CN112266023A - Manganese dioxide nanostructure with controllable morphology, preparation method and application thereof - Google Patents
Manganese dioxide nanostructure with controllable morphology, preparation method and application thereof Download PDFInfo
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- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
Abstract
The invention discloses a manganese dioxide nano structure with controllable morphology, a preparation method and application thereof, belonging to the technical field of inorganic synthesis and environmental science. The invention takes a surfactant as a template agent, takes soluble manganese salt as a manganese source, carries out hydrothermal reaction on a high-valence manganese salt aqueous solution and a low-valence manganese salt aqueous solution in a reaction kettle at different temperatures, and obtains the manganese dioxide nanostructure after precipitation, washing and drying. The nano manganese dioxide prepared by the method has the advantages of simple process, low raw material cost and environmental friendliness, can be used As a repairing agent for heavy metal polluted soil/water bodies such As As, Cd, Pb, Cu, Co, Ni, Zn, Hg and the like, and has a good repairing effect and a high application value.
Description
Technical Field
The invention belongs to the technical field of inorganic synthetic materials, and particularly relates to a manganese dioxide nano structure with controllable morphology, and a preparation method and application thereof.
Background
Manganese dioxide (MnO)2) Is an important inorganic functional material, is the most stable oxide in the manganese series and is commonly present in pyrolusite. China, which is the country with the largest storage capacity of Asian manganese ore resources at present, has rich sources, cheap raw materials and environmental protection, thereby arousing the wide attention of many scientific researchers. Due to MnO2Has unique and excellent physical and chemical properties, is widely applied to materials such as super capacitors, alloy stainless steel, biosensors and the like, and has attracted great attention in the fields of catalysis, oxidation, adsorption and the like. And nano-sized MnO2The nano-composite material not only has the characteristics of transition metal oxide, but also has a nano effect, thereby endowing the nano-composite material with more characteristics and applications. However, nano MnO2The performance of the compound depends on the shape, the crystal form and the size, and the determining factors influence each other and are relatively independent.
Currently, the synthesis of nano MnO2The method has a plurality of different synthetic methods, and the obtained nano MnO2The shape, crystal form and particle size of the crystal are all different. The chemical solid phase method is divided into a low-temperature solid phase and a high-temperature solid phase, and the former needs to be subjected to the steps of mixing, grinding, centrifuging, roasting and the like, so that the method is complicated; the latter at high temperatures may result in MnO2Lose oxygen and become Mn2O3Or Mn3O4Lower-valence manganese, and less use. The electrolytic method is more common in industry, but MnO is prepared2Generally, the crystallinity is poor and the appearance is irregular. The sol-gel method can obtain the nano MnO with high purity and good chemical uniformity2However, it is easily affected by the drying conditions and easily occursAgglomeration phenomenon. The chemical precipitation method has simple and convenient synthesis conditions and simple principle, but the reaction speed is slow, and the obtained MnO is2The crystal form is single. Although researchers synthesize nano MnO of different shapes and crystal forms by different methods2But nanometer MnO with different shapes can be completed in the same system2The controlled synthesis of (a) still presents certain challenges. The invention adopts a mild method to prepare MnO with controllable appearance in the same system2The nano structure is simple and convenient in synthesis method, and the nano structure is used As a heavy metal passivator, so that high-efficiency and rapid passivation on heavy metals such As As, Cd, Pb, Cu, Co, Ni, Zn, Hg and the like in polluted soil and sewage can be realized.
Disclosure of Invention
The invention aims to provide a manganese dioxide nano structure with controllable appearance, a preparation method and application.
Based on the above purposes, the technical scheme adopted by the invention is as follows:
a preparation method of a manganese dioxide nanostructure with controllable morphology comprises the steps of adding a mixed solution of a low-valence manganese salt aqueous solution and a template agent into a sodium hydroxide solution, adding a high-valence manganese salt aqueous solution, carrying out hydrothermal reaction at 80-240 ℃ for 8-24 h, washing after the reaction is finished, and drying to obtain the manganese dioxide nanostructure, wherein the addition amount of the template agent is 5% -28% of the mole number of the low-valence manganese salt, and the mole ratio of the high-valence manganese salt to the low-valence manganese salt is 1: 1.3-2.6.
Preferably, the template used is cetyltrimethylammonium chloride (CTAC), cetyltrimethylammonium bromide (CTAB), Sodium Dodecyl Sulfate (SDS), polyethylene glycol (PEG, molecular weight 200-.
Preferably, the high-valence manganese salt is one of high-valence soluble manganese salts such as potassium permanganate or sodium permanganate, and the low-valence manganese salt is one of low-valence soluble manganese salts such as manganese sulfate, manganese chloride and manganese nitrate.
Further, the concentration of the sodium hydroxide solution was 0.12 mol. L-1B, carrying out the following steps of; the concentration of the high-valence manganese salt aqueous solution is 0.15-1.36 mol.L-1The concentration of the low-valence manganese salt aqueous solution is 0.10 to 1.11 mol.L-1The molar concentration of the template agent is 5-28% of that of the low-valence manganese salt, and the template agent is hydrogen and oxygenThe volume ratio of the sodium dissolving solution to the mixed solution of the low-valence manganese salt aqueous solution and the template agent to the high-valence manganese salt aqueous solution is 175:45: 22.
The manganese dioxide-containing nano structure is applied to passivation of heavy metals, the heavy metals are at least one of As, Cd, Pb, Cu, Co, Ni, Zn and Hg, and the consumption of a passivating agent is 0.1-10% of the mass of polluted soil or sewage.
The manganese dioxide obtained by the method has controllable shape of the nano structure and many surface active sites, and has more efficient and stable restoration to heavy metal polluted soil or water.
Drawings
FIG. 1 is an SEM image of manganese dioxide nanostructures obtained in example 1;
FIG. 2 is an SEM image of manganese dioxide nanostructures obtained in example 2;
FIG. 3 is an SEM image of manganese dioxide nanostructures obtained in example 3;
FIG. 4 is an SEM image of manganese dioxide nanostructures obtained in example 4;
FIG. 5 is an SEM image of manganese dioxide nanostructures obtained in example 5;
FIG. 6 shows the nano-structure of manganese dioxide obtained in example 1 vs. Pb in the mixed solution2+、Cd2+、Co2+Passivation performance map of (a);
FIG. 7 is a graph showing the passivation performance of the manganese dioxide nanostructure obtained in example 2 on Pb, Cd, and As in contaminated soil.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the drawings and the specific embodiments of the specification, but the scope of the present invention is not limited thereto.
Example 1
A preparation method of a manganese dioxide nano structure with controllable appearance comprises the following steps: 175 mL of 0.12 mol. L was measured-1NaOH solution, 45 mL of 0.50 mol. L was added with stirring-1 MnSO4And 0.025 mol. L-1Mixed solution of CTAB; then 22 mL of 0.40 mol. L were added-1 NaMnO4A solution; then hydrothermal at 120 deg.CReacting for 8 hours; naturally cooling to room temperature after the reaction is finished, washing the precipitate to be neutral by using ethanol and water, and dissolving the precipitate in water at 60 DEG CoC is dried for 24 hours to obtain pin-shaped MnO with large head2Nanostructures (fig. 1). As can be seen from FIG. 1, MnO was obtained2Is pin-like, one end of which is in a shape of a sheet, the length of the pin is about 750 nm, and the width of the pin is about 25 nm.
0.30 g of MnO prepared as described above was weighed2Adding to 30 mL of Pb2+、Cd2+、Co2+Mixed ion solution (Pb)2+Initial concentration 29.91 mg.L-1、Cd2+Initial concentration 31.02 mg.L-1、Co2+Initial concentration 14.72 mg.L-1) Mixing, sealing, and shaking at constant temperature for 180 r min-1Oscillation 2 h (25)oC) And taking out, centrifuging, and carrying out ICP characterization on the supernatant. ICP analysis As shown in FIG. 6, MnO prepared2Nano structure for Pb in mixed solution2+、Cd2+、Co2+The passivation rates of the silicon nitride and the silicon nitride are respectively 98.08%, 99.51% and 99.70%, and the silicon nitride have good passivation performance.
Example 2
A preparation method of a manganese dioxide nano structure with controllable appearance comprises the following steps: 175 mL of 0.12 mol. L was measured-1NaOH solution, 45 mL of 0.10 mol. L was added with stirring-1 Mn(NO3)2And 0.028 mol. L-1Mixed solution of CTAB; then 22 mL of 0.15 mol. L were added-1 KMnO4A solution; then carrying out hydrothermal reaction for 12 h at 80 ℃; naturally cooling to room temperature after the reaction is finished, washing the precipitate to be neutral by using ethanol and water, and dissolving the precipitate in water at 60 DEG CoC is dried for 24 hours to obtain MnO2Nanostructures (fig. 2). As shown in FIG. 2, the obtained manganese dioxide sample is bamboo leaves, the length of the bamboo leaves is about 370 nm, and the appearance is uniform.
5.00 g of a soil sample (from a farmland polluted by economic resources, effective-state content: As: 0.29 mg/kg)-1、Cd：2.60 mg·kg-1、Pb：333.3 mg·kg-1) In a 100 mL leaching vessel, 0.30 g of MnO prepared above was added2And 25 mL of DTPA solution (containing 0.005 mol. L-1 DTPA and 0.01 mol. L)-1 CaCl2、 0.1 mol·L-1 TEA，pH = 7.30) Mixing, sealing, and shaking at constant temperature 25oC oscillating for 2 h (180 r.min)-1) And taking out and standing for 1 h, filtering, and carrying out ICP analysis on the supernatant. ICP analysis As shown in FIG. 7, MnO prepared2The passivation rates of the nano structure on As, Pb and Cd in soil are respectively 99.99%, 51.21% and 59.51%, and the nano structure has good passivation performance.
Example 3
A preparation method of a manganese dioxide nano structure with controllable appearance comprises the following steps: 175 mL of 0.12 mol. L was measured-1NaOH solution, 45 mL of 1.11 mol. L was added with stirring-1 MnCl2And 0.10 mol. L-1A mixture of PEG 200; then 22 mL of 1.36 mol. L were added-1 NaMnO4A solution; then carrying out hydrothermal reaction for 24h at 200 ℃; naturally cooling to room temperature after the reaction is finished, washing the precipitate to be neutral by using ethanol and water, and dissolving the precipitate in water at 60 DEG CoC is dried for 24 hours to obtain MnO2The nano-rod (figure 3) obtained is about 1000 nm long and about 54 nm wide.
Weighing 0.20 g MnO2Adding to 30 mL of Pb2+、Hg2+Mixed ion solution (Pb)2+Initial concentration 20.05 mg.L-1、Hg2+Initial concentration 23.62 mg. L-1) Mixing, sealing, and shaking at constant temperature for 180 r min-1Oscillation 2 h (25)oC) And taking out, centrifuging, and carrying out ICP characterization on the supernatant. ICP analysis found that MnO was obtained2Nano structure for Pb in mixed solution2+、Hg2+The passivation rates of the silicon nitride and the silicon nitride are respectively 92.93% and 37.85%, and the silicon nitride have better passivation performance.
Example 4
A preparation method of a manganese dioxide nano structure with controllable appearance comprises the following steps: 175 mL of 0.12 mol. L was measured-1NaOH solution, 45 mL of 0.10 mol. L was added with stirring-1 Mn(NO3)2And 0.028 mol. L-1Mixed solution of CTAB; then 22 mL of 0.15 mol. L were added-1 KMnO4A solution; then carrying out hydrothermal reaction for 12 h at 160 ℃; naturally cooling to room temperature after the reaction is finished, washing the precipitate to be neutral by using ethanol and water, and dissolving the precipitate in water at 60 DEG CoC is dried for 24 hours to obtain MnO2The nano-rods (figure 4) obtained are about 1700 nm long and 28 nm wide.
Weighing 0.30 g MnO2Adding to 30 mL of Pb2+、Cd2+、Co2+Mixed ion solution (Pb)2+Initial concentration 29.91 mg.L-1、Cd2+Initial concentration 31.02 mg.L-1、Co2+Initial concentration 14.72 mg.L-1) Mixing, sealing, and shaking at constant temperature for 180 r min-1Oscillation 2 h (25)oC) And taking out, centrifuging, and carrying out ICP characterization on the supernatant. ICP analysis found MnO made2Nano structure for Pb in mixed solution2+、Cd2+、Co2+The passivation rates of the passivation solution are respectively 99.08%, 99.76% and 99.95%, and the passivation solution has better passivation performance.
Example 5
A preparation method of a manganese dioxide nano structure with controllable appearance comprises the following steps: 175 mL of 0.12 mol. L was measured-1NaOH solution, 45 mL of 0.8 mol. L was added with stirring-1 MnCl2And 0.05 mol. L-1A mixed solution of SDS; then 22 mL of 1.00 mol. L were added-1 NaMnO4A solution; then carrying out hydrothermal reaction for 24h at 240 ℃; naturally cooling to room temperature after the reaction is finished, washing the precipitate to be neutral by using ethanol and water, and dissolving the precipitate in water at 60 DEG CoC is dried for 24 hours to obtain short rod-shaped MnO2(FIG. 5), it can be seen from FIG. 5 that the prepared short rods had a length of about 8.6 μm and a width of about 31 μm.
5.00 g of a soil sample (from a farmland polluted by economic resources, As available state content: 0.29 mg/kg)-1) In a 100 mL leaching flask, 0.50 g MnO was added2And 25 mL of DTPA solution (containing 0.005 mol. L-1 DTPA and 0.01 mol. L)-1CaCl2、 0.1 mol·L-1TEA, pH = 7.30), mixed well and sealed, in a constant temperature shaker 25oC oscillating for 2 h (180 r.min)-1) And taking out and standing for 1 h, filtering, and carrying out ICP analysis on the supernatant. ICP analysis found MnO made2The sample has 59.02% passivation rate to As in soil.
According to the invention, through design and regulation of key factors such As high-price/low-price soluble manganese salt proportion, template agent type/addition amount, hydrothermal temperature/time and the like, manganese dioxide nano structures with controllable different shapes are obtained, and the nano structures are used As passivators, so that efficient and rapid repair of As, Cd, Pb, Cu, Co, Ni, Zn and Hg polluted soil or polluted water is realized.
Although the present invention has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present invention, which is intended to be covered by the claims.
Claims (7)
1. The preparation method of the manganese dioxide nanostructure with controllable morphology is characterized by adding a mixed solution of a low-valence manganese salt aqueous solution and a template agent into a sodium hydroxide solution, adding a high-valence manganese salt aqueous solution, carrying out hydrothermal reaction at 80-240 ℃ for 8-24 h, washing after the reaction is finished, and drying to obtain the manganese dioxide nanostructure, wherein the addition amount of the template agent is 5-28% of the mole number of the low-valence manganese salt, and the mole ratio of the high-valence manganese salt to the low-valence manganese salt is 1: 1.3-2.6.
2. The method for synthesizing manganese dioxide nanostructures according to claim 1, wherein the method comprises the following steps: the template agent is: cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, sodium dodecyl sulfate or polyethylene glycol.
3. The method for synthesizing nano manganese dioxide with controllable morphology according to claim 1, wherein: the high-valence manganese salt is potassium permanganate or sodium permanganate, and the divalent manganese salt is manganese sulfate, manganese chloride or manganese nitrate.
4. The method for synthesizing nano manganese dioxide with controllable morphology according to claim 1, wherein: the concentration of the sodium hydroxide solution is 0.12 mol.L-1175 mL of the solution is used; the concentration of the high-valence manganese salt aqueous solution is 0.15-1.36 mol.L-1Low-valence manganese salt water solutionThe concentration of the solution is 0.10 to 1.11 mol.L-1And the molar concentration of the template agent is 5-28% of that of the low-valence manganese salt.
5. Manganese dioxide nanostructures produced by the method of any one of claims 1 to 4.
6. Use of the manganese dioxide nanostructures of claim 5 for passivating heavy metals.
7. The application of claim 6, wherein the heavy metal is at least one of As, Cd, Pb, Cu, Co, Ni, Zn and Hg, and the dosage of the passivating agent is 0.1-10% of the mass of the polluted soil or sewage.
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| CN113926450A (en) * | 2021-10-20 | 2022-01-14 | 浙江新火原新材料科技有限公司 | Preparation method and application of catalyst for indoor air purification |
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