CN114212829B - Preparation method of zinc manganate nanosphere material - Google Patents
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- CN114212829B CN114212829B CN202111525334.7A CN202111525334A CN114212829B CN 114212829 B CN114212829 B CN 114212829B CN 202111525334 A CN202111525334 A CN 202111525334A CN 114212829 B CN114212829 B CN 114212829B
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention discloses a preparation method of a zinc manganate nanosphere material, which comprises the following steps: (1) Preparing solution containing solid rhombic dodecahedron ZIF-8 nano particles by adopting a chemical precipitation method at room temperature, centrifuging to separate precipitate, and obtaining absolute ethyl alcoholWashing and drying to obtain solid rhombic dodecahedron ZIF-8 nano particles; (2) Mixing a solid rhombic dodecahedron ZIF-8 ethanol solution with a tetrahydrate manganese chloride ethanol solution, and performing solvothermal reaction to obtain a solution containing ZnMn 2 O 4 Centrifuging the solution of the nanospheres to separate precipitate, washing with absolute ethyl alcohol, and drying to obtain ZnMn 2 O 4 Nanosphere particles; (3) ZnMn to be obtained 2 O 4 Grinding the nanosphere particles, and calcining at high temperature to obtain the zinc manganate nanosphere material with good crystallinity. The invention is simple and easy to operate, short in time consumption and low in cost.
Description
Technical Field
The invention relates to the technical field of nano material production, in particular to a preparation method of a zinc manganate nanosphere material.
Background
Composition ZnMn 2 O 4 The element of the substance has abundant reserves on the earth and is environment-friendly, and the substance is considered to be one of materials which have potential application in the fields of gas sensor sensitive materials, lithium ion battery electrode materials, photocatalytic materials and the like. Similarly, for ZnMn 2 O 4 The shape design and nanocrystallization of the material are particularly important.
Chinese patent CN 106848289B discloses lotus root like spinel type ZnMn 2 O 4 The preparation method of the powder comprises the steps of enabling a reaction solution to quickly reach a reaction temperature of about 180 ℃ through microwave irradiation, reacting for about 3 hours to obtain a precursor product with a specific morphology, and calcining the precursor product at a high temperature of about 600 ℃ to obtain lotus root-like flaky spinel type ZnMn 2 O 4 And (3) powder. The method not only can lead ZnMn to be reacted with 2 O 4 The powder is uniformly dispersed, and the prepared ZnMn 2 O 4 The powder has a unique lotus root-like sheet structure, and has a larger specific surface area and a sheet structure. However, the method needs expensive microwave irradiation reaction equipment, the prepared nano material has single morphology, and the used reaction solvent is harmful to human bodies.
Chinese patent CN 102660770A discloses αmnO 2 Preparation of ZnMn by nano rod template method 2 O 4 Method of nanorods using alpha MnO 2 Nano rod is used as template, zinc salt solution and alkaline solution are added, and then alpha MnO is prepared through reaction 2 /Zn(OH) 2 The precursor is calcined to obtain ZnMn 2 O 4 Nanorod material. The method is a typical hard template preparation method, and the synthesized sample has good appearance and high structural order. However, the method has the disadvantages of complicated operation flow, long time for hydrothermal reaction, low overall efficiency, and high danger degree of treatment of acidic and alkaline waste liquid generated by using HCI and NaOH solutions in the preparation process.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc manganate nanosphere material, which is simple and feasible, short in time consumption and low in cost.
The technical scheme adopted for solving the technical problems is as follows:
the preparation method of the zinc manganate nanosphere material comprises the following steps:
(1) Preparing a solution containing solid rhombic dodecahedron ZIF-8 nano particles by adopting a chemical precipitation method at room temperature, centrifugally separating and precipitating, washing with absolute ethyl alcohol, and drying to obtain the solid rhombic dodecahedron ZIF-8 nano particles;
(2) Mixing a solid rhombic dodecahedron ZIF-8 ethanol solution with a tetrahydrate manganese chloride ethanol solution, and performing solvothermal reaction to obtain a solution containing ZnMn 2 O 4 Centrifuging the solution of the nanospheres to separate precipitate, washing with absolute ethyl alcohol, and drying to obtain ZnMn 2 O 4 Nanosphere particles;
(3) ZnMn to be obtained 2 O 4 Grinding the nanosphere particles, and calcining at high temperature to obtain the zinc manganate nanosphere material with good crystallinity.
The innovation point of the invention is that the adsorption characteristic of the ZIFs material is utilized to prepare the zinc manganate nanosphere material, the ZIFs material has larger specific surface area and excellent pore structure, is used as a waste liquid adsorbent for more and more researches, but is not used as a metal ion adsorbent for synthesizing special metal oxide with regular morphologyStudy of the material. The ZIF-8 can be used as an adsorbent material for adsorbing heavy metal manganese ions in a solution, and the ZIF-8 can also be used as a zinc source for reacting with tetrahydrate manganese chloride to form ZnMn 2 O 4 And finally preparing the zinc manganate nanosphere material with good crystallinity through high-temperature annealing.
In the synthesis process of the product, tetravalent manganese ions are adsorbed on the surface of a ZIF-8 material in a very short time through ultrasonic oscillation, the diffusion rate of the manganese ions is accelerated through solvothermal reaction, most of the manganese ions are adsorbed in the ZIFs material, and the nucleation and growth of zinc manganate particles are promoted at a higher temperature of 80-85 ℃, so that the zinc manganate nanosphere structure is finally obtained.
Preferably, the specific process of step (1) is as follows:
preparing an aqueous solution A containing 2-methylimidazole and an aqueous solution B containing zinc chloride at room temperature; pouring the aqueous solution B into the aqueous solution A quickly, and stirring for 0.5-1h.
Preferably, in the aqueous solution a, 2-methylimidazole: deionized water = 8-10 g:150 mL.
Preferably, in the aqueous solution B, zinc chloride: deionized water = 200-300 mg:30 mL.
Preferably, the specific process of step (2) is as follows:
preparing an ethanol solution C containing solid rhombic dodecahedron ZIF-8 nano particles and an ethanol solution D containing manganese chloride tetrahydrate at room temperature; then pouring the solution C into the solution D, carrying out ultrasonic vibration, and finally pouring into a polytetrafluoroethylene lining and placing into a reaction kettle for solvothermal reaction.
Preferably, in the solution C, the mass volume ratio of the solid diamond-shaped dodecahedron ZIF-8 nano particles to the absolute ethyl alcohol is 100mg to 30-40mL.
Preferably, in the solution D, the mass volume ratio of the manganese chloride tetrahydrate to the absolute ethyl alcohol is 100 mg:30-40 mL.
Preferably, the solvothermal reaction temperature is 80-85 ℃ and the reaction time is 1.5-5h.
Preferably, in the step (3), the high-temperature calcination is carried out at a temperature of 450-600 ℃, a heating rate of 2-5 ℃/min and a calcination time of 1.5-5h.
The beneficial effects of the invention are as follows:
1. as one branch of the metal organic framework structure, the zeolite imidazole salt Framework Structure (ZIFs) has obvious advantages compared with other MOFs in terms of construction space morphology due to higher thermal stability and chemical stability;
2. ZIF-8 synthesized by room temperature method has uniform size, is not easy to agglomerate and is finally synthesized at higher temperature 2 O 4 The nanosphere material has a regular shape;
3. synthetic ZnMn 2 O 4 The nanosphere material has a porous structure and a larger specific surface area;
4. the method is simple to operate, nontoxic and pollution-free, adopts common chemical experiment medicines, has low price, and is favorable for industrialized popularization;
5. the preparation time is short, acid-base solution is not needed, waste liquid is easy to treat, and energy resources are saved.
Drawings
FIG. 1 is ZnMn 2 O 4 Schematic of the synthesis of nanospheres.
FIG. 2 is ZnMn prepared in examples 1-4 2 O 4 X-ray diffraction pattern of nanospheres.
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a precursor solid diamond dodecahedral ZIF-8 prepared in examples 1-4.
FIG. 4 is the final product ZnMn prepared in example 1 2 O 4 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 5 is the final product ZnMn prepared in example 2 2 O 4 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 6 is a final product ZnMn prepared in example 3 2 O 4 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 7 is a final product ZnMn prepared in example 4 2 O 4 Scanning Electron Microscope (SEM) pictures of (a).
FIG. 8 is a photograph of the sample of example 3Final product ZnMn 2 O 4 Element distribution map (EDS).
FIG. 9 is ZnMn prepared in comparative example 1 2 O 4 X-ray diffraction pattern of material and scan picture.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples.
In the present invention, the materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
the preparation method of the zinc manganate nanosphere material comprises the following steps:
1. synthesis of ZIF-8:
272.6mg of zinc chloride is dissolved in 30mL of deionized water to form solution A, and the solution A is rapidly stirred for 10min to form a transparent emulsion solution rich in foam; 9.08g of 2 methylimidazole is dissolved in 150mL of deionized water to form a solution B, and the solution B is stirred for 10min to be uniformly stirred to be in a colorless transparent state; dissolving the solution A in the solution B rapidly to form a solution C, and stirring the solution C for 1h at room temperature to uniformly stir the solution to be in a milky opaque state; and then, carrying out centrifugal operation on the solution C prepared in the above way, centrifuging at 8000rpm for 4 times, washing the precipitate with absolute ethyl alcohol for 7min at one time, and drying at 60 ℃ overnight to obtain the ZIF-8 material. The scan is shown in fig. 3.
2. ZnMn (zinc sulfide) 2 O 4 Synthesis of nanospheres:
(1) Firstly, 100mg of a ZIF-8 material with complete drying is weighed and placed in a beaker containing 30mL of absolute ethyl alcohol, the solution is made to be relatively uniform by ultrasonic treatment for 2min (ultrasonic power is 70W), and stirring is continued for 5min to obtain a solution C. Next, 100mg of manganese chloride tetrahydrate was weighed and put in 30mL of absolute ethanol, and the solution was stirred for 5 minutes to uniformly obtain a solution D. Finally, pouring the solution C into the solution D, performing ultrasonic treatment for 1min (ultrasonic power is 70W), and stirring for 2min; pouring the stirred solution into a polytetrafluoroethylene lining of 80mL, placing the solution into a reaction kettle, preserving heat at 80 ℃ and reacting for 4h. After the reaction is completed, the solution is separatedWashing heart, washing with absolute ethanol, centrifuging for 4 times, oven drying at 60deg.C, and collecting to obtain ZnMn 2 O 4 A nanosphere.
(2) ZnMn for obtaining high crystallinity 2 O 4 Nanospheres, which are obtained by centrifugal drying in (1) 2 O 4 Calcining the nanosphere material in a muffle furnace, setting the heat preservation temperature to be 500 ℃, the heating rate to be 2 ℃/min, cooling to room temperature along with the furnace, and calcining for 3 hours to obtain ZnMn with high crystallinity 2 O 4 Nanosphere material. ZnMn (zinc sulfide) 2 O 4 The synthesis flow chart of the nanosphere material is shown in figure 1. Example 1 synthetic ZnMn 2 O 4 The scan of the nanosphere material is shown in FIG. 4, and the X-ray diffraction pattern is shown in FIG. 2 (c).
Example 2:
this embodiment differs from embodiment 1 in that: the muffle furnace calcination in the second step was not performed, and the other steps were the same as in example 1. The scan is shown in FIG. 5, and the X-ray diffraction pattern is shown in FIG. 2 (a).
Example 3:
this embodiment differs from embodiment 1 in that: in the second step, the muffle furnace calcination was performed at a temperature of 450℃for 90 minutes, and the procedure was the same as in example 1. The scan is shown in FIG. 6, the X-ray diffraction pattern is shown in FIG. 2 (b), and the elemental distribution map (EDS) is shown in FIG. 8.
Example 4:
this embodiment differs from embodiment 1 in that: in the second step, the muffle furnace calcination was performed at 600℃for 5 hours, and the procedure was the same as in example 1. The scan is shown in FIG. 7, and the X-ray diffraction pattern is shown in FIG. 2 (d).
Comparative example 1:
100mg of zinc chloride and 100mg of manganese chloride tetrahydrate are respectively weighed and put into absolute ethyl alcohol containing 60mL, and stirring and ultrasonic treatment are carried out for 5min to ensure that the solution is uniform. Finally, mixing and stirring the solution for 5min; pouring the stirred solution into a polytetrafluoroethylene lining of 80mL, placing the solution into a reaction kettle, preserving heat at 80 ℃ and reacting for 4h. After the reaction is completed, the solution is centrifugally washed, washed and centrifuged for 4 times by absolute ethyl alcohol, and then baked at 60 DEG CCollecting after drying to obtain ZnMn 2 O 4 A material.
ZnMn for obtaining high crystallinity 2 O 4 Nanospheres, we obtained ZnMn by centrifugal drying 2 O 4 Calcining the material in a muffle furnace, setting the heat preservation temperature to be 500 ℃, the heating rate to be 2 ℃/min, cooling to room temperature along with the furnace, and calcining for 3 hours to obtain ZnMn with high crystallinity 2 O 4 A material.
The X-ray diffraction pattern and scan are shown in fig. 9.
The ZnMn prepared by the invention is next 2 O 4 Analyzing and characterizing the appearance of the nanosphere material:
ZnMn prepared from examples 1, 2, 3, 4 in FIG. 2 2 O 4 X-ray diffraction pattern of nanosphere material, XRD diffraction peaks of uncalcined material and material prepared at different calcination temperatures, and ZnMn of tetragonal system (JCPDS No. 24-1133) 2 O 4 No impurity peak of other substances appears, diffraction peaks correspond to ZnMn at 2 theta = 29.3 °, 32.9 °, 36.4 °, 59.0 ° and 60.8 ° respectively 2 O 4 The (112), (103), (211), (321), (224) crystal face characteristic peaks. Description of ZnMn obtained 2 O 4 The nanosphere structure has no impurities and high purity. It can be seen that the peak intensity of the material increases gradually with increasing treatment temperature, and the peak shape becomes more and more sharp, that is, the crystal grains grow with increasing temperature, and the order and crystallinity of the material are continuously enhanced. Indicating that temperature is an important factor affecting the properties of the material.
Fig. 3 is a scanning electron microscope picture of a precursor rhombic dodecahedron ZIF-8, and it can be seen from the picture that the synthesized ZIF-8 is a rhombic dodecahedron structure different from a sphere, and has the advantages of smooth surface, good dispersibility, uniform particle size and about 400-500 nanometers.
Fig. 5 is a scanning electron microscope picture of example 2. The regular spherical morphology can be seen from the pictures, the surface is smooth, the size is 0.9-1.5 microns, and the dispersibility is good.
As can be seen from FIGS. 4, 6 and 7, the calcination temperature is at the present pointPlays a critical role in the invention, and ZnMn is added with the rising of the calcination temperature 2 O 4 The crystal grains on the surface of the nanospheres gradually grow up, the order and crystallinity of the material are continuously enhanced, and the conclusion drawn here is consistent with the result obtained by the X-ray diffraction. From the pictures, we can also see that the size of the nanospheres is gradually reduced along with the increase of the calcination temperature and the calcination time, and we speculate that the nanospheres are caused by the fact that the weight loss ratio is larger and larger due to the sufficient combustion of C, H and other elements in the calcination process, thereby causing ZnMn 2 O 4 Shrinkage of nanosphere size.
The uniform element distribution of Mn, O and Zn can be seen from the scanning electron microscope mirror surface scanning element distribution of FIG. 8, and the synthesized ZnMn is more intuitively and clearly shown 2 O 4 The components of each part of the nanosphere structure are uniformly distributed.
From comparative example 1, it can be seen that there is no ZIFs material acting as an adsorbent, and that only zinc ions and manganese ions are added to the solution for hydrothermal operation, and the prepared product is ZnMn 2 O 4 The material, however, has no specific regular morphology, further demonstrates the unique advantage of ZIFs materials as adsorbents for the preparation of iso-metal oxides.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (9)
1. The preparation method of the zinc manganate nanosphere material is characterized by comprising the following steps of:
(1) Preparing a solution containing solid rhombic dodecahedron ZIF-8 nano particles by adopting a chemical precipitation method at room temperature, centrifugally separating and precipitating, washing with absolute ethyl alcohol, and drying to obtain the solid rhombic dodecahedron ZIF-8 nano particles;
(2) Mixing a solid rhombic dodecahedron ZIF-8 ethanol solution with a tetrahydrate manganese chloride ethanol solution, and performing solvothermal reaction to obtain a solution containing ZnMn 2 O 4 Centrifuging the solution of nanospheres to precipitate, and obtaining absolute ethyl alcoholWashing and drying to obtain ZnMn 2 O 4 Nanosphere particles;
(3) ZnMn to be obtained 2 O 4 Grinding the nanosphere particles, and calcining at high temperature to obtain the zinc manganate nanosphere material with good crystallinity.
2. The preparation method according to claim 1, wherein the specific process of step (1) is as follows:
preparing an aqueous solution A containing 2-methylimidazole and an aqueous solution B containing zinc chloride at room temperature; pouring the aqueous solution B into the aqueous solution A quickly, and stirring for 0.5-1h.
3. The preparation method according to claim 2, wherein in the aqueous solution a, 2-methylimidazole: deionized water = 8-10 g:150 mL.
4. The method according to claim 2, wherein in the aqueous solution B, zinc chloride: deionized water = 200-300 mg:30 mL.
5. The preparation method according to claim 1, wherein the specific process of step (2) is as follows:
preparing an ethanol solution C containing solid rhombic dodecahedron ZIF-8 nano particles and an ethanol solution D containing manganese chloride tetrahydrate at room temperature; then pouring the solution C into the solution D, carrying out ultrasonic vibration, and finally pouring into a polytetrafluoroethylene lining and placing into a reaction kettle for solvothermal reaction.
6. The method according to claim 5, wherein the mass-volume ratio of the solid rhombic dodecahedral ZIF-8 nanoparticles to the absolute ethanol in the solution C is 100 mg/30-40 mL.
7. The preparation method according to claim 5, wherein the mass-volume ratio of the manganese chloride tetrahydrate to the absolute ethyl alcohol in the solution D is 100 mg/30-40 mL.
8. The preparation method according to claim 1, wherein the solvothermal reaction temperature is 80-85 ℃ and the reaction time is 1.5-5h.
9. The method according to claim 1, wherein in the step (3), the high-temperature calcination is performed at a temperature of 450 to 600 ℃, a temperature rising rate of 2 to 5 ℃/min, and a calcination time of 1.5 to 5 hours.
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| CN113697844A (en) * | 2021-08-26 | 2021-11-26 | 杭州恒毅智创科技有限公司 | Fe-doped ZnO nanoparticle with dodecahedron structure |
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| CN113697844A (en) * | 2021-08-26 | 2021-11-26 | 杭州恒毅智创科技有限公司 | Fe-doped ZnO nanoparticle with dodecahedron structure |
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