CN115477374B - MoO (MoO)2Preparation and application methods of hollow structural material @ NHCS - Google Patents
MoO (MoO)2Preparation and application methods of hollow structural material @ NHCSInfo
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- CN115477374B CN115477374B CN202210858573.2A CN202210858573A CN115477374B CN 115477374 B CN115477374 B CN 115477374B CN 202210858573 A CN202210858573 A CN 202210858573A CN 115477374 B CN115477374 B CN 115477374B
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 6
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Abstract
The invention discloses a preparation method of MoO 2 @NHCS nanomaterial, which comprises the steps of strongly stirring a mixed solution containing tetraethyl silicate, ethanol, ammonia water and deionized water, adding a dopamine hydrochloride solution into the mixed solution, stirring, centrifugally collecting a product SiO 2 @PDA from the mixed solution after the reaction is completed, cleaning, and drying; calcining the prepared SiO 2 @PDA in a nitrogen atmosphere to form a nitrogen-doped silicon dioxide carbon sphere; dispersing the obtained product into hydrofluoric acid aqueous solution, continuously stirring, centrifugally collecting, and drying to obtain nitrogen-doped hollow carbon spheres; dispersing ammonium molybdate into a mixed solvent of deionized water and ethylene glycol, adding the prepared nitrogen-doped hollow carbon spheres, ultrasonically pouring the mixture into a high-pressure reaction kettle for reaction, collecting and washing the obtained solid with deionized water and ethanol, and calcining the solid in a nitrogen atmosphere to obtain the molybdenum dioxide coupled nitrogen-doped hollow carbon spheres. When the nano material is used for removing Pb 2+ in a water body by a capacitive deionization method, higher removal efficiency can be realized.
Description
Technical Field
The invention relates to a preparation method and an application method of a nano material, in particular to a preparation method and an application method of a MoO 2 @NHCS hollow structure material.
Background
With the rapid growth of population and the continuous expansion of cities, the problems of excessive energy consumption and environmental pollution are caused, so that the contradiction between supply and demand of drinking water worldwide is more prominent. Water pollution and shortage of clean water will be a great challenge worldwide. Heavy metals are ubiquitous in water bodies, and are the most common nuisance that endangers human health and the ecological environment. Lead is a main toxic metal pollutant in groundwater, is considered by world health organization as a chemical pollutant causing public health problem, is difficult to degrade, and can cause serious injury to human body in trace amount, and directly affects organisms, kidneys, livers, reproductive systems, nervous systems and the like. Therefore, the development of an environment-friendly and efficient lead ion water treatment method has important significance.
In recent years, various effective methods for removing lead ions in water have been proposed, such as adsorption, chemical precipitation, ion exchange, phytoremediation, membrane separation, and the like. In addition, various materials have been explored as adsorbents such as metal oxide nanostructures and metal hydroxides for capturing lead ions in aqueous environments. However, these methods require extensive pretreatment steps and chemical additives, and the adsorbents are also unstable in solution and it is difficult to completely remove lead ions from the solution. Meanwhile, various heavy metal ions exist in the wastewater, so that it is difficult to selectively remove lead ions in the wastewater. Therefore, an effective technique for selectively removing lead must be developed to achieve sustainable development of the environment.
Capacitive Deionization (CDI) technology originated in the 70 s of the last century, and the principle of operation is shown in fig. 1: the charged ions are removed from the solution mainly by forming an electric double layer on the surface of the electrode material and in the pore canal after voltage is applied to the two ends of the electrode, the ions are temporarily fixed in the solution, and the regeneration and energy recovery of the electrode are achieved by short-circuiting or applying reverse voltage. As can be seen from the above working principle, in CDI devices, the electrodes are a key part of achieving the whole ion adsorption and desorption process. Compared with other methods, the method has the advantages of low energy consumption, easy regeneration, environmental protection and the like due to the unique working principle. At present, capacitive deionization technology is mostly used in the desalination field, and few reports are made on the aspect of heavy metal removal, so that the selective removal of heavy metal ions by adopting the capacitive deionization technology is a novel and attractive method.
Disclosure of Invention
The invention aims to provide a preparation method and an application method of a MoO 2 @NHCS hollow structure material. The method develops the anode material with low price, simple preparation method and high efficiency, and the anode material is used for removing Pb 2+ in the water body by the capacitive deionization method, shows high-efficiency removal performance and provides a thought for removing heavy metal ions in the environmental water body.
The technical scheme of the invention is as follows: the preparation method of the MoO 2 @NHCS hollow structure material comprises the following steps:
A: firstly, strongly stirring a mixed solution containing tetraethyl silicate, ethanol, ammonia water and deionized water, adding a dopamine hydrochloride solution into the mixed solution, stirring, centrifugally collecting a product SiO 2 @PDA after the reaction is completed, cleaning, and drying;
B: calcining the prepared SiO 2 @PDA in a nitrogen atmosphere to form nitrogen-doped silicon dioxide carbon spheres, dispersing the obtained product into hydrofluoric acid aqueous solution, continuously stirring, centrifugally collecting, and drying to obtain the nitrogen-doped hollow carbon spheres;
C: dispersing ammonium molybdate into a mixed solvent of deionized water and ethylene glycol, adding the prepared nitrogen-doped hollow carbon spheres, ultrasonically pouring the mixture into a polytetrafluoroethylene lining type high-pressure reaction kettle for reaction, collecting and washing the obtained solid with deionized water and ethanol, and calcining the solid in a nitrogen atmosphere to obtain the molybdenum dioxide coupled nitrogen-doped hollow carbon spheres.
In the preparation method of the MoO 2 @NHCS hollow structural material, the specific preparation method comprises the following steps:
A: firstly, a mixed solution containing 1mL of tetraethyl silicate, 24mL of ethanol, 1mL of 28% NH 3·H2 O and 80mL of deionized water is strongly stirred for 30min, then 8mL of dopamine hydrochloride solution of 50 mg.mL -1 is added into the mixed solution, stirring is carried out for 24h, after the reaction is finished, the mixed solution is centrifugally collected, the product is washed with deionized water and ethanol for several times, the obtained SiO 2 @PDA is collected, and then the obtained product is dried at 80 ℃ for 24h;
b: calcining the prepared SiO 2 @PDA at a heating rate of 5 ℃/min in an N 2 atmosphere for 2 hours at the temperature of 800 ℃ to form nitrogen-doped silicon dioxide carbon spheres, dispersing the obtained product into 10wt% hydrofluoric acid aqueous solution, continuously stirring for 1 hour, thoroughly removing silicon dioxide cores, centrifugally collecting, and drying at 80 ℃ to obtain the nitrogen-doped hollow carbon spheres;
C: dispersing 0.3g of ammonium molybdate powder into a mixed solvent of 60mL of deionized water and 6mL of ethylene glycol, adding 0.06g of prepared nitrogen-doped hollow carbon spheres, carrying out ultrasonic treatment for 30min, pouring into a polytetrafluoroethylene lining type high-pressure reaction kettle, heating at 150 ℃ for 10h, collecting and washing the obtained solid with deionized water and ethanol, and calcining at a heating rate of 5 ℃/min for 5h in an atmosphere of N 2 at 800 ℃ to obtain the final product molybdenum dioxide coupling nitrogen-doped hollow carbon spheres.
An application method of MoO 2 @NHCS hollow structural material is characterized in that the MoO 2 @NHCS hollow structural material is used as an anode and applied to lead ion removal by a capacitive deionization method.
In the application method of the MoO 2 @NHCS hollow structure material, the method for removing lead ions by a capacitive deionization method comprises the following steps of: uniformly mixing and stirring MoO 2 @NHCS material, conductive carbon black, polyvinylidene fluoride and N-methyl pyrrolidone, wherein the mass ratio of MoO 2 @NHCS material, conductive carbon black and polyvinylidene fluoride is 8:1:1, coating graphite paper as a working electrode, filling a solution containing Pb (NO 3)2) into a beaker, applying working voltage by a blue electric battery test system, and performing liquid circulation by a peristaltic pump to remove Pb 2+ in the water body by a capacitive deionization method.
In the application method of the MoO 2 @NHCS hollow structure material, in the process of removing Pb 2+ in the water body by a capacitive deionization method, the concentration of Pb 2+ is 10-100 ppm; the pH value is 3-8; the applied voltage is 0.6-1.2V.
In the application method of the MoO 2 @NHCS hollow structure material, in the process of removing Pb 2+ in the water body by a capacitive deionization method, the concentration of Pb 2+ is 10-100 ppm; the pH value is 6; the applied voltage was 1.2V.
The invention has the beneficial effects that: compared with the prior art, the MoO 2 @NHCS hollow structure material has the advantages that the hollow spherical structure of the material increases the surface area, is doped with carbon, has enhanced electrochemical performance, and is favorable for adapting to volume change during charge and discharge. When the material prepared by the method is used for removing Pb 2+ in a water body by a capacitive deionization method, higher removal efficiency (the removal rate of 10ppm Pb 2+ solution reaches more than 85%) can be realized, and the energy consumption and the cost are greatly reduced.
Drawings
FIG. 1 is a schematic diagram of the synthesis of MoO 2 @NHCS hollow structural material of the invention;
FIG. 2 is a diagram showing the morphological characterization result of MoO 2 @NHCS prepared by the method of the invention;
( In the figure, (a-b) are SEM of MoO 2 @NHCS; (c-e) TEM with MoO 2 @NHCS; (f) element mapping of C, N, O, mo for MoO 2 @NHCS )
FIG. 3 is a schematic diagram of the structural characterization result of MoO 2 @NHCS prepared by the method of the invention;
(in the figure, (a) is an XRD spectrum of MoO 2 @ NHCS, (b) is a Raman spectrum, (C) is a C1 s fine spectrum, (d) is an N1 s fine spectrum, (e) is an O1 s fine spectrum, and (f) is a Mo 3d fine spectrum)
FIG. 4 is a schematic view showing Pb 2+ removal efficiency when a prepared by the present invention is used as an anode material;
(in the figure, (a) is pH 3-8, (b) is adsorption capacity of Pb 2+ under the condition of applying voltage of 0.6-1.2V; in the figure, (c) adsorption capacity of Pb 2+ concentration (pH 6 and applying voltage of 1.2V) with different concentration, and (d) is removal experiment of 10ppm Pb 2+ (pH 6 and applying voltage of 1.2V).
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
Example 1 of the present invention: a preparation method of MoO 2 @NHCS hollow structural material is shown in figure 1, and the specific preparation method comprises the following steps:
A: first, a mixed solution containing 1mL tetraethyl silicate (TEOS), 24mL ethanol, 1mL, 28% NH 3·H2 O, and 80mL deionized water was vigorously stirred for 30min. Thereafter, 8mL of dopamine hydrochloride solution (50 mg. Multidot. ML -1) was added to the above mixed solution, and stirred for another 24 hours. After the reaction was completed, the mixed solution was centrifuged to collect the product, which was washed several times with deionized water and ethanol. The obtained SiO 2 @ PDA was collected and then dried at 80℃for 24 hours;
B: the prepared SiO 2 @PDA is calcined at a temperature rising rate of 5 ℃/min for 2 hours in an N 2 atmosphere at 800 ℃ to form the nitrogen-doped silicon dioxide carbon spheres. Dispersing the obtained product into 10wt% hydrofluoric acid aqueous solution, continuously stirring for 1h, thoroughly removing silicon dioxide cores, centrifugally collecting, and drying at 80 ℃ to obtain nitrogen-doped hollow carbon spheres;
C: ammonium molybdate powder (0.3 g) was dispersed in a mixed solvent of 60mL of deionized water and 6mL of ethylene glycol, and the prepared nitrogen-doped hollow carbon spheres (0.06 g) were added, and after ultrasonic treatment for 30min, poured into a 100mL polytetrafluoroethylene-lined autoclave, and heated at 150 ℃ for 10 hours. The resulting solid was collected and washed with deionized water and ethanol, and then calcined at a temperature ramp rate of 5 ℃/min for 5 hours in an atmosphere of N 2. The final product MoO 2 @NHCS is obtained.
An application method of MoO 2 @NHCS hollow structure material, wherein the MoO 2 @NHCS hollow structure is used as an anode material and applied to Pb 2+ removal by a capacitive deionization method.
The method for removing lead ions by the capacitive deionization method comprises the following steps: uniformly mixing and stirring MoO 2 @NHCS material, conductive carbon black, polyvinylidene fluoride and N-methyl pyrrolidone, wherein the mass ratio of MoO 2 @NHCS material, conductive carbon black and polyvinylidene fluoride is 8:1:1, a step of; then coating on graphite paper as a working electrode, filling a solution containing Pb (NO 3)2) in a beaker, applying working voltage by a blue-electric battery test system, and performing liquid circulation by a peristaltic pump to remove Pb 2+ in the water body by a capacitive deionization method.
In the process of removing Pb 2+ in the water body by a capacitance deionization method, the concentration of Pb 2+ is 10-100 ppm; the pH value is 3-8; the applied voltage is 0.6-1.2V.
Fig. 2 is a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) of MoO 2 @ NHCS, from which it can be observed that MoO 2 @ NHCS overall exhibits a hollow sphere morphology with a larger specific surface area, which can provide more adsorption sites. As can be seen in the element mapping graph, the four elements of the prepared catalyst C, N, O, mo are distributed very uniformly.
The crystal structure of the catalyst was characterized by XRD diffractometry (fig. 3 (a)), with distinct diffraction peaks of molybdenum dioxide. Furthermore, XPS refinement spectra of C1 s of MoO 2 @ NHCS showed four main peaks at 284.8, 286, 287 and 288.7 eV (fig. 2 (b)), corresponding to C-C, C-N, C-O and c=o functionalities, respectively. Four different types of nitrogen appear in the XPS fine spectrum of MoO 2 @ NHCS N1 s in fig. 2 (c), pyridine N (398.3 eV), pyrrole N (399.9 eV), graphite N (401 eV) and oxidized N (402.6 eV). Comparing the XPS fine spectra of O1 s in fig. 2 (d), it was found that MoO 2 @ NHCS contained Mo-O (530.4 eV), c=o (531.22 eV), c=o (532.8 eV) and three oxygen containing functional groups. The XPS refinement spectrum of Mo 3d (fig. 2 (e)) showed that c=o contained Mo (IV) peaks of 232.6 eV and 235.7 eV, confirming successful coupling of MoO 2.
In order to verify how the MoO 2 @NHCS nanomaterial prepared by the method disclosed by the invention has the performance, the following test is specially carried out:
Pb 2+ removal Performance test
Under natural conditions, the performance of MoO 2 @NHCS serving as an anode material for removing Pb 2+ in water body by a capacitive deionization method is studied.
The specific test method is as follows: mixing and stirring 0.16g of MoO 2 @NHCS, 0.02g of conductive carbon black, 0.02g of polyvinylidene fluoride and N-dimethyl pyrrolidone for 24 hours to uniformly mix the slurry, taking a proper amount of slurry each time, coating the slurry on graphite paper, and wiping the slurry to be 4 x 4cm as a working electrode. In a 100mL beaker, 65mL Pb (in NO 3)2 solution, moO 2 @NHCS electrode is used as anode, and active carbon electrode is used as cathode to test Pb 2+ removal performance under different pH and applied voltage conditions.
As shown in fig. 4 (a), the effect at ph=3 to 8 was studied, and the result showed that Pb 2+ adsorption capacity was maximum at ph=6. As shown in fig. 4 (b), when voltages of 0.6V, 0.8V, 1.0V, and 1.2V are applied, the adsorption capacity of Pb 2+ increases as the applied voltage increases from 0.6V to 1.2V, and the adsorption capacity is maximized at a voltage of 1.2V. In summary, the optimal conditions for Pb 2+ removal are: ph=6, applied voltage 1.2V. Then, under the optimal conditions, the adsorption capacities of Pb 2+ at the concentrations of 10, 30, 50, 80 and 100ppm were tested, and the results show that the adsorption capacities also increase with the increase of the concentrations.
To evaluate the stability of the material, one electrode was reused 20 times. As can be seen from fig. 4 (d), the removal efficiency of the electrode loaded with MoO 2 @ NHCS was not significantly reduced after repeated use for 20 times, indicating that the material has good cycling stability.
Claims (1)
1. An application method of MoO 2 @NHCS hollow structural material is characterized by comprising the following steps: the preparation method of the MoO 2 @NHCS hollow structure material comprises the following steps:
A: firstly, strongly stirring a mixed solution containing tetraethyl silicate, ethanol, ammonia water and deionized water, adding a dopamine hydrochloride solution into the mixed solution, stirring, centrifugally collecting a product SiO 2 @PDA after the reaction is completed, cleaning, and drying;
B: calcining the prepared SiO 2 @PDA in a nitrogen atmosphere to form nitrogen-doped silicon dioxide carbon spheres, dispersing the obtained product into hydrofluoric acid aqueous solution, continuously stirring, centrifugally collecting, and drying to obtain the nitrogen-doped hollow carbon spheres;
C: dispersing ammonium molybdate into a mixed solvent of deionized water and ethylene glycol, adding the prepared nitrogen-doped hollow carbon spheres, ultrasonically pouring the mixture into a polytetrafluoroethylene lining type high-pressure reaction kettle for reaction, collecting and washing the obtained solid with deionized water and ethanol, and calcining the solid in a nitrogen atmosphere to obtain molybdenum dioxide coupled nitrogen-doped hollow carbon spheres;
The preparation method comprises the following steps:
A: firstly, a mixed solution containing 1mL of tetraethyl silicate, 24mL of ethanol, 1mL of 28% NH 3·H2 O and 80mL of deionized water is strongly stirred for 30min, then 8mL of dopamine hydrochloride solution of 50 mg.mL -1 is added into the mixed solution, stirring is carried out for 24h, after the reaction is finished, the mixed solution is centrifugally collected, the product is washed with deionized water and ethanol for several times, the obtained SiO 2 @PDA is collected, and then the obtained product is dried at 80 ℃ for 24h;
b: calcining the prepared SiO 2 @PDA at a heating rate of 5 ℃/min in an N 2 atmosphere for 2 hours at the temperature of 800 ℃ to form nitrogen-doped silicon dioxide carbon spheres, dispersing the obtained product into 10wt% hydrofluoric acid aqueous solution, continuously stirring for 1 hour, thoroughly removing silicon dioxide cores, centrifugally collecting, and drying at 80 ℃ to obtain the nitrogen-doped hollow carbon spheres;
C: dispersing 0.3g of ammonium molybdate powder into a mixed solvent of 60mL of deionized water and 6mL of ethylene glycol, adding 0.06g of prepared nitrogen-doped hollow carbon spheres, carrying out ultrasonic treatment for 30min, pouring into a polytetrafluoroethylene lining type high-pressure reaction kettle, heating at 150 ℃ for 10h, collecting and washing the obtained solid with deionized water and ethanol, and calcining at a heating rate of 5 ℃/min at 800 ℃ in an N 2 atmosphere for 5h to obtain a final product molybdenum dioxide coupling nitrogen-doped hollow carbon spheres;
MoO 2 @NHCS hollow structural material is used as an anode and applied to lead ion removal by a capacitive deionization method;
The method for removing lead ions by the capacitive deionization method comprises the following steps: uniformly mixing and stirring MoO 2 @NHCS material, conductive carbon black, polyvinylidene fluoride and N-methyl pyrrolidone, wherein the mass ratio of MoO 2 @NHCS material, conductive carbon black and polyvinylidene fluoride is 8:1:1, coating on graphite paper as working electrode, filling Pb (NO 3)2) -containing solution in beaker, applying working voltage by blue electric battery test system, circulating liquid by peristaltic pump, and removing Pb in water body by capacitive deionization method 2+;
In the process of removing Pb 2+ in the water body by a capacitance deionization method, the concentration of Pb 2+ is 10-100 ppm; the pH value is 6; the applied voltage was 1.2V.
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| CN108539163A (en) * | 2018-04-08 | 2018-09-14 | 齐鲁工业大学 | A kind of preparation method of mesoporous hollow nitrogen-doped carbon nanosphere/manganese dioxide Zinc ion battery positive electrode |
| CN111129475A (en) * | 2020-01-15 | 2020-05-08 | 扬州大学 | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery |
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| CN108539163A (en) * | 2018-04-08 | 2018-09-14 | 齐鲁工业大学 | A kind of preparation method of mesoporous hollow nitrogen-doped carbon nanosphere/manganese dioxide Zinc ion battery positive electrode |
| CN111129475A (en) * | 2020-01-15 | 2020-05-08 | 扬州大学 | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery |
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