CN112604693B - Mesoporous manganese-based composite oxide and preparation method and application thereof - Google Patents
Mesoporous manganese-based composite oxide and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011572 manganese Substances 0.000 title claims abstract description 66
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- 150000002696 manganese Chemical class 0.000 claims abstract description 22
- -1 transition metal salt Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 117
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 99
- 238000003756 stirring Methods 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 26
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 26
- 239000011565 manganese chloride Substances 0.000 claims description 26
- 229940099607 manganese chloride Drugs 0.000 claims description 26
- 235000002867 manganese chloride Nutrition 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 159000000021 acetate salts Chemical class 0.000 claims description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical class [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001868 water Inorganic materials 0.000 abstract description 10
- 239000002905 metal composite material Substances 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 238000005303 weighing Methods 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000010941 cobalt Substances 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 11
- 238000003795 desorption Methods 0.000 description 11
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GHNRLPUEWCZDRA-UHFFFAOYSA-N manganese;methanol Chemical compound [Mn].OC GHNRLPUEWCZDRA-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- MHXYZGKQLPFRHQ-UHFFFAOYSA-N chloroform manganese Chemical compound [Mn].ClC(Cl)Cl MHXYZGKQLPFRHQ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AQNXACCXVLZMFJ-UHFFFAOYSA-N ethanol;manganese Chemical compound [Mn].CCO AQNXACCXVLZMFJ-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- HASMZALMSXEIIE-UHFFFAOYSA-N manganese;propan-2-ol Chemical compound [Mn].CC(C)O HASMZALMSXEIIE-UHFFFAOYSA-N 0.000 description 1
- ZMSZLDBJHSORJY-UHFFFAOYSA-N manganese;propan-2-one Chemical compound [Mn].CC(C)=O ZMSZLDBJHSORJY-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J35/615—
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a mesoporous manganese-based composite oxide and a preparation method and application thereof, belonging to the field of materials. The method comprises the steps of mixing organic solution of bivalent manganese salt and bivalent transition metal salt with organic solution of inorganic base containing organic amine, carrying out in-situ redox reaction, and carrying out precipitation, centrifugation, washing, drying and roasting treatment to obtain the mesoporous manganese-based composite oxide. The invention has the advantages of simple preparation process flow, rich raw materials and low cost, and is suitable for industrial application; the manganese-based composite oxide prepared by the method has high specific surface area and large pore volume, generates a large amount of stable oxygen vacancies, is used as an ozone decomposition catalyst, shows high-efficiency ozone decomposition activity, stability and water resistance at room temperature, and has important value in the fields of porous metal composite oxide material preparation and ozone treatment for preventing and treating atmospheric pollution.
Description
Technical Field
The invention relates to preparation of a porous metal composite oxide, in particular to a mesoporous manganese-based composite oxide and a preparation method and application thereof.
Background
Compared with the block-shaped metal oxide, the transition metal oxide nano material has a special nano effect under a mesoscopic scale, has a wide application prospect in the fields of catalysis, energy, medicine and the like, is concerned by researchers, and is still a hot spot of current research. The mesoporous transition metal composite oxide is a composite oxide material with a three-dimensional nano structure, has a high specific surface area, a large pore volume and a three-dimensionally communicated mesoporous structure, has good stability and can overcome the agglomeration of nanoparticles.
There are various methods for preparing the mesoporous transition metal composite oxide material, and common methods include a self-assembly template method, a hydrothermal method and the like. At present, the preparation methods of mesoporous transition metal composite oxides in literature reports include: (1) yuan, m.; shan, z.; tian, B.; tu, b.; yang, P.; zhao, D.preparation of high order meso WO3-TiO2 as matrix in matrix-associated laser desorption/ionization mass spectrometry, Microporous and meso Materials 2005; 78:37-41, the article reports that mesoporous tungsten oxide/titanium oxide composite oxide is prepared by utilizing a solvent evaporation induced self-assembly method and an acid-base pairing mode, and the specific surface area of the composite oxide is 150m2g-1(ii) a (2) Wang, n.; shen, k.; huang, l.; yu, x.; qian, w.; chu, W.simple Route for Synthesizing Ordered Mesoporous Ni-Ce-Al Oxide Materials and the same Catalytic Performance for Methane Dry Reforming to Hydrogen and Synthesis. ACS Catalysis 2013; 3:1638-51, the article reports that the mesoporous nickel-cerium-aluminum composite oxide is prepared by using an organic block copolymer as a soft template and adopting an organic-inorganic self-assembly method, and the specific surface of the composite oxide is 49m2 g-1。(3)Li,Y.；Liu,W.；Yan,R.；Liang,J.；Dong,T.；Mi,Y.；Wu,P.；Wang,Z.；Peng,H.；An,T.Hierarchical three-dimensionally ordered macroporous Fe-V binary metal oxide catalyst for low temperature selective catalytic reduction of NOx from marine diesel engine exhaust.Applied Catalysis B:Environmental 2019:118455。The article reports that the three-dimensional mesoporous iron-vanadium composite oxide is prepared by taking polymethyl methacrylate microspheres as a hard template and taking triblock copolymer F127 as a soft template, and the specific surface area is as follows. CN106966442A and CN 109437326A disclose methods for preparing mesoporous metal composite oxides, respectively, glucose and the like are used as organic structure directing agents or auxiliary agents for forming mesopores of the metal composite oxides, and the prepared composite oxides of cobalt, zirconium, cerium, cobalt and the like have the specific surface area of 200m at most2g-1. The mesoporous metal composite oxide prepared by the method utilizes organic matters such as surfactant and the like as pore-forming agents for forming mesopores, and simultaneously needs high-temperature roasting to remove a template, so that the preparation process is complicated, and the industrial application of the mesoporous metal composite oxide is limited.
Disclosure of Invention
The invention provides a mesoporous manganese-based composite oxide and a preparation method and application thereof aiming at the technical problems.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide a mesoporous manganese-based composite oxide, a preparation method thereof and application thereof in catalytic decomposition of ozone, aiming at the existing problems. The invention generates oxidation-reduction reaction in organic solvent, and in the presence of organic amine, inorganic metal salt is formed in situ for pore-forming to prepare the mesoporous manganese-based composite oxide, and the oxide has high specific surface area, contains a large amount of stable oxygen vacancies, and shows good catalytic performance in the ozone catalytic decomposition reaction at room temperature.
The invention provides a preparation method of a mesoporous manganese-based composite oxide, which comprises the following specific steps:
a preparation method of a mesoporous manganese-based composite oxide comprises the following steps:
(1) adding a divalent manganese salt and a divalent transition metal salt into an organic solvent, and stirring until the manganese salt and the transition metal salt are completely dissolved to obtain a metal salt organic solution;
wherein: divalent transition metal salt: the molar ratio of the divalent manganese salt is 0.01-5: 1;
(2) sequentially adding inorganic base and organic amine into an organic solvent, and stirring until the inorganic base is completely dissolved to obtain an inorganic base organic solution containing the organic amine;
wherein: the molar ratio of the organic amine to the inorganic base is 0.1-4: 1;
(3) adding the organic solution of inorganic base containing organic amine prepared in the step (2) into the organic solution of metal salt in the step (1), stirring to form turbid liquid, and centrifuging, washing and drying to obtain a precursor of the manganese-based composite oxide;
wherein: the molar ratio of the divalent manganese salt to the inorganic base is 1: 1-10;
(4) and (4) placing the manganese-based composite oxide precursor prepared in the step (3) into a tubular furnace for roasting treatment, and naturally cooling to room temperature after roasting is finished to obtain the mesoporous manganese-based composite oxide material.
A mesoporous manganese-based composite oxide is prepared by the following method:
(1) adding a divalent manganese salt and a divalent transition metal salt into an organic solvent, and stirring until the manganese salt and the transition metal salt are completely dissolved to obtain a metal salt organic solution;
wherein: divalent transition metal salt: the molar ratio of the divalent manganese salt is 0.01-5: 1;
(2) sequentially adding inorganic base and organic amine into an organic solvent, and stirring until the inorganic base is completely dissolved to obtain an inorganic base organic solution containing the organic amine;
wherein: the molar ratio of the organic amine to the inorganic base is 0.1-4: 1;
(3) adding the organic solution of inorganic base containing organic amine prepared in the step (2) into the organic solution of metal salt in the step (1), stirring to form turbid liquid, and centrifuging, washing and drying to obtain a precursor of the manganese-based composite oxide;
wherein: the molar ratio of the divalent manganese salt to the inorganic base is 1: 1-10;
(4) and (4) placing the manganese-based composite oxide precursor prepared in the step (3) into a tubular furnace for roasting treatment, and naturally cooling to room temperature after roasting is finished to obtain the mesoporous manganese-based composite oxide material.
The technical scheme of the invention is as follows: the divalent manganese salt in the step (1) is manganese chloride or manganese acetate; the divalent transition metal salt is one of magnesium salt, iron salt, cobalt salt, nickel salt, copper salt and zinc salt.
The technical scheme of the invention is as follows: the divalent transition metal salt in step (1) is in the form of a chloride salt, a nitrate salt or an acetate salt.
The technical scheme of the invention is as follows: the mole ratio of the divalent transition metal to the divalent manganese in the step (1) is (0.05-3): 1. preferably, the method comprises the following steps: the molar ratio of the divalent transition metal, the divalent manganese and the organic solvent in the step (1) is (0.05-3): 1: (70-300).
The technical scheme of the invention is as follows: the organic solvent in the step (1) is one of methanol, ethanol, isopropanol, DMF, diethyl ether, acetone, chloroform and acetonitrile.
The technical scheme of the invention is as follows: in the step (2), the inorganic base is one of lithium hydroxide, sodium hydroxide and potassium hydroxide, and the organic amine is one of triethylamine, ethylenediamine and n-butylamine.
The technical scheme of the invention is as follows: the molar ratio of the organic amine to the inorganic base in the step (2) is (0.1-2): 1. preferably, the method comprises the following steps: the mol ratio of the organic amine, the inorganic base and the organic solvent in the step (2) is (0.1-2): 1: (50-120).
The technical scheme of the invention is as follows: the molar ratio of the divalent manganese salt to the inorganic base is 1: 2 to 7.
The technical scheme of the invention is as follows: the gas in the roasting treatment in the step (4) is one of nitrogen, hydrogen and carbon monoxide, the roasting temperature is 150-.
The technical scheme of the invention is as follows: the composite oxide prepared by the method is applied to the aspect of ozone decomposition catalysis.
The invention has the beneficial effects that:
the preparation method is simple, low in cost and rich in raw materials; the prepared mesoporous manganese-based composite oxide has high specific surface area and large pore volume, and the surface of the mesoporous manganese-based composite oxide contains a large amount of stable oxygen vacancies. The composite oxide catalyzes ozone at room temperature to show high-efficiency and stable catalytic performance, and the ozone decomposition rate is more than 99 percent. In addition, the catalyst has high stability against water. Is especially suitable for treating ozone in preventing and treating air pollution.
Drawings
Fig. 1 shows a nitrogen adsorption curve of the mesoporous nickel-manganese composite oxide material prepared in example 1.
Fig. 2 is a transmission electron microscope image of the mesoporous nickel-manganese composite oxide material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1:
(1) weighing 0.13g of nickel chloride and 1.26g of manganese chloride, sequentially adding the nickel chloride and the manganese chloride into 36.8g of ethanol, and stirring until the nickel chloride and the manganese chloride are completely dissolved to obtain a nickel and manganese mixed ethanol solution; wherein the molar ratio of nickel, manganese and ethanol is 0.1: 1: 80.
(2) respectively weighing 0.51g of triethylamine and 1.0g of sodium hydroxide, adding the triethylamine and the 1.0g of sodium hydroxide into 103.5g of ethanol, and stirring until the sodium hydroxide is completely dissolved to obtain an organic solution of the sodium hydroxide; wherein the molar ratio of triethylamine to sodium hydroxide to ethanol is 0.2: 1: 90.
(3) adding the sodium hydroxide organic solution obtained in the step (2) into the nickel and manganese ethanol solution obtained in the step (1), stirring for 7 hours at the temperature of 20 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a nickel-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali sodium hydroxide is 1: 2.5.
(4) placing the nickel-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting for 6 hours at 200 ℃ in a nitrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain the mesoporous nickel-manganese composite oxide material, wherein the nitrogen adsorption and desorption curve is shown in figure 1, and the specific surface area is 131m2g-1The ozone decomposition rate of the catalyst is 100% at 25 ℃, and the ozone decomposition rate is 99.5% after 24h of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 2:
(1) weighing 0.65g of cobalt chloride and 1.26g of manganese chloride, sequentially adding the cobalt chloride and the manganese chloride into 89.6g of methanol, and stirring until the cobalt chloride and the manganese chloride are completely dissolved to obtain a cobalt and manganese methanol solution; wherein the molar ratio of cobalt, manganese and methanol is 0.5: 1: 280.
(2) respectively weighing 1.89g of ethylenediamine and 1.96g of potassium hydroxide, adding the ethylenediamine and the potassium hydroxide into 123.2g of methanol, and stirring until the potassium hydroxide is completely dissolved to obtain an organic solution of potassium hydroxide; wherein the molar ratio of ethylenediamine, potassium hydroxide and methanol is 0.9: 1: 110.
(3) adding the potassium hydroxide organic solution obtained in the step (2) into the cobalt and manganese methanol solution obtained in the step (1), stirring for 5 hours at 40 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a cobalt-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the potassium hydroxide is 1: 3.5.
(4) placing the cobalt-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting at 250 ℃ for 5 hours in nitrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain a mesoporous cobalt-manganese composite oxide material, and measuring the specific surface area of the mesoporous cobalt-manganese composite oxide material to be 164m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.8% at 25 ℃, and the ozone decomposition rate is tested to be 99.3% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 3:
(1) weighing 0.95g of zinc nitrate and 1.26g of manganese chloride, sequentially adding the zinc nitrate and the manganese chloride into 146g of DMF, and stirring until the zinc nitrate and the manganese chloride are completely dissolved to obtain a DMF solution of zinc and manganese; wherein the molar ratio of zinc, manganese and DMF is 0.5: 1: 200.
(2) respectively weighing 2.92g of n-butylamine and 1.6g of sodium hydroxide, adding into 175.2g of DMF, and stirring until the sodium hydroxide is completely dissolved to obtain an organic solution of sodium hydroxide; wherein the molar ratio of n-butylamine to sodium hydroxide to DMF is 1: 1: 60.
(3) adding the sodium hydroxide organic solution obtained in the step (2) into the DMF solution of zinc and manganese obtained in the step (1), stirring for 4 hours at 50 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a zinc-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali sodium hydroxide is 1: 4.
(4) will be provided withPlacing the zinc-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting at 400 ℃ for 2 hours in nitrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain the mesoporous zinc-manganese composite oxide material, and measuring the specific surface area to be 157m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.1% at 25 ℃, and the ozone decomposition rate is tested to be 98.3% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 4:
(1) weighing 1.74g of ferrous acetate and 1.26g of manganese chloride, sequentially adding the ferrous acetate and the manganese chloride into 145g of acetone, and stirring until the ferrous acetate and the manganese chloride are completely dissolved to obtain an acetone solution of iron and manganese; wherein the molar ratio of iron to manganese to DMF is 1: 1: 250.
(2) respectively weighing 4.93g of n-butylamine and 1.8g of sodium hydroxide, adding into 208.8g of acetone, and stirring until the sodium hydroxide is completely dissolved to obtain an organic solution of the sodium hydroxide; wherein the molar ratio of n-butylamine, sodium hydroxide and acetone is 1.5: 1: 80.
(3) adding the sodium hydroxide organic solution obtained in the step (2) into the iron and manganese acetone solution obtained in the step (1), stirring for 8 hours at 10 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain an iron-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali sodium hydroxide is 1: 4.5.
(4) placing the iron-manganese composite oxide precursor obtained in the step (3) in a tubular furnace, roasting for 4 hours at 300 ℃ in a hydrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain a mesoporous iron-manganese composite oxide material, and measuring the specific surface area to be 157m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.4% at 25 ℃, and the ozone decomposition rate is tested to be 98.9% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 5:
(1) weighing 2.69g of copper chloride and 1.73g of manganese acetate, sequentially adding the copper chloride and the manganese acetate into 131.34g of chloroform, and stirring until the copper chloride and the manganese acetate are completely dissolved to obtain chloroform solutions of copper and manganese; wherein the molar ratio of copper, manganese and chloroform is 2: 1: 110.
(2) respectively weighing 3.29g of triethylamine and 3.64g of potassium hydroxide, adding the triethylamine and the potassium hydroxide into 234g of chloroform, and stirring until the potassium hydroxide is completely dissolved to obtain an organic solution of potassium hydroxide; wherein the molar ratio of n-butylamine, potassium hydroxide and chloroform is 0.5: 1: 60.
(3) adding the potassium hydroxide organic solution in the step (2) into the copper and manganese chloroform solution in the step (1), stirring for 2 hours at 80 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a copper-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali potassium hydroxide is 1: 6.5.
(4) placing the copper-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting at 450 ℃ for 1.5h in a carbon monoxide atmosphere, naturally cooling to room temperature after roasting is finished to obtain a mesoporous copper-manganese composite oxide material, and measuring the specific surface area to be 143m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.8% at 25 ℃, and the ozone decomposition rate is tested to be 99.5% after 24h of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 6:
(1) weighing 1.30g of cobalt chloride and 1.73g of manganese acetate, sequentially adding the cobalt chloride and the manganese acetate into 115.08g of acetonitrile, and stirring until the cobalt chloride and the manganese acetate are completely dissolved to obtain a chloroform solution of cobalt and manganese; wherein the molar ratio of cobalt to manganese to chloroform is 1: 1: 280.
(2) respectively weighing 1.01g of triethylamine and 2.8g of potassium hydroxide, adding the triethylamine and the potassium hydroxide into 164.4g of acetonitrile, and stirring until the potassium hydroxide is completely dissolved to obtain an organic solution of potassium hydroxide; wherein the molar ratio of triethylamine to potassium hydroxide to acetonitrile is 0.2: 1: 80.
(3) adding the potassium hydroxide organic solution obtained in the step (2) into the cobalt and manganese acetonitrile solution obtained in the step (1), stirring for 1h at 90 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a cobalt-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali potassium hydroxide is 1: 5.
(4) placing the cobalt-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting at 450 ℃ for 1.5h in the atmosphere of carbon monoxide, and naturally cooling to room temperature after roasting to obtain the mesoporous cobalt-manganese composite oxide materialThe specific surface area of the material is 172m measured by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.2% at 25 ℃, and the ozone decomposition rate is tested to be 98.7% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 7:
(1) weighing 0.06g of magnesium chloride and 1.26g of manganese chloride, sequentially adding the magnesium chloride and the manganese chloride into 90g of isopropanol, and stirring until the magnesium chloride and the manganese chloride are completely dissolved to obtain an isopropanol solution of magnesium and manganese; wherein the molar ratio of magnesium, manganese and isopropanol is 0.06: 1: 150.
(2) respectively weighing 0.96g of ethylenediamine and 1.6g of sodium hydroxide, adding into 192g of isopropanol, and stirring until the sodium hydroxide is completely dissolved to obtain an organic solution of sodium hydroxide; wherein the molar ratio of ethylenediamine to sodium hydroxide to isopropanol is 0.4: 1: 80.
(3) adding the sodium hydroxide organic solution obtained in the step (2) into the magnesium and manganese isopropanol solution obtained in the step (1), stirring for 9 hours at the temperature of 0 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a magnesium-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali potassium hydroxide is 1: 4.
(4) placing the magnesium-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting at 300 ℃ for 3h in nitrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain the mesoporous magnesium-manganese composite oxide material, and measuring the specific surface area to be 136m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.1% at 25 ℃, and the ozone decomposition rate is tested to be 98.3% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Example 8:
(1) weighing 0.63g of nickel chloride and 1.26g of manganese chloride, sequentially adding into 111g of diethyl ether, and stirring until the nickel chloride and the manganese chloride are completely dissolved to obtain diethyl ether solution of the nickel and the manganese; wherein the molar ratio of nickel, manganese and diethyl ether is 0.5: 1: 150.
(2) respectively weighing 2.92g of n-butylamine and 1.6g of sodium hydroxide, adding into 207.2g of diethyl ether, and stirring until the sodium hydroxide is completely dissolved to obtain an organic solution of the sodium hydroxide; wherein the molar ratio of n-butylamine to sodium hydroxide to diethyl ether is 1: 1: 70.
(3) adding the sodium hydroxide organic solution obtained in the step (2) into the nickel and manganese ether solution obtained in the step (1), stirring for 3 hours at the temperature of 60 ℃ to form turbid liquid, and centrifuging, washing and drying to obtain a nickel-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the inorganic alkali potassium hydroxide is 1: 4.
(4) placing the magnesium-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting for 5h at 200 ℃ in the atmosphere of carbon monoxide, naturally cooling to room temperature after roasting is finished to obtain the mesoporous nickel-manganese composite oxide material, and measuring the specific surface area to be 183m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 99.7% at 25 ℃, and the ozone decomposition rate is tested to be 99.1% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Comparative example 1:
(1) weighing 0.13g of nickel chloride and 1.26g of manganese chloride, sequentially adding the nickel chloride and the manganese chloride into 14.4g of water, and stirring until the nickel chloride and the manganese chloride are completely dissolved to obtain a nickel and manganese aqueous solution; wherein the molar ratio of nickel, manganese and water is 0.1: 1: 80.
(2) weighing 1.0g of sodium hydroxide, adding the sodium hydroxide into 40.5g of water, and stirring until the sodium hydroxide is completely dissolved to obtain a sodium hydroxide aqueous solution; wherein the molar ratio of sodium hydroxide to water is 1: 90.
(3) adding the sodium hydroxide aqueous solution obtained in the step (2) into the nickel and manganese aqueous solution obtained in the step (1), stirring for 7 hours at the temperature of 20 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a nickel-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the added sodium hydroxide is 1: 2.5.
(4) placing the nickel-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting for 6 hours at 200 ℃ in nitrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain a nickel-manganese composite oxide material, and measuring the specific surface area of the nickel-manganese composite oxide material to be 46m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 80.2% at 25 ℃, and the ozone decomposition rate is 57.3% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Comparative example 2:
(1) weighing 0.65g of cobalt chloride and 1.26g of manganese chloride, sequentially adding the cobalt chloride and the manganese chloride into 50.4g of water, and stirring until the cobalt chloride and the manganese chloride are completely dissolved to obtain a cobalt and manganese aqueous solution; wherein the molar ratio of cobalt, manganese and water is 0.5: 1: 280.
(2) weighing 1.96g of potassium hydroxide, adding the potassium hydroxide into 69.3g of water, and stirring until the potassium hydroxide is completely dissolved to obtain a potassium hydroxide aqueous solution; wherein the molar ratio of potassium hydroxide to water is 1: 110.
(3) adding the potassium hydroxide aqueous solution obtained in the step (2) into the cobalt and manganese aqueous solution obtained in the step (1), stirring for 5 hours at 40 ℃ to form a turbid solution, and centrifuging, washing and drying to obtain a cobalt-manganese composite oxide precursor; wherein the molar ratio of the added manganese to the potassium hydroxide is 1: 3.5.
(4) placing the cobalt-manganese composite oxide precursor obtained in the step (3) in a tube furnace, roasting at 250 ℃ for 5 hours in nitrogen atmosphere, naturally cooling to room temperature after roasting is finished to obtain a cobalt-manganese composite oxide material, and measuring the specific surface area of the cobalt-manganese composite oxide material to be 37m by nitrogen adsorption and desorption2g-1The ozone decomposition rate of the catalyst is tested to be 75.4% at 25 ℃, and the ozone decomposition rate is 49.5% after 24 hours of catalytic ozone decomposition reaction under the condition of 60% humidity.
Claims (7)
1. A preparation method of mesoporous manganese-based composite oxide is characterized by comprising the following steps: the preparation method of the mesoporous manganese-based composite oxide comprises the following steps:
(1) adding a divalent manganese salt and a divalent transition metal salt into an organic solvent, and stirring until the manganese salt and the transition metal salt are completely dissolved to obtain a metal salt organic solution;
wherein: divalent transition metal salt: the molar ratio of the divalent manganese salt is 0.01-5: 1;
(2) sequentially adding inorganic base and organic amine into an organic solvent, and stirring until the inorganic base is completely dissolved to obtain an inorganic base organic solution containing the organic amine;
wherein: the molar ratio of the organic amine to the inorganic base is 0.1-4: 1;
(3) adding the organic solution of inorganic base containing organic amine prepared in the step (2) into the organic solution of metal salt in the step (1), stirring to form turbid liquid, and centrifuging, washing and drying to obtain a precursor of the manganese-based composite oxide;
wherein: the molar ratio of the divalent manganese salt to the inorganic base is 1: 1-10;
(4) placing the manganese-based composite oxide precursor prepared in the step (3) into a tubular furnace for roasting treatment, and naturally cooling to room temperature after roasting to obtain a mesoporous manganese-based composite oxide material;
wherein: in the step (2), the inorganic base is one of lithium hydroxide, sodium hydroxide and potassium hydroxide, and the organic amine is one of triethylamine, ethylenediamine and n-butylamine;
the divalent manganese salt in the step (1) is manganese chloride or manganese acetate; the divalent transition metal salt is one of ferric salt, cobalt salt, nickel salt, copper salt and zinc salt; the divalent transition metal salt is in the form of a chloride, nitrate or acetate salt;
the gas in the roasting treatment in the step (4) is one of nitrogen, hydrogen and carbon monoxide, the roasting temperature is 150-.
2. The method of claim 1, wherein: the molar ratio of the divalent transition metal to the divalent manganese is (0.05-3): 1.
3. the method of claim 1, wherein: the organic solvent in the step (1) is one of methanol, ethanol, isopropanol, DMF, diethyl ether, acetone, chloroform and acetonitrile.
4. The method of claim 1, wherein: the molar ratio of the organic amine to the inorganic base in the step (2) is (0.1-2): 1.
5. the method of claim 1, wherein: the molar ratio of the divalent manganese salt to the inorganic base is 1: 2 to 7.
6. A mesoporous manganese-based composite oxide characterized by: the mesoporous manganese-based composite oxide is prepared by the following method:
(1) adding a divalent manganese salt and a divalent transition metal salt into an organic solvent, and stirring until the manganese salt and the transition metal salt are completely dissolved to obtain a metal salt organic solution;
wherein: divalent transition metal salt: the molar ratio of the divalent manganese salt is 0.01-5: 1;
(2) sequentially adding inorganic base and organic amine into an organic solvent, and stirring until the inorganic base is completely dissolved to obtain an inorganic base organic solution containing the organic amine;
wherein: the molar ratio of the organic amine to the inorganic base is 0.1-4: 1;
(3) adding the organic solution of inorganic base containing organic amine prepared in the step (2) into the organic solution of metal salt in the step (1), stirring to form turbid liquid, and centrifuging, washing and drying to obtain a precursor of the manganese-based composite oxide;
wherein: the molar ratio of the divalent manganese salt to the inorganic base is 1: 1-10;
(4) placing the manganese-based composite oxide precursor prepared in the step (3) into a tubular furnace for roasting treatment, and naturally cooling to room temperature after roasting to obtain a mesoporous manganese-based composite oxide material;
wherein: in the step (2), the inorganic base is one of lithium hydroxide, sodium hydroxide and potassium hydroxide, and the organic amine is one of triethylamine, ethylenediamine and n-butylamine;
the divalent manganese salt in the step (1) is manganese chloride or manganese acetate; the divalent transition metal salt is one of ferric salt, cobalt salt, nickel salt, copper salt and zinc salt; the divalent transition metal salt is in the form of a chloride, nitrate or acetate salt;
the gas in the roasting treatment in the step (4) is one of nitrogen, hydrogen and carbon monoxide, the roasting temperature is 150-.
7. The use of the composite oxide prepared by the method according to claim 1 as a catalyst for catalytic decomposition of ozone.
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