CN109279656B - Micro-nano mesoporous spherical Mn2O3Preparation method of (1) - Google Patents
Micro-nano mesoporous spherical Mn2O3Preparation method of (1) Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 19
- 239000011858 nanopowder Substances 0.000 claims abstract description 56
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 41
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 41
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 26
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- 235000019441 ethanol Nutrition 0.000 claims description 54
- 239000011572 manganese Substances 0.000 claims description 46
- 239000007810 chemical reaction solvent Substances 0.000 claims description 34
- 150000002696 manganese Chemical class 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000007790 solid phase Substances 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000000975 dye Substances 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 41
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012071 phase Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a micro-nano mesoporous spherical Mn2O3The preparation method comprises the following steps: spherical MnCO3The nano powder is roasted for at least 4 hours at the temperature of 350-650 ℃ in the air or oxygen atmosphere to obtain the micro-nano mesoporous spherical Mn2O3(ii) a Wherein, the spherical MnCO3The grain diameter of the nano powder is 0.5-2 μm. The invention uses spherical MnCO with specific grain diameter3The nano powder is used as a raw material and is directly roasted under the conditions of specific roasting atmosphere, temperature, time and the like, so that the mesoporous spherical Mn with the micro-nano structure can be simply obtained2O3. The micro-nano mesoporous spherical Mn obtained by the preparation method2O3Has good dispersibility, specific surface area and pore size distribution, is particularly suitable for adsorbing organic dyes and shows higher adsorption performance.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to micro-nano mesoporous spherical Mn2O3The preparation method of (1).
Background
Mn, an important transition metal oxide2O3Has various applications in various fields, not only is an important manganese source for synthesizing lithium manganate with different stoichiometric proportions, but also can be used for catalytically decomposing N2O, removing organic waste gas in the synthesized semiconductor material, improving the thermal stability of the piezoelectric ceramic, and being used as a lithium ion battery cathode material, a capacitor electrode material and the like; in addition, the adsorbent material is also an excellent adsorbent material, and can be used for adsorbing organic dyes to solve the problem of wastewater pollution caused by printing and dyeing industries and the like.
At present, Mn2O3The synthesis method mainly comprises a hydrothermal method, a sol-gel method, a microemulsion method and a precursor method. The hydrothermal method mostly utilizes KMnO4The method has higher requirements on the proportion of raw materials, is easy to obtain manganese oxides with other valence states, and has rod-like appearance, low specific surface area and small pore diameter, which is not beneficial to adsorbing organic dye; the synthesis steps of the sol-gel method are complicated, and it is difficult to synthesize spherical Mn2O3(ii) a The microemulsion method is characterized in that chemical reaction is carried out in microemulsion droplets formed in a water-in-oil phase, and Mn is synthesized by controlling the size of the droplets2O3The pollution is serious, and pure phase Mn is difficult to obtain2O3。
In addition, when Mn2O3When the Mn-Mn composite adsorbent is used as an adsorbent, the size, the shape, the crystallinity, the purity, the particle size, the dispersibility and other physicochemical properties of the Mn-Mn composite adsorbent have important influence on the adsorption performance, and how to control the conditions to synthesize Mn with good dispersibility, uniform particle size, high purity and larger adsorption performance2O3Has been a research hotspot and difficulty in recent years. Mesoporous spherical Mn with high-dispersity micro-nano structure2O3The above problems can be solved to a large extent, however, at presentIn many studies, Mn synthesized by the method2O3The above properties cannot be achieved simultaneously, which also results in low adsorption performance when used in an adsorbent.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides micro-nano mesoporous spherical Mn2O3Based on a specific spherical MnCO3The mesoporous spherical Mn with the micro-nano structure can be simply obtained by simply controlling the roasting atmosphere, the temperature, the time and the like of the nano powder2O3。
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
micro-nano mesoporous spherical Mn2O3The preparation method comprises the following steps: spherical MnCO3The nano powder is roasted for at least 4 hours at the temperature of 350-650 ℃ in the air or oxygen atmosphere to obtain the micro-nano mesoporous spherical Mn2O3(ii) a Wherein the spherical MnCO3The grain diameter of the nano powder is 0.5-2 μm.
Further, the spherical MnCO3The preparation method of the nano powder comprises the following steps:
s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the ratio of the water-soluble manganese salt to the ammonia water is 0.25g to 1 mL-0.5 g to 1mL, and the ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.04g to 1 mL-0.2 g to 1 mL;
s2, introducing CO into the reaction mixture2Reacting for 2-6 h at 60-80 ℃ under the condition of (1) to obtain a reaction product;
s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
Further, in the step S1, the alcohol component is ethylene glycol.
Further, in the step S1, the volume percentage of the alcohol component in the alcohol reaction solvent is not less than 20%.
Further, in the step S2, CO2The feeding rate of (2) is 0.5L/min-2L/min.
Further, in the step S1, the water-soluble manganese salt is manganese chloride, manganese sulfate, or manganese acetate.
Further, in step S3, a specific method for washing the solid phase is: washing the solid phase with deionized water for three times, and then washing the solid phase with absolute ethyl alcohol for one time; the specific method for drying the washed solid phase comprises the following steps: and (3) placing the washed solid phase in a vacuum drying oven to be dried for at least 8h at the temperature of 70-90 ℃.
Further, the spherical MnCO is roasted3The temperature rising rate of the nano powder is 1-20 ℃/min.
Further, the micro-nano mesoporous spherical Mn2O3Has a particle diameter of 0.5-2 μm and a specific surface area of not less than 36m2(ii)/g, the pore size distribution is 20nm to 25 nm.
The invention uses spherical MnCO with specific grain diameter3The nano powder is used as a raw material and is directly roasted under the conditions of specific roasting atmosphere, temperature, time and the like, so that the mesoporous spherical Mn with the micro-nano structure can be simply obtained2O3. The micro-nano mesoporous spherical Mn obtained by the preparation method2O3Has good dispersibility, specific surface area and pore size distribution, is particularly suitable for adsorbing organic dyes and shows higher adsorption performance.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a micro-nano mesoporous spherical Mn according to the present invention2O3A flow chart of the steps of the preparation method of (1);
FIG. 2 is a spherical MnCO according to example 1 of the present invention3FE-SEM picture of the nano powder;
FIG. 3 is a spherical MnCO according to example 1 of the present invention3Thermogravimetric analysis of nanopowderAnalyzing the result;
FIG. 4 is a micro-nano mesoporous spherical Mn according to example 1 of the present invention2O3XRD pictures of (1);
FIG. 5 is a micro-nano mesoporous spherical Mn according to example 1 of the present invention2O3SEM picture of (a);
FIG. 6 is a micro-nano mesoporous spherical Mn according to example 2 of the present invention2O3XRD pictures of (1);
FIG. 7 is a micro-nano mesoporous spherical Mn according to example 3 of the present invention2O3XRD pictures of (1);
FIG. 8 is a micro-nano mesoporous spherical Mn according to example 4 of the present invention2O3SEM picture of (a);
FIG. 9 is a micro-nano mesoporous spherical Mn according to example 4 of the present invention2O3SEM picture of (a);
FIG. 10 is a micro-nano mesoporous spherical Mn according to example 5 of the present invention2O3SEM picture of (a);
FIG. 11 is a micro-nano mesoporous spherical Mn according to example 6 of the present invention2O3SEM picture of (a);
FIG. 12 is a micro-nano mesoporous spherical Mn according to example 7 of the present invention2O3SEM picture of (a);
FIG. 13 is an XRD picture of a comparative product according to the invention of comparative example 1;
FIG. 14 is an SEM picture of a comparative product of comparative example 1 according to the present invention;
FIG. 15 shows a micro-nano mesoporous spherical Mn obtained according to example 1 of the present invention2O3A graph of adsorption capacity versus time at the time of application;
FIG. 16 shows a micro-nano mesoporous spherical Mn obtained according to example 1 of the present invention2O3Equilibrium adsorption capacity versus initial concentration at the time of application.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
The invention is based on the general mesoporous spherical Mn in the prior art2O3The preparation method can not simultaneously meet the physicochemical properties of good dispersibility, specific surface area, pore size distribution and the like which have important influence on the adsorption performance, thereby providing a spherical MnCO based on the specific structure3Micro-nano mesoporous spherical Mn of nano powder2O3The preparation method of the organic dye has the advantages of obtaining good dispersibility, specific surface area and pore size distribution, and particularly showing higher adsorption performance when the organic dye is adsorbed.
The invention relates to micro-nano mesoporous spherical Mn2O3The preparation method only needs to mix spherical MnCO3The nano powder is roasted for at least 4 hours at the temperature of 350-650 ℃ in the air or oxygen atmosphere to obtain the micro-nano mesoporous spherical Mn2O3。
Specifically, spherical MnCO3The grain diameter of the nano powder is 0.5-2 μm.
More specifically, referring to fig. 1, the micro-nano mesoporous spherical Mn2O3The preparation method specifically comprises the following steps:
in step S1, a water-soluble manganese salt and aqueous ammonia are dissolved in an alcohol reaction solvent to obtain a reaction mixture.
Further, controlling the proportion of the water-soluble manganese salt to the ammonia water to be 0.25g:1 mL-0.5 g:1mL, and controlling the proportion of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent to be 0.04g:1 mL-0.2 g:1 mL; i.e. the above-mentioned ratios are the ratio of the mass of the solid phase to the volume of the liquid phase.
Further, the alcohol reaction solvent is pure alcohol solvent or mixed solution of alcohol solvent and deionized water; in the alcohol reaction solvent, the volume percentage of the alcohol component is not less than 20 percent; and the alcohol component is preferably ethylene glycol.
It is worth noting that the alcohol reaction solvent in the present invention is effective for ultimately obtaining spheroidal MnCO3Is crucial, wherein the composition of the alcohol is very critical for controlling the product to exhibit a spherical morphology; in addition, in the alcohol reaction solvent, the dosage of the alcohol component can also have influence on the purity, the dispersibility and the particle size of a final product, namely, the purpose of regulating and controlling the performance of the product can be achieved by adjusting the specific composition of the alcohol reaction solvent.
The water-soluble manganese salt used in this step may be a divalent manganese salt soluble in water, such as manganese chloride, manganese sulfate, or manganese acetate.
In step S2, the reaction mixture is passed through CO2Reacting for 2-6 h at 60-80 ℃ to obtain a reaction product.
Specifically, control of CO2The feeding rate of (2) is 0.5L/min-2L/min.
In step S3, the reaction product is cooled and solid-liquid separated, and the obtained solid phase is washed and dried to obtain spherical MnCO3And (3) nano powder.
Preferably, the specific method for washing the solid phase is: washing the solid phase with deionized water for three times, and then washing the solid phase with absolute ethyl alcohol for one time; the specific method for drying the washed solid phase comprises the following steps: and (3) placing the washed solid phase in a vacuum drying oven, and drying for at least 8 hours at the temperature of 70-90 ℃.
In step S4, spherical MnCO is put into3The nano powder is roasted for at least 4 hours at the temperature of 350-650 ℃ in the air or oxygen atmosphere to obtain the micro-nano mesoporous spherical Mn2O3。
Thus, only the specific spherical MnCO can be used3The nano powder is simply roasted under specific roasting atmosphere, temperature and time to obtain the micro-nano mesoporous spherical Mn which simultaneously has good dispersibility, specific surface area and aperture distribution2O3. The obtained micro-nano mesoporous spherical Mn2O3Has a particle diameter of 0.5 to 2 μm and a specific surface area of not less than 36m2(ii)/g, the pore size distribution is 20nm to 25 nm.
The micro-nano mesoporous spherical Mn will be described by specific examples2O3The present invention is not limited thereto, and the following examples are only specific examples of the above-mentioned production method of the present invention, and are not intended to limit the entirety thereof.
Example 1
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.5g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.04g to 1mL, and the alcohol reaction solvent is formed by mixing 70mL of deionized water and 70mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2The introduction rate of (2) is 0.5L/min) at 60 ℃ for 6h to obtain a reaction product; s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
For the spherical MnCO of the present example3The nano powder was subjected to a field emission scanning electron microscope (hereinafter abbreviated as FE-SEM) test, and the results are shown in FIG. 2. As can be seen from FIG. 2, the spherical MnCO obtained in this example3The particle size of the nano powder is about 500 nm.
First, 1g of spherical MnCO3Placing the nano powder in a crucible; then, the crucible is put in a high-temperature electric furnace, the temperature is raised to 550 ℃ at the heating rate of 10 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 1.
For the spherical MnCO of the present example3Thermogravimetric analysis (hereinafter abbreviated as "TG") of the baking process of the nano powder was performed, and the result is shown in fig. 3. As can be seen from FIG. 3, the spherical MnCO3The weight loss of the nano powder is about 30 percent at the temperature of 250-500 ℃, mainly due to MnCO3And O2Conversion to Mn by reaction2O3I.e. 4MnCO3+O2→2Mn2O3+CO2The weight remained essentially unchanged after 500 ℃.
The product 1 was subjected to an X-ray diffraction test (hereinafter, abbreviated as XRD) and a scanning electron microscope test (hereinafter, abbreviated as SEM), and the results thereof are shown in fig. 4 and 5, respectively. As can be seen from FIG. 4, the appearance of characteristic peaks at 23.1 °, 32.9 °, 38.2 °, 45.1 °, 49.2 °, 53.3 °, 55.1 °, 60.7 °, 64.1 °, 65.7 °, 67.4 °, 68.9 ° and 73.9 ° 2 θ indicates that product 1 prepared under these conditions is Mn2O3 (JCPDS card No.71-0636) with unit cell parameters of Mn2O3 (JCPDS card No.71-0636)
α ═ β ═ γ ═ 90 °, no other miscellaneous peaks appeared in the XRD pictures, indicating that Mn produced under these conditions2O3Is a pure phase. FIG. 5 shows that the product 1 has a typical micro-nano structure, good dispersibility, uniform size and a particle size of about 500 nm; in comparison with FIG. 2, after firing under this condition, the spherical MnCO3The crystal structure of the nano powder is changed by MnCO3To Mn2O3However, the product 1 obtained is still in contact with spherical MnCO3The nano powder has the same shape, keeps the spherical shape unchanged, basically keeps the particle size unchanged, and is still about 500 nm.
Micro-nano mesoporous spherical Mn prepared in this example2O3Has a specific surface area of 37.18m2(ii)/g, the pore size distribution is 20nm to 25 nm.
Example 2
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.25g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.04g to 1mL, and the alcohol reaction solvent is 140mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2At an introduction rate of 1.8L/min) at 60 ℃ for 6h to obtainObtaining a reaction product; s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
The spherical MnCO obtained3The size of the nano powder is 0.5-2 μm.
First, 1g of spherical MnCO3Placing the nano powder in a crucible; then, the crucible is put in a high-temperature electric furnace, the temperature is raised to 350 ℃ at the heating rate of 10 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 2.
XRD measurements were performed on product 2, and the results are shown in fig. 6. As can be seen from FIG. 6, the appearance of characteristic peaks at 23.1 °, 32.9 °, 38.2 °, 42.9 °, 45.1 °, 49.3 °, 55.1 ° and 65.7 ° 2 θ indicates that the product 2 produced under these conditions had Mn as the major phase2O3(JCPDS card No.71-0636), but it has impurity peaks at 18.1, 21.7 and 28.7 degrees 2 theta, indicating that it contains a small amount of Mn3O4And MnO2Impurities and main phase Mn2O3The content of (A) is more than 80%.
Meanwhile, the micro-nano mesoporous spherical Mn prepared by the embodiment2O3Has a particle diameter of about 500nm and a specific surface area of 36.51m2(ii)/g, the pore size distribution is 20nm to 25 nm.
Example 3
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.5g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.2g to 1mL, and the alcohol reaction solvent is formed by mixing 110mL of deionized water and 30mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2The introduction rate of (2L/min) at 60 ℃ for 6h to obtain a reaction product; s3, cooling and carrying out solid-liquid separation on the reaction product to obtainWashing and drying the solid phase to obtain spherical MnCO3And (3) nano powder.
The spherical MnCO obtained3The average size of the nanopowder was 500 nm.
First, 1g of spherical MnCO3Placing the nano powder in a crucible; then, the crucible is put in a high-temperature electric furnace, the temperature is raised to 450 ℃ at the heating rate of 10 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 3.
XRD testing was performed on product 3, the results of which are shown in fig. 7. As can be seen from FIG. 7, it does not change much from FIG. 6, and the main phase of product 3 is Mn2O3While containing a small amount of Mn3O4And MnO2Impurities and main phase Mn2O3The content of (A) is more than 80%.
Meanwhile, the micro-nano mesoporous spherical Mn prepared by the embodiment2O3Has a particle diameter of about 700nm and a specific surface area of 36.28m2(ii)/g, the pore size distribution is 20nm to 25 nm.
Example 4
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.25g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.2g to 1mL, and the alcohol reaction solvent is 140mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2The introduction rate of (1.1L/min) at 60 ℃ for 4h to obtain a reaction product; s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
The spherical MnCO obtained3The size of the nano powder is about 500 nm.
First, 1g of spherical MnCO3Placing the nano powder in a crucible; however, the device is not suitable for use in a kitchenThen, the crucible is put in a high-temperature electric furnace, the temperature is raised to 650 ℃ at the heating rate of 10 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 4.
XRD test and SEM test were performed on the product 4, respectively, and the results are shown in fig. 8 and 9, respectively. As can be seen from FIG. 8, product 4 is Mn2O3Pure phase, where the impurity peaks disappeared compared to fig. 6, fig. 7. As can be seen from fig. 9, the spherical structure starts to exhibit a tendency to be broken, the crystal grains are refined, and an undesirable tendency to be easily agglomerated is exhibited, resulting in a decrease in dispersibility.
Meanwhile, the micro-nano mesoporous spherical Mn prepared by the embodiment2O3Has a particle diameter of about 800nm and a specific surface area of 36.07m2(ii)/g, the pore size distribution is 20nm to 25 nm.
It can be seen that the micro-nano mesoporous spherical Mn of the invention2O3The preparation method of (2) has the roasting temperature controlled to be 650 ℃ at most, and the spherical morphology cannot be maintained due to the higher roasting temperature.
Example 5
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.5g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.2g to 1mL, and the alcohol reaction solvent is formed by mixing 100mL of deionized water and 40mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2The introduction rate of (2) is 0.5L/min) at 60 ℃ for 6h to obtain a reaction product; s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
The spherical MnCO obtained3The average size of the nanopowder was 500 nm.
First of all, the first step is to,1g of spherical MnCO3Placing the nano powder in a crucible; then, the crucible is put in a high-temperature electric furnace, the temperature is raised to 550 ℃ at the heating rate of 1 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 5.
SEM testing was performed on product 5, the results of which are shown in figure 10. As can be seen from fig. 10, the morphology of the particles remained spherical, and the particle size remained around 500 nm.
Meanwhile, the micro-nano mesoporous spherical Mn prepared in the embodiment2O3Has a specific surface area of 38.24 m2(ii)/g, the pore size distribution is 20nm to 25 nm.
Example 6
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.5g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.2g to 1mL, and the alcohol reaction solvent is 140mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2The introduction rate of (1.5L/min) at 80 ℃ for 6h to obtain a reaction product; s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
The spherical MnCO obtained3The average size of the nano powder is about 500 nm.
First, 1g of spherical MnCO3Placing the nano powder in a crucible; then, the crucible is put in a high-temperature electric furnace, the temperature is raised to 550 ℃ at the heating rate of 5 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 6.
SEM testing was performed on product 6, the results of which are shown in figure 11. As can be seen from fig. 11, the morphology of the particles remained spherical, and the particle size remained around 500 nm.
Meanwhile, the micro-nano mesoporous spherical Mn prepared in the embodiment2O3Has a specific surface area of 38.09 m2(ii)/g, the pore size distribution is 20nm to 25 nm.
Example 7
This example uses spherical MnCO prepared in advance3The nanometer powder is used as a roasting raw material.
Specifically, the spherical MnCO3The specific preparation process of the nano powder comprises the following steps: s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the mass-volume ratio of the water-soluble manganese salt to the ammonia water is 0.5g to 1mL, the mass-volume ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.04g to 1mL, and the alcohol reaction solvent is formed by mixing 70mL of deionized water and 70mL of ethylene glycol; s2, introducing CO into the reaction mixture2(CO2The introduction rate of 1L/min) at 60-80 ℃ for 6h to obtain a reaction product; s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3And (3) nano powder.
The spherical MnCO obtained3The average size of the nano powder is about 500 nm.
First, 1g of spherical MnCO3Placing the nano powder in a crucible; then, the crucible is put in a high-temperature electric furnace, the temperature is raised to 550 ℃ at the heating rate of 20 ℃/min, and the crucible is subjected to heat preservation and roasting for 4 hours to obtain a roasted product; and finally, naturally cooling the roasted product to obtain a product 7.
SEM testing was performed on product 7, the results of which are shown in fig. 12. As can be seen from fig. 12, the morphology of the particles remained spherical, and the particle size remained around 500 nm.
In the preparation of the above-mentioned examples 1 to 7, the firing atmosphere was air, but it was changed to O2The reaction can be carried out under the atmosphere; it is to be noted, however, that the above-mentioned firing process cannot be carried out in an inert gas, and for this reason, the following comparative experiment was carried out.
Meanwhile, the micro-nano mesoporous spherical Mn prepared in the embodiment2O3Has a specific surface area of 36.88 m2(ii)/g, the pore size distribution is 20nm to 25 nm.
Comparative example 1
The parts of comparative example 1 which are the same as those of example 1 are not described again, and only the differences from example 1 will be described. Comparative example 1 is different from example 1 in that 1g of previously prepared spherical MnCO is added3Placing the nano powder in a crucible, placing the crucible in a tubular furnace, and introducing argon to ensure that roasting is carried out in an argon atmosphere; the remainder is described with reference to example 1, corresponding to the comparative product.
The comparative product was subjected to XRD test and SEM test, respectively, and the results are shown in fig. 13 and 14, respectively. As can be seen in FIG. 13, its appearance of characteristic peaks, in terms of 2 θ, at 18.0 °, 28.9 °, 31.0 °, 32.4 °, 36.5 °, 38.1 °, 44.4 °, 50.8 °, 53.9 °, 58.5 °, 60.0 ° and 64.6 ° indicates that the comparative product prepared under these conditions is Mn3O4(JCPDS card No.80-0382), the unit cell parameters were
α ═ β ═ γ ═ 90 °, no other miscellaneous peaks appeared in the XRD pictures, indicating that Mn produced under these conditions3O4Is a pure phase. As can be seen from FIG. 14, Mn was produced3O4The porous material also has a micro-nano porous structure, but the pore diameter is smaller.
Therefore, the method can be seen that when roasting is carried out in inert atmosphere such as argon, the micro-nano mesoporous spherical Mn to be prepared by the method cannot be prepared on the premise that other roasting conditions are not changed2O3So as to obtain micro-nano mesoporous spherical Mn3O4。
To illustrate the micro-nano mesoporous spherical Mn obtained by the preparation method of the invention2O3The micro-nano mesoporous spherical Mn prepared in the example 1 has better application effect due to good dispersibility, specific surface area and pore size distribution2O3As an adsorbent for adsorbing Congo red dye, the following was performedAnd (5) carrying out experiments.
Test experiment 1
Preparing 15mg of micro-nano mesoporous spherical Mn2O3Adding into 140mg/L Congo red solution for adsorption experiment, collecting supernatant at certain intervals for concentration measurement, and after adsorption balance, using formula Qt＝(C0 -Ct) V/W calculated adsorption amount, wherein QtIs the amount of adsorption at time t, C0Is the initial Congo Red concentration, CtThe concentration of Congo red at the time t, V the volume of the Congo red solution, and W the added micro-nano mesoporous spherical Mn2O3Mass of adsorbent.
Adsorption capacity QtThe relationship with time t is shown in FIG. 15; as can be seen from FIG. 15, the adsorption equilibrium is reached at about 120min, the adsorption capacity can reach 135.5mg/g, and the Congo red removal rate can reach 91.8%.
Test experiment 2
The micro-nano mesoporous spherical Mn in the test experiment 1 is adopted2O3The same adsorption experiment test is carried out on 20 mg/L-180 mg/L series Congo red solution.
Equilibrium adsorption capacity QeAnd initial Congo red concentration C0The relationship is shown in FIG. 16; as can be seen from FIG. 16, the maximum adsorption amount still reached 135 mg/g.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (6)
1. Micro-nano mesoporous spherical Mn2O3The method for preparing (1) is characterized by comprising the following steps:
the method comprises the following steps: preparation of spherical MnCO3A nanopowder comprising:
s1, dissolving water-soluble manganese salt and ammonia water in an alcohol reaction solvent to obtain a reaction mixture; wherein the ratio of the water-soluble manganese salt to the ammonia water is 0.25g to 1 mL-0.5 g to 1mL, and the ratio of the water-soluble manganese salt to the alcohol component in the alcohol reaction solvent is 0.04g to 1 mL-0.2 g to 1 mL; wherein the alcohol component is ethylene glycol, and the volume percentage of the alcohol component in the alcohol reaction solvent is not less than 20 percent;
s2, introducing CO into the reaction mixture2Reacting for 2-6 h at 60-80 ℃ under the condition of (1) to obtain a reaction product;
s3, cooling the reaction product, carrying out solid-liquid separation, washing and drying the obtained solid phase to obtain the spherical MnCO3Nano powder;
step two: the spherical MnCO3The nano powder is roasted for at least 4 hours at the temperature of 350-650 ℃ in the air or oxygen atmosphere to obtain the micro-nano mesoporous spherical Mn2O3(ii) a Wherein the spherical MnCO3The grain diameter of the nano powder is 0.5-2 μm.
2. The method according to claim 1, wherein in the step S2, CO2The feeding rate of (2) is 0.5L/min-2L/min.
3. The method according to claim 1, wherein in step S1, the water-soluble manganese salt is manganese chloride, manganese sulfate, or manganese acetate.
4. The method according to claim 1, wherein in step S3, the solid phase is washed by: washing the solid phase with deionized water for three times, and then washing the solid phase with absolute ethyl alcohol for one time; the specific method for drying the washed solid phase comprises the following steps: and (3) placing the washed solid phase in a vacuum drying oven to be dried for at least 8h at the temperature of 70-90 ℃.
5. The production method according to any one of claims 1 to 4, wherein the spherical MnCO is calcined3The temperature rising rate of the nano powder is 1-20 ℃/min.
6. According to the claimsThe preparation method of any one of claims 1 to 4, wherein the micro-nano mesoporous spherical Mn is2O3Has a particle diameter of 0.5-2 μm and a specific surface area of not less than 36m2(ii)/g, the pore size distribution is 20nm to 25 nm.
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