CN116002765A - Manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction and preparation method thereof - Google Patents
Manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction and preparation method thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 77
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 70
- 239000011029 spinel Substances 0.000 title claims abstract description 70
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 59
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 23
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- 239000002243 precursor Substances 0.000 claims abstract description 21
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 239000002184 metal Substances 0.000 claims abstract description 9
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- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 5
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- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 5
- 239000011565 manganese chloride Substances 0.000 claims abstract description 5
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- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 230000008439 repair process Effects 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- 238000012512 characterization method Methods 0.000 description 16
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 12
- 230000004913 activation Effects 0.000 description 10
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction and a preparation method thereof, belonging to the technical field of environmental repair functional materials. Firstly, manganese chloride and potassium permanganate are utilized to obtain an amorphous manganese dioxide nanoparticle precursor under an alkaline condition, then metal salt is used as a transition metal supply source, and manganese-based spinel material with a cubic structure is synthesized through reaction under the reduction condition of excessive sodium borohydride solution. The manganese-based cubic spinel material prepared by the method has lower electron transfer resistance, and the cooperative gain exists in the promotion of the regeneration cycle of transition metal and manganese oxidation reduction, so that the manganese-based cubic spinel material prepared by the method can efficiently activate the peroxymonosulfate, and realize the efficient removal of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of environmental repair functional materials, and particularly relates to a manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction and a preparation method thereof.
Background
At present, advanced oxidation technology is widely applied to the research and practice of repairing organic pollutants in environmental media. Based on sulfate radicals (SO 4 ·－ ) Advanced oxidation techniques of (2) are of general interest due to their higher oxidation potential, wider applicable pH range, more stable mass transfer capacity and greater durability. SO (SO) 4 ·－ Can be obtained by activating an oxidizing agent such as Peroxodisulfate (PS) or Peroxomonosulfate (PMS). Common activation methods include homogeneous activation methods such as transition metal ions, heat, light, alkali, etc., and heterogeneous activation methods such as metal oxides, activated carbon, etc.
However, the homogeneous activation of PS or PMS has irreparable drawbacks. For example, both thermal and uv activation are energy intensive processes, while alkali activation can result in a reaction system with too high a pH. In addition, too many transition metal ions can lead to SO 4 ·－ And inevitably produce a metal-containing sludge. Thus, heterogeneous catalysis has been widely investigated for activation of PS and PMS over the past decades. Heterogeneous catalysis has the advantages of energy conservation, easy operation, mild reaction conditions, less leaching of metal ions and the like. Among the heterogeneous catalyst materials, since the spinel-structured nanomaterial has a higher activation ability by controlling the structure, it has been widely studied and applied to form unique magnetic, electric and energy phase conversion characteristics.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction and a preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: a preparation method of a manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction comprises the following steps:
(1) Mixing a manganese chloride solution and a potassium permanganate solution under an alkaline condition to obtain a brown precipitate, and carrying out suction filtration, drying, grinding and sieving on the brown precipitate to obtain an amorphous manganese dioxide nanoparticle precursor;
(2) Mixing the amorphous manganese dioxide nanoparticle precursor obtained in the step (1) with a metal salt to obtain a solution A;
(3) Sodium borohydride is dissolved in sodium hydroxide solution to obtain solution B;
(4) Slowly dripping the solution B obtained in the step (3) into the solution A obtained in the step (2) to obtain a precipitate;
(5) And (3) carrying out suction filtration, washing, drying, grinding and sieving, roasting, and grinding and sieving again on the precipitate obtained in the step (4) to obtain the manganese-based cubic spinel material.
Further, in the step (1), the molar ratio of the manganese chloride solution to the potassium permanganate solution is 3:2.
Further, in step (1), the alkaline condition is ph=12.
Further, in the step (1), the temperature of the drying is 60 ℃ and the time is 12 hours; the grinding and sieving are carried out by a 200-mesh sieve.
Further, in step (2), the molar ratio of the amorphous manganese dioxide nanoparticle precursor to the metal salt is 1:2.
Further, in the step (2), the metal salt is CoCl 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O、CuSO 4 Or FeCl 3 ·6H 2 O。
Further, in the step (3), the concentration of the sodium hydroxide solution is 0.1mol/L, and the mass-volume ratio of the sodium borohydride to the sodium hydroxide solution is 2.0 g/0.1L.
Further, in the step (4), the slow dropping is as follows: solution B was added dropwise to solution A at a drop rate of 10 drops/min with stirring at a rate of 250 to 400 rpm.
Further, in the step (5), the washing is respectively washing the ethanol and the ultrapure water for 2 to 3 times; the drying temperature is 80 ℃ and the drying time is 12 hours; the grinding and sieving and the regrinding and sieving are both 200-mesh sieves; the roasting temperature is 300-400 ℃ and the roasting time is 8 hours.
The second technical scheme of the invention is as follows: the manganese-based cubic spinel material for the heterogeneous catalytic oxidation reaction is prepared by the preparation method of the manganese-based cubic spinel material for the heterogeneous catalytic oxidation reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts amorphous MnO 2 The nano particles are used as precursors, and the manganese-based cubic spinel material can be obtained based on the addition of different metal salts under the room temperature condition. The manganese-based cubic spinel material prepared by the method has lower electron transfer resistance, and the transition metal and Mn have cooperative gain on the improvement of regeneration cycle, so that the manganese-based cubic spinel material can efficiently activate PMS and realize the efficient removal of organic pollutants.
At room temperature, a low Mn ratio (0 to 1.3) results in a cubic spinel phase. Theoretically, since ≡mn (III) (3 d 4) in the octahedral voids of the cubic spinel lattice structure exhibits a lower Jahn-Teller effect, the crystal symmetry of cubic phase spinel is higher than that of tetragonal phase spinel, and thus heterogeneous catalytic ability thereof can be remarkably improved.
The invention uses amorphous MnO with short diffusion distance and large surface area 2 The nano particles are used as precursors, so that the promotion of solid diffusion and deep interface contact is realized. At the same time [ MnO ] 6 ]The formation of octahedral building blocks will affect the final state structure of the spinel material. [ MnO ] 6 ]The octahedron has lower activation energy barrier, is favorable for the lattice reconstruction of the random arrangement structural units and promotes the amorphous MnO 2 Transition to highly crystalline spinel.
The large amount of hydrogen generated in the reaction process of manganese dioxide and sodium borohydride enables the synthetic material to form a reticular porous structure, and the higher specific surface area and the porosity not only can improve the diffusion/mass transfer rate of the catalytic reaction, but also can effectively improve the trapping performance of pollutants and oxidants thereof; meanwhile, a large number of functional groups on the surface and in the pores of the material are used as active sites to effectively activate the oxidant, so that the efficient degradation of pollutants is realized; in addition, the active electron transfer process of the manganese-based cubic spinel material can effectively promote the redox circulation of metal elements in the structure, so that the utilization efficiency of the oxidant and the stability of the material structure are improved. The manganese-based cubic spinel material can be used as a heterogeneous catalyst for repairing organic pollutants in different environmental media.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the X-ray diffraction characterization result of the manganese-based cubic spinel material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope characterization of the manganese-based cubic spinel material prepared according to example 1 of the present invention;
FIG. 3 is a high resolution transmission electron microscope characterization of the manganese-based cubic spinel material prepared according to example 1 of the present invention;
FIG. 4 is an X-ray photoelectron spectrum characterization result of the manganese-based cubic spinel material prepared in example 1 of the present invention;
FIG. 5 is an X-ray diffraction characterization result of the manganese-based cubic spinel material prepared in example 2 of the present invention;
FIG. 6 is a scanning electron microscope characterization of the manganese-based cubic spinel material prepared according to example 2 of the present invention;
FIG. 7 is a high resolution transmission electron microscope characterization of the manganese-based cubic spinel material prepared according to example 2 of the present invention;
FIG. 8 is an X-ray photoelectron spectrum characterization result of the manganese-based cubic spinel material prepared in example 2 of the present invention;
FIG. 9 is an X-ray diffraction characterization result of the manganese-based cubic spinel material prepared in example 3 of the present invention;
FIG. 10 is a scanning electron microscope characterization of the manganese-based cubic spinel material prepared according to example 3 of the present invention;
FIG. 11 is a high resolution transmission electron microscope characterization of the manganese-based cubic spinel material prepared according to example 3 of the present invention;
FIG. 12 is an X-ray photoelectron spectrum characterization result of the manganese-based cubic spinel material prepared in example 3 of the present invention;
FIG. 13 is an X-ray diffraction characterization result of the manganese-based cubic spinel material prepared in example 4 of the present invention;
FIG. 14 is a scanning electron microscope characterization of the manganese-based cubic spinel material prepared according to example 4 of the present invention;
FIG. 15 is a high resolution transmission electron microscope characterization of the manganese-based cubic spinel material prepared according to example 4 of the present invention;
FIG. 16 is an X-ray photoelectron spectrum characterization result of the manganese-based cubic spinel material prepared in example 4 of the present invention;
FIG. 17 is a graph showing the X-ray diffraction pattern of the manganese-based tetragonal spinel material prepared according to comparative example 1 of the present invention;
FIG. 18 is a graph showing the X-ray diffraction pattern of the manganese-based tetragonal spinel material prepared according to comparative example 2 of the present invention;
FIG. 19 is a graph showing the X-ray diffraction pattern of the manganese-based tetragonal spinel material prepared according to comparative example 3 of the present invention;
FIG. 20 is a graph showing the X-ray diffraction pattern of the manganese-based tetragonal spinel material prepared according to comparative example 4 of the present invention;
FIG. 21 is a graph showing the effect of the cubic manganese-based cubic spinel material prepared in examples 1 to 4 of the present invention and the manganese-based tetragonal spinel material prepared in comparative examples 1 to 4 on catalyzing PMS to degrade volatile organic pollutants Trichloroethylene (TCE).
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In the examples below, the room temperature is 25.+ -. 2 ℃.
Example 1
Manganese-based cubic spinel material Co for heterogeneous catalytic oxidation reaction 2 MnO 4 Is prepared from
1) 3mol of MnCl 2 Solution and 2molKMnO 4 The solution was mixed homogeneously (ph=12 of the solution was controlled) to give a brown precipitate, brownFiltering the precipitate, oven drying at 60deg.C, grinding, and sieving with 200 mesh sieve to obtain amorphous MnO 2 A nanoparticle precursor;
2) 1mol of amorphous MnO obtained in step 1) 2 Nanoparticle precursors and 2molCoCl 2 ·6H 2 O is evenly mixed in ultrapure water, and magnetically stirred at room temperature to obtain solution A;
3) Will 2.0g NaBH 4 Dissolving in a NaOH solution of 0.1L0.1M to obtain a solution B;
4) Slowly adding the solution B obtained in the step 3) into the solution A obtained in the step 2) according to the dropping speed of 10 drops/min under the condition of rapid stirring speed of 400rpm to obtain a precipitate;
5) Filtering the precipitate obtained in the step 4), respectively washing with ethanol and ultrapure water for 2 times, vacuum drying at 80 ℃ for 12 hours, grinding, sieving with a 200-mesh sieve, roasting at 300 ℃ in a tubular furnace, grinding again, sieving with a 200-mesh sieve to obtain Co 2 MnO 4 (wherein the Mn element ratio is 1.0).
Co prepared in example 1 2 MnO 4 X-ray diffraction test, scanning electron microscope test, high resolution transmission electron microscope test and X-ray photoelectron spectrum test are carried out, the test results are shown in figures 1-4, and the characteristic diffraction peaks and Co of the synthetic material can be found from figures 1-4 2 MnO 4 The characteristic peaks of (JCCPDSNo. 23-1237) are consistent and have typical (311) crystal faces, the microstructure presents a nano sphere shape, and Co elements on the surface are Co 2+ And Co 3+ In the form of Mn element 3+ And Mn of 4+ The O element is mainly lattice oxygen and surface adsorption oxygen, indicating successful synthesis of the material.
Example 2
Manganese-based cubic spinel material Zn for heterogeneous catalytic oxidation reaction 2 MnO 4 Is prepared from
1) 3mol of MnCl 2 Solution and 2molKMnO 4 Uniformly mixing the solutions (controlling the pH of the solution to be=12) to obtain brown precipitate, filtering the brown precipitate, drying the brown precipitate at 60 ℃, grinding the brown precipitate and sieving the brown precipitate with a 200-mesh sieve to obtain amorphous MnO 2 A nanoparticle precursor;
2) 1mol of amorphous MnO obtained in step 1) 2 Nanoparticle precursor with 2mol Zn (NO 3 ) 2 ·6H 2 O is evenly mixed in ultrapure water, and magnetically stirred at room temperature to obtain solution A;
3) Will 2.0g NaBH 4 Dissolving in a NaOH solution of 0.1L0.1M to obtain a solution B;
4) Slowly adding the solution B obtained in the step 3) into the solution A obtained in the step 2) according to the dropping speed of 10 drops/min under the condition of rapid stirring speed of 400rpm to obtain a precipitate;
5) Filtering the precipitate obtained in the step 4), respectively washing with ethanol and ultrapure water for 2 times, vacuum drying at 80 ℃ for 12 hours, grinding, sieving with a 200-mesh sieve, roasting at 300 ℃ in a tube furnace, grinding again, sieving with a 200-mesh sieve, and obtaining the Zn 2 MnO 4 (wherein the Mn element ratio is 1.0).
For Zn prepared in example 2 2 MnO 4 X-ray diffraction test, scanning electron microscope test, high resolution transmission electron microscope test and X-ray photoelectron spectrum test are carried out, the test results are shown in figures 5-8, and the characteristic diffraction peak and Zn of the synthetic material can be found from figures 5-8 2 MnO 4 The characteristic peaks of (JCCPDSNo. 19-1495) are consistent and have typical (100) crystal faces, microcosmic structures and surface Zn elements as Zn 0 And Zn 2+ In the form of Mn element 3+ And Mn of 4+ The O element is mainly lattice oxygen and surface adsorption oxygen, indicating successful synthesis of the material.
Example 3
Manganese-based cubic spinel material Cu for heterogeneous catalytic oxidation reaction 2 MnO 4 Is prepared from
1) 3mol of MnCl 2 Solution and 2molKMnO 4 Uniformly mixing the solutions (controlling the pH of the solution to be=12) to obtain brown precipitate, filtering the brown precipitate, drying the brown precipitate at 60 ℃, grinding the brown precipitate and sieving the brown precipitate with a 200-mesh sieve to obtain amorphous MnO 2 A nanoparticle precursor;
2) 1mol of amorphous MnO obtained in step 1) 2 Nanoparticle precursors and 2mol CuSO 4 In the superUniformly mixing the materials in pure water, and magnetically stirring the materials at room temperature to obtain a solution A;
3) Will 2.0g NaBH 4 Dissolving in a NaOH solution of 0.1L0.1M to obtain a solution B;
4) Slowly adding the solution B obtained in the step 3) into the solution A obtained in the step 2) according to the dropping speed of 10 drops/min under the condition of rapid stirring speed of 400rpm to obtain a precipitate;
5) Filtering the precipitate obtained in the step 4), respectively washing with ethanol and ultrapure water for 2 times, vacuum drying at 80 ℃ for 12 hours, grinding, sieving with a 200-mesh sieve, roasting at 300 ℃ in a tube furnace, grinding again, sieving with a 200-mesh sieve to obtain Cu 2 MnO 4 (wherein the Mn element ratio is 1.0).
For Cu prepared in example 3 2 MnO 4 X-ray diffraction test, scanning electron microscope test, high resolution transmission electron microscope test and X-ray photoelectron spectrum test are carried out, the test results are shown in figures 9-12, and it can be found from figures 9-12 that the characteristic diffraction peak and Cu of the synthetic material 2 MnO 4 The characteristic peaks of (JCCPDSNo. 01-084-0543) are consistent and have typical (111) crystal face, microcosmic structure and Cu element on the surface + And Cu 2+ In the form of Mn element 3+ And Mn of 4+ The O element is mainly lattice oxygen and surface adsorption oxygen, indicating successful synthesis of the material.
Example 4
Manganese-based cubic spinel material Fe for heterogeneous catalytic oxidation reaction 2 MnO 4 Is prepared from
1) 3mol of MnCl 2 Solution and 2molKMnO 4 Uniformly mixing the solutions (controlling the pH of the solution to be=12) to obtain brown precipitate, filtering the brown precipitate, drying the brown precipitate at 60 ℃, grinding the brown precipitate and sieving the brown precipitate with a 200-mesh sieve to obtain amorphous MnO 2 A nanoparticle precursor;
2) 1mol of amorphous MnO obtained in step 1) 2 Nanoparticle precursors and 2mol FeCl 3 ·6H 2 O is evenly mixed in ultrapure water, and magnetically stirred at room temperature to obtain solution A;
3) Will 2.0g NaBH 4 Dissolving in a NaOH solution of 0.1L0.1M to obtain a solution B;
4) Slowly adding the solution B obtained in the step 3) into the solution A obtained in the step 2) according to the dropping speed of 10 drops/min under the condition of rapid stirring speed of 400rpm to obtain a precipitate;
5) Filtering the precipitate obtained in the step 4), respectively washing with ethanol and ultrapure water for 2 times, vacuum drying at 80 ℃ for 12 hours, grinding, sieving with a 200-mesh sieve, roasting at 300 ℃ in a tube furnace, grinding again, sieving with a 200-mesh sieve, and obtaining the Fe 2 MnO 4 (wherein the Mn element ratio is 1.0).
For Fe prepared in example 4 2 MnO 4 X-ray diffraction test, scanning electron microscope test, high resolution transmission electron microscope test and X-ray photoelectron spectrum test are carried out, the test results are shown in figures 13-16, and the characteristic diffraction peaks and Fe of the synthetic material can be found from figures 13-16 2 MnO 4 The characteristic peaks of (JCPSS No. 38-0435) are consistent and have typical (311) crystal faces, the microstructure presents a nano sphere shape, and the surface Fe element is Fe 2+ And Fe (Fe) 3+ In the form of Mn element 3+ And Mn of 4+ The O element is mainly lattice oxygen and surface adsorption oxygen, indicating successful synthesis of the material.
Comparative example 1
The same as in example 1, except that step 2) 2mol of the amorphous MnO obtained in step 1) 2 Nanoparticle precursors and 1mol cocl 2 ·6H 2 O is evenly mixed in ultrapure water, and magnetically stirred at room temperature to obtain solution A;
CoMn obtained in step 5) 2 O 4 (wherein the Mn element ratio is 2.0).
For CoMn prepared in comparative example 1 2 O 4 X-ray photoelectron spectroscopy was performed and the results are shown in FIG. 17, which demonstrate successful synthesis of the tetragonal spinel material.
Comparative example 2
As in example 2, 2mol of the amorphous MnO obtained in step 1) 2 Nanoparticle precursor with 1mol Zn (NO 3 ) 2 ·6H 2 O is uniformly mixed in ultrapure water and magnetic force is generated at room temperatureStirring to obtain a solution A; .
ZnMn obtained in step 5) 2 O 4 (wherein the Mn element ratio is 2.0)
ZnMn prepared in comparative example 2 2 O 4 An X-ray photoelectron spectroscopy test was performed and the results are shown in fig. 18, which demonstrate successful synthesis of the tetragonal spinel material.
Comparative example 3
The same as in example 3, except that step 2) was carried out by adding 2mol of the amorphous MnO obtained in step 1) 2 Nanoparticle precursor and 1mol CuSO 4 Uniformly mixing in ultrapure water, and magnetically stirring at room temperature to obtain a solution A;
CuMn obtained in step 5) 2 O 4 (wherein the Mn element ratio is 2.0)
For CuMn prepared in comparative example 3 2 O 4 X-ray photoelectron spectroscopy was performed and the results are shown in FIG. 19, which demonstrate successful synthesis of the tetragonal spinel material.
Comparative example 4
The same as in example 4, except that step 2) was carried out by adding 2mol of the amorphous MnO obtained in step 1) 2 Nanoparticle precursor and 1mol FeCl 3 ·6H 2 O is evenly mixed in ultrapure water, and magnetically stirred at room temperature to obtain solution A;
FeMn obtained in step 5) 2 O 4 (wherein the Mn element ratio is 2.0)
For FeMn prepared in comparative example 4 2 O 4 X-ray photoelectron spectroscopy was performed and the results are shown in FIG. 20, which demonstrate successful synthesis of the tetragonal spinel material.
Activation of PMS to remove TCE in water
100mL of TCE solution (kept sealed) having a concentration of 0.15mM was added to the conical flask, the manganese-based cubic spinel material and PMS prepared in examples 1 to 4 or the manganese-based tetragonal spinel material and PMS prepared in comparative examples 1 to 4 were added in a mass ratio of 1:2, 1mL of the reaction solution was collected at a set sampling time (15 min), filtered using a needle filter, rapidly filled into a brown vial containing 1mL of n-hexane solution, and the supernatant was taken after shaking for 1min to detect the TCE concentration. After the reaction is finished, the catalyst is recovered by adopting a magnetic separation method, washed by deionized water for 3 times, dried at 60 ℃ and then reused for the next round of experiments, and 5 times of experiments are continuously carried out.
The test results are shown in fig. 17, and it can be found from fig. 17 that the cubic spinel material exhibits higher catalytic performance than the tetragonal spinel. Wherein Co is 2 MnO 4 The PMS can be efficiently activated, the TCE removal rate of the first-round experiment is up to 99.9%, the TCE removal efficiency can still reach 90% after five times of repeated use, and the efficient catalytic performance and stable material structure of the cubic manganese-based spinel material are illustrated.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments, and any person skilled in the art, within the scope of the present invention, should be covered by the protection scope of the present invention by equally replacing or changing the technical scheme and the inventive concept thereof.
Claims (10)
1. A method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation reaction, which is characterized by comprising the following steps:
(1) Mixing a manganese chloride solution and a potassium permanganate solution under an alkaline condition to obtain a brown precipitate, and carrying out suction filtration, drying, grinding and sieving on the brown precipitate to obtain an amorphous manganese dioxide nanoparticle precursor;
(2) Mixing the amorphous manganese dioxide nanoparticle precursor obtained in the step (1) with a metal salt to obtain a solution A;
(3) Sodium borohydride is dissolved in sodium hydroxide solution to obtain solution B;
(4) Slowly dripping the solution B obtained in the step (3) into the solution A obtained in the step (2) to obtain a precipitate;
(5) And (3) carrying out suction filtration, washing, drying, grinding and sieving, roasting, and grinding and sieving again on the precipitate obtained in the step (4) to obtain the manganese-based cubic spinel material.
2. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (1), the molar ratio of the manganese chloride solution to the potassium permanganate solution is 3:2.
3. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (1), the alkaline condition is ph=12.
4. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (1), the drying temperature is 60 ℃ and the time is 12 hours.
5. The method of preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (2), the molar ratio of the amorphous manganese dioxide nanoparticle precursor to metal salt is 1:2.
6. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (2), the metal salt is CoCl 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O、CuSO 4 Or FeCl 3 ·6H 2 O。
7. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (3), the concentration of sodium hydroxide solution is 0.1mol/L, and the mass-to-volume ratio of sodium borohydride to sodium hydroxide solution is 2.0 g/0.1L.
8. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (4), the slow dropping is: solution B was added dropwise to solution A at a drop rate of 10 drops/min with stirring at a rate of 250 to 400 rpm.
9. The method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to claim 1, wherein in step (5), the washing is respectively washing with ethanol and ultrapure water 2 to 3 times; the drying temperature is 80 ℃ and the drying time is 12 hours; the roasting temperature is 300-400 ℃ and the roasting time is 8 hours.
10. A manganese-based cubic spinel material for heterogeneous catalytic oxidation prepared by the method for preparing a manganese-based cubic spinel material for heterogeneous catalytic oxidation according to any one of claims 1 to 9.
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