol water solution is 1-5mg/mL, and the volume of one membrane is 75-90mL.
Further, in the step (8), the addition amount of the cobalt nitrate is 1-4mmol, and the volume of the deionized water is 56-70mL.
Further, in the step (9), the addition amount of the sodium molybdate is 1-4mmol, and the addition amount of the carbon quantum dot solid is 50-200mg.
Further, in the step (10), the volume of the high-pressure reaction kettle is 90-110mL, the temperature of the reaction is 110-130 ℃, the reaction time is 4-8h, and the temperature of the vacuum drying is 50-80 ℃.
In the step (10), the cobalt molybdate is put at a certain angle to grow on the polypyrrole film through chemical bonding, otherwise, the cobalt molybdate generated in the solution can be settled on the film instead of being compounded through bonding, so that the cobalt molybdate can be put vertically or obliquely.
Further, in the step (11), the inert gas atmosphere is Ar or N 2 Can be heated twice, firstly heated to 330-380 ℃ at a heating rate of 8-12 ℃/min, kept at 1-2h, cooled to room temperature, then heated to 600-720 ℃ at 3-6 ℃/min, and kept at 1-2h.
In summary, the molar ratio of anhydrous ferric chloride to methyl orange is critical to the formation of the tubular morphology during polypyrrole synthesis, which also determines the microstructure of the final composite. Carbon quantum dot capable of inducing polypyrrole surface to grow CoMoO by interface 4 The pyrolysis temperature and time of the preparation determine the surface functional groups and the particle size of the final product, thereby affecting CoMoO 4 Microscopic morphology grown on the polypyrrole surface. In addition, the addition of cobalt nitrate and sodium molybdate affects CoMoO 4 The loading mass, the rate of temperature rise and the calcination temperature of (C) also directly affect CoMoO 4 Phase, morphology and surface chemistry of @ CQDs-NCNTs materials. Thus, the parameters in the various steps of the above synthesis process act synergistically to form the final CoMoO 4 @CQDs-NCNTs。
Sodium ion removal material CoMoO 4 @CQDs-NCNTs, which are obtained by the preparation method described above.
The sodium ion removal material CoMoO 4 Application of @ CQDs-NCNTs in capacitive deionization desalination.
By adopting the scheme, the invention has the beneficial effects that:
the surface of the carbon quantum dot obtained by high-temperature pyrolysis of citric acid contains a large amount of oxygen-containing functional groups, can be used as a structure guiding agent for nucleation growth, can effectively adsorb cobalt ions, and can successfully grow loaded CoMoO on the surface of polypyrrole under hydrothermal conditions 4 。
Second, the chemical bond is formed by high-temperature carbonization of polypyrrole, so as to effectively lead CoMoO 4 Anchoring on the surface of the carbon nano tube, avoiding the dissolution of cobalt ions, improving the circulation stability of the material, and simultaneously, carbonizing to obtain the carbon nano tube which is CoMoO 4 A conductive network is provided to enhance the desalination properties of the material.
Thirdly, oxygen-containing functional groups with different concentrations can be formed on the surface of polypyrrole by adding carbon quantum dots with different masses, so that the content of adsorbed cobalt ions is different, the content of cobalt molybdate with different growth loads is different, and CoMoO with different loads is obtained through regulation and control 4 The electrochemical capacity of the whole composite material is different, and the desalination capacity is also different; the preparation method of the invention has simple equipment and simple and feasible process, and can be operated continuously, thereby being suitable for large-scale production.
Drawings
FIG. 1 shows the preparation of sodium ion removing material CoMoO according to the present invention 4 Schematic flow chart of @ CQDs-NCNTs.
FIG. 2 is a sodium ion removing material CoMoO in example 2 of the present invention 4 XRD pattern of @ CQDs-NCNTs.
FIG. 3 is a sodium ion removing material CoMoO in example 2 of the present invention 4 SEM images of @ CQDs-NCNTs.
FIG. 4 is a sodium ion removing material CoMoO in example 2 of the present invention 4 N of @ CQDs-NCNTs 2 Adsorption/desorption isotherms and corresponding specific surface areas.
FIG. 5 is a drawing of example 2 of the present inventionMedium sodium ion removal material CoMoO 4 Different current densities of @ CQDs-NCNTs and desalination capacity at constant pressure.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1:
the sodium ion removing material CoMoO of this example 4 The preparation method of the @ CQDs-NCNTs comprises the following steps:
(1) Placing 10 g anhydrous citric acid in a 100 mL ceramic crucible, heating at 160deg.C for 36 h, and cooling to room temperature to obtain tan solid;
(2) Regulating pH to neutrality with 10 mol/L sodium hydroxide, filtering out large carbon particles with 0.22 μm polysulfone ether filter membrane, dialyzing with dialysis bag 48 and h to obtain carbon quantum dot solution, and oven drying at 40deg.C to obtain carbon quantum dot solid;
(3) Weighing 0.002 mol of methyl orange, adding into 100 mL deionized water, and stirring for 30 min at 0 ℃ under the ice bath condition to obtain a first mixed solution;
(4) Adding 0.01 mol/L anhydrous ferric chloride into the first mixed solution, and stirring for 2h under the ice bath condition at the temperature of 0 ℃ to obtain a second mixed solution;
(5) Adding pyrrole monomer of 0.25 mL into the obtained second mixed solution, and stirring and reacting for 20 h under the ice bath condition of 0 ℃ to obtain a third mixed solution;
(6) Filtering the third mixed solution to obtain polypyrrole solid, washing the polypyrrole solid with an ethanol water solution with the volume fraction of 33% until the polypyrrole solid is colorless, and soaking the polypyrrole solid in a hydrochloric acid water solution with the volume fraction of 0.5 mol/L for 12 h to obtain a fourth mixed solution;
(7) Centrifugally separating the fourth mixed solution at 3500 rpm, washing the fourth mixed solution with deionized water for several times to prepare a polypyrrole ethanol aqueous solution with the concentration of 1 mg/mL and 80 mL, and carrying out suction filtration to obtain a polypyrrole film;
(8) 1 mmol of Co (NO) was weighed out 3 ） 2 Adding the mixture into 60 mL deionized water, and stirring until the mixture is completely dissolved to obtain a fifth mixed solution;
(9) Adding 1 mm to the fifth mixed solutionNa of ol 2 MoO 4 Stirring until the carbon quantum dots are completely dissolved, adding 50 mg carbon quantum dot solids, and stirring until the carbon quantum dots are completely dissolved to obtain a sixth mixed solution;
(10) Adding the sixth mixed solution into a 100 mL high-pressure reaction kettle, vertically putting the polypyrrole film into the solution, reacting at 120 ℃ for 4 h, washing with deionized water and ethanol for several times after the reaction is finished, and vacuum drying at 60 ℃;
(11) Heating to 350 ℃ at a heating rate of 10 ℃/min under Ar atmosphere, keeping 2h, cooling to room temperature, heating to 600 ℃ at 5 ℃/min, and keeping 2h to obtain sodium ion removal material CoMoO 4 @CQDs-NCNTs。
Example 2:
the sodium ion removing material CoMoO of this example 4 The preparation method of the @ CQDs-NCNTs comprises the following steps:
(1) Placing 30 g anhydrous citric acid in a 100 mL ceramic crucible, heating at 175 ℃ for 40 h, and cooling to room temperature to obtain a tan solid;
(2) Regulating pH to neutrality with 10 mol/L sodium hydroxide, filtering out large carbon particles with 0.22 μm polysulfone ether filter membrane, dialyzing with dialysis bag 48 and h to obtain carbon quantum dot solution, and oven drying at 40deg.C to obtain carbon quantum dot solid;
(3) Weighing 0.0035 mol of methyl orange, adding the methyl orange into 100 mL deionized water, and stirring for 30 min under the ice bath condition at the temperature of 0 ℃ to obtain a first mixed solution;
(4) Adding 0.035 mol/L anhydrous ferric chloride into the first mixed solution, and stirring for 2h under the ice bath condition of 0 ℃ to obtain a second mixed solution;
(5) Adding pyrrole monomer of 0.25 mL into the obtained second mixed solution, and stirring and reacting under the ice bath condition of 0 ℃ for 24 h to obtain a third mixed solution;
(6) Filtering the third mixed solution to obtain polypyrrole solid, washing the polypyrrole solid with an ethanol water solution with the volume fraction of 33% until the polypyrrole solid is colorless, and soaking the polypyrrole solid in a hydrochloric acid water solution with the volume fraction of 0.5 mol/L for 12 h to obtain a fourth mixed solution;
(7) Centrifugally separating the fourth mixed solution at 3500 rpm, washing the fourth mixed solution with deionized water for several times to prepare a polypyrrole ethanol aqueous solution with the concentration of 1 mg/mL and 80 mL, and carrying out suction filtration to obtain a polypyrrole film;
(8) Weigh 2.5 mmol Co (NO) 3 ） 2 Adding the mixture into 60 mL deionized water, and stirring until the mixture is completely dissolved to obtain a fifth mixed solution;
(9) To the fifth mixture was added 2.5 mmol of Na 2 MoO 4 Stirring until the carbon quantum dots are completely dissolved, adding 125 mg carbon quantum dot solids, and stirring until the carbon quantum dots are completely dissolved to obtain a sixth mixed solution;
(10) Adding the sixth mixed solution into a 100 mL high-pressure reaction kettle, vertically putting the polypyrrole film into the solution, reacting at 120 ℃ for 6 h, washing with deionized water and ethanol for several times after the reaction is finished, and vacuum drying at 60 ℃;
(11) Heating to 350 ℃ at a heating rate of 10 ℃/min under Ar atmosphere, keeping 2h, cooling to room temperature, heating to 660 ℃ at 5 ℃/min, and keeping 2h to obtain sodium ion removal material CoMoO 4 @CQDs-NCNTs。
Example 3:
the sodium ion removing material CoMoO of this example 4 The preparation method of the @ CQDs-NCNTs comprises the following steps:
(1) Placing 50g anhydrous citric acid in a 100 mL ceramic crucible, heating at 190 ℃ for 45h, and cooling to room temperature to obtain a tan solid;
(2) Regulating pH to neutrality with 10 mol/L sodium hydroxide, filtering out large carbon particles with 0.22 μm polysulfone ether filter membrane, dialyzing with dialysis bag 48 and h to obtain carbon quantum dot solution, and oven drying at 40deg.C to obtain carbon quantum dot solid;
(3) Weighing 0.005 mol of methyl orange, adding into 100 mL deionized water, and stirring for 30 min at 0 ℃ under the ice bath condition to obtain a first mixed solution;
(4) Adding 0.06mol/L anhydrous ferric chloride into the first mixed solution, and stirring for 2h under the ice bath condition at the temperature of 0 ℃ to obtain a second mixed solution;
(5) Adding pyrrole monomer of 0.25 mL into the obtained second mixed solution, and stirring for reaction under the ice bath condition of 0 ℃ for 28h to obtain a third mixed solution;
(6) Filtering the third mixed solution to obtain polypyrrole solid, washing the polypyrrole solid with an ethanol water solution with the volume fraction of 33% until the polypyrrole solid is colorless, and soaking the polypyrrole solid in a hydrochloric acid water solution with the volume fraction of 0.5 mol/L for 12 h to obtain a fourth mixed solution;
(7) Centrifugally separating the fourth mixed solution at 3500 rpm, washing the fourth mixed solution with deionized water for several times to prepare a polypyrrole ethanol aqueous solution with the concentration of 1 mg/mL and 80 mL, and carrying out suction filtration to obtain a polypyrrole film;
(8) Weigh 4mmol Co (NO) 3 ） 2 Adding the mixture into 60 mL deionized water, and stirring until the mixture is completely dissolved to obtain a fifth mixed solution;
(9) To the fifth mixture obtained was added 4mmol of Na 2 MoO 4 Stirring until the carbon quantum dots are completely dissolved, adding 200mg carbon quantum dot solids, and stirring until the carbon quantum dots are completely dissolved to obtain a sixth mixed solution;
(10) Adding the sixth mixed solution into a 100 mL high-pressure reaction kettle, vertically putting the polypyrrole film into the solution, reacting at 120 ℃ for 6 h, washing with deionized water and ethanol for several times after the reaction is finished, and vacuum drying at 60 ℃;
(11) Heating to 350 ℃ at a heating rate of 10 ℃/min under Ar atmosphere, keeping 2h, cooling to room temperature, heating to 720 ℃ at a heating rate of 5 ℃/min, and keeping 2h to obtain sodium ion removal material CoMoO 4 @CQDs-NCNTs。
< experiment >
Sodium ion removal Material CoMoO prepared in example 2 4 The @ CQDs-NCNTs products were each tested as follows.
< experiment 1>
The purpose of this experiment was to characterize example 2 sodium ion removal material CoMoO 4 Crystalline forms of @ CQDs-NCNTs.
As shown in fig. 2, XRD characterization test was performed using an X-ray diffractometer to obtain XRD diffraction peaks of the sample at 13.1 °, 19.0 °, 23.3 °, 25.5 °, 26.4 °, 27.2 °, 28.4 °, 32.0 °, 33.6 °, 36.6 °, 38.8 °, 40.1 °, 43.3 °, 45.0 °, 47%Diffraction peaks at 4℃correspond to CoMoO, respectively 4 The peaks of the product of the invention are almost in one-to-one correspondence with the peaks in the standard card (PDF#21-0868), indicating successful loading of cobalt molybdate onto the nitrogen-doped carbon nanotubes.
< experiment 2>
The topographical features of the samples were obtained using a Scanning Electron Microscope (SEM).
The purpose of this experiment was to explore the sodium ion removal material CoMoO 4 Topography of @ CQDs-NCNTs.
As shown in FIG. 3, the prepared individual CoMoO 4 In the shape of a tube, for CoMoO 4 The composite material @ CQDs-NCNTs, the tubular morphology, coMoO, is also obtained after polypyrrole carbonization 4 Is supported on the surface of the carbon nano tube in the form of particles.
< experiment 3>
The purpose of this experiment was to explore the sodium ion removal material CoMoO 4 N of @ CQDs-NCNTs 2 Adsorption/desorption curves and specific surface area.
Weighing a certain mass of sample, preprocessing the sample by using a BELSORP analyzer, testing the nitrogen adsorption and desorption curve of the sample under the condition of 77K, and processing the sample by using a Brunauer-Emmett-Teller (BET) method to obtain the specific surface area value of the sample.
As shown in fig. 4, coMoO 4 N of @ CQDs-NCNTs 2 The adsorption/desorption curve belongs to Type IV, which shows that the material has mesoporous distribution, and is favorable for ion migration in the desalting process. Specific surface area up to 151.31 m 2 g -1 More ion adsorption active sites can be provided.
< experiment 4>
The purpose of this experiment was to explore the sodium ion removal material CoMoO 4 Desalination properties of @ CQDs-NCNTs.
As shown in FIG. 5, at different current densities (30, 60, 100 mA g -1 ) And under constant pressure operating conditions of 1.2V CoMoO 4 Desalination capacities of @ CQDs-NCNTs are CoMoO alone 4 Is more than 2 times that of 30 mA g -1 And a desalination capacity of up to about 83 mg g at 1.2V -1 Excellent desalination performance is exhibited due to the nitrogen doped carbon nanotubes providing an excellent conductive network for cobalt molybdate.
It will be apparent to those skilled in the art that the present invention has been described in detail by way of illustration only, and it is not intended to limit the practice of the invention to the particular embodiments described, but to limit the scope of the invention to the various insubstantial modifications of the method concepts and concepts of the invention, or to the applications of the concepts and concepts of the invention directly to other applications without any modifications thereto.
Claims (3)
1. Sodium ion removal material CoMoO 4 The preparation method of the @ CQDs-NCNTs is characterized by comprising the following steps: the method comprises the following steps:
(1) Heating anhydrous citric acid, and cooling to room temperature to obtain a solid;
(2) Regulating pH to neutrality with sodium hydroxide, filtering carbon particles with polysulfone ether filter membrane, dialyzing to obtain carbon quantum dot solution, and oven drying at low temperature to obtain carbon quantum dot solid;
(3) Weighing methyl orange, adding the methyl orange into deionized water, and stirring under ice bath conditions to obtain a first mixed solution;
(4) Adding anhydrous ferric chloride into the first mixed solution, and stirring under ice bath conditions to obtain a second mixed solution;
(5) Adding pyrrole monomer into the second mixed solution, and stirring for reaction under ice bath condition to obtain a third mixed solution;
(6) Filtering the third mixed solution to obtain polypyrrole solid, washing the polypyrrole solid with ethanol water solution until the polypyrrole solid is colorless, and soaking the polypyrrole solid in hydrochloric acid water solution to obtain fourth mixed solution;
(7) Centrifugally separating the fourth mixed solution, washing with deionized water to prepare polypyrrole ethanol aqueous solution, and carrying out suction filtration to obtain a polypyrrole film;
(8) Weighing cobalt nitrate, adding the cobalt nitrate into deionized water, and stirring until the cobalt nitrate is completely dissolved to obtain a fifth mixed solution;
(9) Adding sodium molybdate into the fifth mixed solution, stirring until the sodium molybdate is completely dissolved, and obtaining the CoMoO-containing solution 4 Adding the carbon quantum dot solid, and stirring until the carbon quantum dot solid is completely dissolved to obtain a sixth mixed solution;
(10) Adding the sixth mixed solution into a high-pressure reaction kettle, then placing the polypyrrole film into the solution for high-temperature reaction, washing with deionized water and ethanol after the reaction is finished, and drying in vacuum;
(11) Heating up and heating up under inert gas atmosphere to obtain sodium ion removal material CoMoO 4 @CQDs-NCNTs；
In the step (1), the addition amount of the anhydrous citric acid is 10-50g, the heating temperature is 160-190 ℃, and the heating time is 36-45h;
in the step (2), the concentration of sodium hydroxide is 9-12mol/L, and the pore diameter of the polysulfone ether filter membrane is 0.18-0.25 mu m; the dialysis time is 48-50h, and the low-temperature drying temperature is 36-45 ℃;
in the step (3), the volume of deionized water is 90-110mL, the molar concentration of methyl orange is 0.002-0.005 mol/L, the temperature of ice bath condition is (-2) -0deg.C, and the stirring time is 30-35min;
in the step (4), the molar concentration of the anhydrous ferric chloride is 0.01-0.06mol/L, the molar concentration ratio of the anhydrous ferric chloride to the methyl orange in the first mixed solution is 10:1-30:1, and the stirring time is 1-3h;
in the step (5), the addition amount of the pyrrole monomer is 0.22-0.30mL, and the stirring time is 20-28h;
in the step (6), the volume ratio of the ethanol to the deionized water in the ethanol aqueous solution is 1:2, the concentration of the hydrochloric acid aqueous solution is 0.2-0.9mol/L, and the soaking time is 10-18h;
in the step (7), the rotating speed of centrifugal separation is 3500-4000rpm, the concentration of the polypyrrole ethanol water solution is 1-5mg/mL, and the volume of one membrane is 75-90mL;
in the step (8), the addition amount of the cobalt nitrate is 1-4mmol, and the volume of the deionized water is 56-70mL;
in the step (9), the addition amount of the sodium molybdate is 1-4mmol, and the addition amount of the carbon quantum dot solid is 50-200mg;
in the step (10), the volume of the high-pressure reaction kettle is 90-110mL, the reaction temperature is 110-130 ℃, the reaction time is 4-8h, and the vacuum drying temperature is 50-80 ℃;
in the step (11), the inert gas atmosphere is Ar or N 2 The heating is carried out twice, the temperature is firstly heated to 330-380 ℃ at the heating rate of 8-12 ℃/min, the temperature is kept for 1-2h, the temperature is cooled to the room temperature, then the temperature is heated to 600-720 ℃ at the temperature of 3-6 ℃/min, and the temperature is kept for 1-2h.
2. Sodium ion removal material CoMoO 4 The @ CQDs-NCNTs is characterized in that: which is obtained by the process according to claim 1.
3. A sodium ion removing material CoMoO according to claim 2 4 Application of @ CQDs-NCNTs, the sodium ion removal material CoMoO 4 Application of @ CQDs-NCNTs in capacitive deionization desalination.
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| CN105914353A (en) * | 2016-05-06 | 2016-08-31 | 复旦大学 | Morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and preparation method |
| WO2017091815A1 (en) * | 2015-11-25 | 2017-06-01 | William Marsh Rice University | Formation of three-dimensional materials by combining catalytic and precursor materials |
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| CN113437307A (en) * | 2021-06-25 | 2021-09-24 | 上海理工大学 | Preparation method of cobaltosic oxide and carbon quantum dot composite material |
| CN113462385A (en) * | 2021-07-20 | 2021-10-01 | 苏州大学 | Composite material capable of realizing photo-thermal blending and preparation method and application thereof |
| CN114792799A (en) * | 2022-06-27 | 2022-07-26 | 天鹏锂能技术(淮安)有限公司 | Cobalt molybdate lithium electrode material, preparation method thereof, positive plate and high-temperature lithium battery |
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| US20180291266A1 (en) * | 2016-03-11 | 2018-10-11 | Dalian University Of Technology | A carbon quantum dot synthesizing method and its application of modifying functional water purification material |
| US20180273659A1 (en) * | 2017-03-22 | 2018-09-27 | Laurentian University Of Sudbury | Process for preparing polymer and carbon nanospheres by catalytic polymerization |
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| WO2017091815A1 (en) * | 2015-11-25 | 2017-06-01 | William Marsh Rice University | Formation of three-dimensional materials by combining catalytic and precursor materials |
| CN105914353A (en) * | 2016-05-06 | 2016-08-31 | 复旦大学 | Morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and preparation method |
| CN109449424A (en) * | 2018-11-14 | 2019-03-08 | 陕西科技大学 | A kind of compound carbon dots lithium ion battery anode material of cobalt molybdate and preparation method thereof |
| CN111498957A (en) * | 2020-05-21 | 2020-08-07 | 内蒙古大学 | Preparation method of molybdenum disulfide @ cobalt disulfide @ titanium dioxide nanotube integral capacitive desalination electrode |
| CN113437307A (en) * | 2021-06-25 | 2021-09-24 | 上海理工大学 | Preparation method of cobaltosic oxide and carbon quantum dot composite material |
| CN113462385A (en) * | 2021-07-20 | 2021-10-01 | 苏州大学 | Composite material capable of realizing photo-thermal blending and preparation method and application thereof |
| CN114792799A (en) * | 2022-06-27 | 2022-07-26 | 天鹏锂能技术(淮安)有限公司 | Cobalt molybdate lithium electrode material, preparation method thereof, positive plate and high-temperature lithium battery |
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