CN109205567B - Method for preparing metal oxide multilevel structure by utilizing MOF derived bimetallic oxide template - Google Patents
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Abstract
The invention relates to the technical field of nano materials, in particular to a method for preparing a metal oxide multilevel structure by utilizing an MOF derived bimetallic oxide template, which comprises the steps of carrying out alkali treatment on the MOF derived bimetallic oxide template to obtain the metal oxide multilevel structure; setting M as the metal in the metal oxide multilevel structure, and the MOF derived double metal oxide template as MMoO4-a MOF-derived bimetallic oxide, said metal oxide having a multilevel structure MxOy. The preparation process is simple, mild and universal, has no special requirement on equipment, does not use a surfactant, and can realize large-scale industrial production; the metal oxide prepared by the method has the advantages of uniform multi-level structure size, stable structure and uniform component distribution.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for preparing a metal oxide multilevel structure by utilizing an MOF derived bimetallic oxide template.
Background
The nano material of the multilevel structure has attracted the attention of extensive research due to its excellent physicochemical properties. Because the nanoscale basic unit provides high surface area, high surface-to-volume ratio and surface functional groups, ideal mechanical properties and chemical properties can be provided for the overall structure of the material. Provides the material scientist with the structure formed by strict organization principles from molecules to macroscopic scale, and the multi-level material composed on any level can generate functional materials.
The micro-nano multilevel structure metal oxide has unique physicochemical properties, has wide application prospects in various fields of energy, environment, catalysis and the like, and becomes a hotspot and key point of the current nano material research. The existing preparation of the metal oxide with the multilevel structure comprises a sol-gel method, a hydrothermal method and the like, wherein the method mostly adopts a surfactant as a soft template agent, and has the problems of unclean template removal, easy introduction of impurities and the like in the preparation process, and needs a separate template removal process step, so that the complexity of the process is greatly increased, the preparation yield is low, and the large-scale industrial development is not facilitated; some hydrothermal methods need toxic organic solvents, which are not environment-friendly.
Disclosure of Invention
The invention provides a method for preparing a metal oxide multilevel structure by utilizing an MOF derived bimetallic oxide template, aiming at overcoming the problems that the traditional metal oxide multilevel structure preparation process depends on a surfactant, is complex in process and is not easy to industrialize, and the preparation process is simple, mild, universal, does not use a surfactant and is suitable for large-scale industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a metal oxide multilevel structure by utilizing an MOF derived bimetal oxide template comprises the steps of carrying out alkali treatment on the MOF derived bimetal oxide template to obtain the metal oxide multilevel structure; setting M as the metal in the metal oxide multilevel structure, and the MOF derived double metal oxide template as MMoO4-a MOF-derived bimetallic oxide, said metal oxide having a multilevel structure MxOy。
Metal-organic frameworks (MOFs) are crystals with a porous network structure formed by combining Metal ions and organic ligands, have a highly ordered pore structure, have a larger specific surface area, and contact more active sites. The MOFs precursor is used as the precursor to prepare the metal oxide, the metal oxide usually has an adjustable porous structure, the MOF derived bimetallic oxide template is obtained by controlling the morphology, the composition and the structure of the MOFs precursor, and the self-sacrifice template method is adopted to obtain the multilevel structure of the metal oxide after alkali treatment, so that the effective adjustment of the components and the structure of the metal oxide is realized.
Preferably, the MMoO is4-a method for the preparation of MOF material comprising the steps of:
(1) adding MoO3Dissolving 2-methylimidazole aqueous solution in deionized water, adding M water-soluble salt solution, heating to 80-180 ℃, stirring for reaction for 10-18 h, cooling, washing and drying to obtain an M/Mo-MOF material;
(2) calcining the M/Mo-MOF material prepared in the step (1) at high temperature in an air atmosphere to prepare the MMoO4-MOF-derived bimetallic oxides.
Preferably, in the step (2), the high-temperature calcination temperature is 300-900 ℃; the calcination time is 1-24 h; the heating rate is 1-20 ℃/min.
Preferably, the alkali treatment is carried out by using a KOH solution with the concentration of 0.01 to 10 mol/L.
Preferably, the alkali treatment is carried out using a KOH solution having a concentration of 0.1 mol/L.
Preferably, the MMoO is4MOF-derived bimetallic oxides with OH-The ratio of the amounts of substances (1): (1-100).
Preferably, the MMoO is4MOF-derived bimetallic oxides with OH-The ratio of the amounts of substances (1): 25.
preferably, the MMoO is4Standing the MOF derived bimetallic oxide in a KOH solution for 0.5-8 h to obtain the metal oxide multilevel structure MxOy。
Preferably, MMoO4-the MOF derived bimetallic oxide was left in KOH solution for 6 h.
Preferably, the M is selected from one of Mn, Cu, Zn, Fe, Mg and Al.
Therefore, the invention has the following beneficial effects:
(1) the preparation process is simple, mild and universal, has no special requirement on equipment, does not use a surfactant, and can realize large-scale industrial production;
(2) the metal oxide prepared by the method has the advantages of uniform multi-level structure size, stable structure and uniform component distribution.
Drawings
FIG. 1 is a topographical structure of the product prepared in example 1:
Mn/Mo-MOF(a,b,b1,b2)；MnMoO4-MOF(c，d，e)；Mn3O4a multilevel structure (f).
FIG. 2 is an XRD spectrum of Mn/Mo-MOF prepared in example 1.
FIG. 3 is MnMoO prepared in example 14-XRD spectrum of MOF.
FIG. 4 is Mn prepared in example 13O4XRD spectrum of multilevel structure.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) A clean beaker is taken, 25ml of deionized water is added, and 0.5g of MoO is weighed3Pouring into deionized water, weighing 0.475g of 2-methylimidazole, pouring into the deionized water, and carrying out ultrasonic dissolution. Another clean beaker is taken and added into 25ml deionized water, 0.26g of Mn (NO) is weighed3)2·4H2Pouring O into deionized water, dissolving by ultrasonic wave, adding the manganese nitrate solution into MoO3In solution. Heating the mixture to 120 ℃ in an oil bath, stirring the mixture for reaction for 12 hours, and naturally cooling the mixture to room temperature after the reaction is stopped. The deionized water centrifugal washing is repeated three times. And dried under vacuum at 60 ℃ for 12 h. Preparing Mn/Mo-MOF;
(2) placing a proper amount of Mn/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, and oxidizing at the high temperature of 500 ℃ for 3h in a tube furnace in the air atmosphere at the heating rate of 10 ℃/min. To obtain MnMoO4-a MOF crystal powder;
(3) taking 10mg of MnMoO4The MOF was placed in a clean vessel and 10ml of 0.1mol/L KOH solution, MnMoO4-the ratio of the amount of MOF to OH-substances is 1: 25; standing at room temperature for 6h, transferring the product into a centrifuge tube after the reaction is finished, centrifugally washing with deionized water, repeating for 3 times, and drying in a vacuum oven at 60 ℃ for 12h to obtain the productMn3O4A multi-level structure.
For Mn/Mo-MOF, MnMoO prepared in example 14-MOF and Mn3O4The multilevel structure is characterized as follows:
(1) and (3) morphology analysis:
SEM analysis:
SEM testing was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation: taking a small amount of the obtained Mn/Mo-MOF crystal powder and MnMoO4Crystal powder, Mn3O4The multilevel structure powder was placed on the surface of a support table with a conductive paste attached, and then placed in an SEM chamber for testing.
High-resolution TEM analysis:
the TEM test was performed on a JEOL 2010F transmission electron microscope, using the following sample preparation method: taking Mn/Mo-MOF crystal powder and MnMoO prepared in the example 34Crystal powder, Mn3O4And (3) respectively dropwise adding about 1ml of deionized water into the powder with the multilevel structure in a trace manner, ultrasonically dispersing for 10min until the powder is uniformly dispersed, dropwise adding a small amount of dispersion liquid onto the surface of the copper mesh with the micro grid (containing the microporous carbon support film) by using a dropping method, and naturally drying at room temperature.
Mn/Mo-MOF Crystal powder, MnMoO, obtained in example 14-MOF crystal powder, Mn3O4SEM image and TEM image of the multi-stage structure powder are shown in FIG. 1, and the overall morphology of the Mn/Mo-MOF material is shown as a rod-shaped structure with a smooth surface in FIG. 1(a, b). FIG. 1(b1, b2) shows that Mn/Mo-MOF has good crystallinity, stable structure and uniform components. FIG. 1(c, d) shows MnMoO produced by high temperature oxidation4The overall appearance of the material is a rod-shaped structure. FIG. 1(e) shows MnMoO4The MOF has good crystallinity, stable structure and uniform components. FIG. 1(f) shows Mn3O4The overall morphology of the multilevel structure material is Mn3O4The nanometer sheets are crossed with each other to form a rod-shaped structure.
FIGS. 2-4 show Mn/Mo-MOF crystal powder, MnMoO, prepared in example 14-MOF crystal powder, Mn3O4Wide angle X of multilevel structure powderRD spectrum, shown in FIG. 2, shows that the obtained Mn/Mo-MOF crystal material has good crystallinity, and the result is consistent with the results shown in FIG. 1(b1, b2), which indicates that the Mn/Mo-MOF material is successfully synthesized, and FIG. 3 shows that MnMoO is obtained by high-temperature oxidation4XRD pattern of powder, diffraction peak and MnMoO in the pattern4The standard cards (PDF #50-1287) are consistent, and prove that the MnMoO is successfully synthesized4A material. FIG. 4 shows Mn obtained by soaking in alkali solution3O4XRD pattern of powder with multilevel structure, diffraction peak and Mn in the pattern3O4The standard card (PDF #24-0734) is consistent, and the successful synthesis of Mn is proved3O4And (3) a multilevel structural material.
Example 2
(1) A clean beaker is taken, 25ml of deionized water is added, and 0.5g of MoO is weighed3Pouring into deionized water, weighing 0.475g of 2-methylimidazole, pouring into the deionized water, and carrying out ultrasonic dissolution. Another clean beaker is taken and added into 25ml deionized water, 0.26g of Mn (NO) is weighed3)2·4H2Pouring O into deionized water, dissolving by ultrasonic wave, adding the manganese nitrate solution into MoO3In solution. Heating the mixture to 80 ℃ in an oil bath, stirring the mixture for reaction for 180 hours, and naturally cooling the mixture to room temperature after the reaction is stopped. The deionized water centrifugal washing is repeated three times. And dried under vacuum at 60 ℃ for 12 h. Preparing Mn/Mo-MOF;
(2) placing a proper amount of Mn/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, and oxidizing at 300 ℃ for 24h in a tube furnace in the air atmosphere at the heating rate of 1 ℃/min. To obtain MnMoO4-a MOF crystal powder;
(3) taking 10mg of MnMoO4The MOF was placed in a clean vessel and 10ml of 0.01mol/L KOH solution, MnMoO4-the ratio of the amount of MOF to OH-substances is 1: 1. standing at room temperature for 6h, transferring the product into a centrifuge tube after the reaction is finished, centrifugally washing with deionized water, repeating for 3 times, and then drying in a vacuum oven at 60 ℃ for 12 h. To obtain Mn3O4A multi-level structure.
Example 3
(1) A clean beaker is taken, 25ml of deionized water is added, and 0.5g of MoO is weighed3Pouring into deionized water, weighing 0.475g of 2-methylimidazole, and pouring into deionized waterDissolving in water by ultrasonic wave. Another clean beaker is taken and added into 25ml deionized water, 0.26g of Mn (NO) is weighed3)2·4H2Pouring O into deionized water, dissolving by ultrasonic wave, adding the manganese nitrate solution into MoO3In solution. Heating to 180 ℃ in an oil bath, stirring for reaction for 12 hours, and naturally cooling to room temperature after the reaction is stopped. The deionized water centrifugal washing is repeated three times. And dried under vacuum at 60 ℃ for 12 h. Preparing Mn/Mo-MOF;
(2) placing a proper amount of Mn/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, and oxidizing at the high temperature of 900 ℃ for 1h in a tube furnace in the air atmosphere at the heating rate of 20 ℃/min. To obtain MnMoO4-a MOF crystal powder;
(3) taking 10mg of MnMoO4The MOF was placed in a clean vessel and 10ml of 10mol/L KOH solution, MMoO4-the ratio of the amount of MOF-derived bimetallic oxide to OH-species is 1: 100, respectively; standing at room temperature for 6h, transferring the product into a centrifuge tube after the reaction is finished, centrifugally washing with deionized water, repeating for 3 times, and drying in a vacuum oven at 60 ℃ for 12h to obtain Mn3O4A multi-level structure.
Example 4
(1) A clean beaker is taken, 25ml of deionized water is added, and 0.5g of MoO is weighed3Pouring into deionized water, weighing 0.475g of 2-methylimidazole, pouring into the deionized water, and carrying out ultrasonic dissolution. Another clean beaker is taken and added into 25ml of deionized water, and 0.306g of Zn (NO) is weighed3)2·6H2Pouring O into deionized water, dissolving with ultrasonic wave, adding zinc nitrate solution into MoO3In solution. Heating the mixture to 120 ℃ in an oil bath, stirring the mixture for reaction for 12 hours, and naturally cooling the mixture to room temperature after the reaction is stopped. Centrifugally washing with deionized water, repeating for three times, and vacuum-drying at 60 ℃ for 12h to prepare Zn/Mo-MOF;
(2) placing a proper amount of Zn/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, oxidizing at the high temperature of 800 ℃ for 5h in a tube furnace in the air atmosphere at the heating rate of 5 ℃/min to prepare ZnMoO4-a MOF crystal powder;
(3) taking 10mg of ZnMoO4The MOF crystal powder was placed in a clean container and 10ml of 0.5molKOH/L solution of ZnMoO4-MOF and OH-The ratio of the amounts of substances (1): and 25, standing at room temperature for 8h, after the reaction is finished, transferring the product into a centrifuge tube, centrifugally washing with deionized water, repeating for 3 times, and then drying in a vacuum oven at 60 ℃ for 12h to obtain the ZnO multilevel structure.
Example 5
(1) A clean beaker is taken, 25ml of deionized water is added, and 0.5g of MoO is weighed3Pouring into deionized water, weighing 0.475g of 2-methylimidazole, pouring into the deionized water, and carrying out ultrasonic dissolution. Another clean beaker is taken and added into 25ml of deionized water, and 0.386g of Al (NO) is weighed3)2·9H2Pouring O into deionized water, dissolving by ultrasonic wave, adding aluminum nitrate solution into MoO3In solution. Heating the mixture to 100 ℃ in an oil bath, stirring the mixture for reaction for 12 hours, and naturally cooling the mixture to room temperature after the reaction is stopped. Carrying out centrifugal washing by deionized water, repeating for three times, and carrying out vacuum drying for 12h at the temperature of 60 ℃ to prepare Al/Mo-MOF;
(2) placing a proper amount of Al/Mo-MOF in a boat-shaped crucible, placing the crucible in the middle of a quartz tube, oxidizing at 350 ℃ for 3h in a tube furnace in the air atmosphere at the heating rate of 10 ℃/min to obtain Al2(MoO4)3-a MOF crystal powder;
(3) taking 10mg of Al2(MoO4)3The MOF crystal powder is placed in a clean container and 10ml of 0.1mol/L KOH solution, Al2(MoO4)3-MOF and OH-The ratio of the amounts of substances (1): 45, standing at room temperature for 10h, transferring the product into a centrifuge tube after the reaction is finished, centrifugally washing with deionized water, repeating for 3 times, and then drying in a vacuum oven at 60 ℃ for 12h to obtain Al2O3A multi-level structure.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (6)
1. A method for preparing a metal oxide multilevel structure by utilizing an MOF derived bimetallic oxide template,the method is characterized in that an MOF derived bimetallic oxide template is subjected to alkali treatment to obtain a metal oxide multilevel structure; setting M as the metal in the metal oxide multilevel structure, and the MOF derived double metal oxide template as MMoO4-a MOF-derived bimetallic oxide, said metal oxide having a multilevel structure MxOy(ii) a The M is selected from one of Mn, Cu, Zn, Fe, Mg and Al; carrying out alkali treatment by using a KOH solution with the concentration of 0.01-10 mol/L; the MMoO4MOF derived bimetallic oxides with OH in KOH solution-The ratio of the amounts of substances (1): (1-100); mixing MMoO4Standing the MOF derived bimetallic oxide in a KOH solution for 0.5-8 h to obtain the metal oxide multilevel structure MxOy。
2. The method for preparing the multilevel structure of metal oxide by using MOF derived bimetallic oxide template according to claim 1, wherein the MMoO is prepared by using the MOF derived bimetallic oxide template4-a method for the preparation of MOF material comprising the steps of:
(1) adding MoO3Dissolving 2-methylimidazole aqueous solution in deionized water, adding M water-soluble salt solution, heating to 80-180 ℃, stirring for reacting for more than 6 hours, cooling, washing and drying to obtain an M/Mo-MOF material;
(2) calcining the M/Mo-MOF material prepared in the step (1) at high temperature in an air atmosphere to prepare the MMoO4-MOF-derived bimetallic oxides.
3. The method for preparing the multilevel structure of the metal oxide by using the MOF derived bimetallic oxide template as claimed in claim 1, wherein in the step (2), the high-temperature calcination temperature is 300-900 ℃; the calcination time is 1-24 h; the heating rate is 1-20 ℃/min.
4. The method for preparing the multilevel structure of the metal oxide by using the MOF derived bimetallic oxide template according to claim 1, wherein the alkali treatment is performed by using a KOH solution with the concentration of 0.1 mol/L.
5. The method for preparing the multilevel structure of metal oxide by using MOF derived bimetallic oxide template according to claim 1, wherein the MMoO is prepared by using the MOF derived bimetallic oxide template4MOF-derived bimetallic oxides with OH-The ratio of the amounts of substances (1): 25.
6. the method for preparing the multilevel structure of metal oxide by using MOF derived bimetallic oxide template according to claim 1, wherein the MMoO is4-the MOF derived bimetallic oxide was left in KOH solution for 6 h.
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| CN110876804B (en) * | 2019-11-04 | 2021-05-18 | 华中科技大学 | Preparation and application of porous mangano-manganic oxide nano probe |
| CN110776650A (en) * | 2019-11-11 | 2020-02-11 | 青岛科技大学 | Zinc-molybdenum bimetal organic framework multilevel structure material and preparation method thereof |
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