CN111268738A - Preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide - Google Patents
Preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide Download PDFInfo
- Publication number
- CN111268738A CN111268738A CN202010158162.3A CN202010158162A CN111268738A CN 111268738 A CN111268738 A CN 111268738A CN 202010158162 A CN202010158162 A CN 202010158162A CN 111268738 A CN111268738 A CN 111268738A
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- gamma
- reaction
- crystal
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 273
- 239000013078 crystal Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 5
- 239000000243 solution Substances 0.000 claims description 89
- 238000001035 drying Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- NDTYTMIUWGWIMO-UHFFFAOYSA-N perillyl alcohol Chemical compound CC(=C)C1CCC(CO)=CC1 NDTYTMIUWGWIMO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 5
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229930007631 (-)-perillyl alcohol Natural products 0.000 claims description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 2
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 claims description 2
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000005693 perillyl alcohol Nutrition 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 abstract description 3
- 229910006287 γ-MnO2 Inorganic materials 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 66
- 238000003756 stirring Methods 0.000 description 65
- 239000008367 deionised water Substances 0.000 description 37
- 229910021641 deionized water Inorganic materials 0.000 description 37
- 239000012065 filter cake Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 29
- 229910001868 water Inorganic materials 0.000 description 29
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 229940099596 manganese sulfate Drugs 0.000 description 26
- 239000011702 manganese sulphate Substances 0.000 description 26
- 235000007079 manganese sulphate Nutrition 0.000 description 26
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 26
- 238000005303 weighing Methods 0.000 description 24
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000000227 grinding Methods 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000002745 absorbent Effects 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 9
- 235000019445 benzyl alcohol Nutrition 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 6
- 239000011565 manganese chloride Substances 0.000 description 6
- 235000002867 manganese chloride Nutrition 0.000 description 6
- 229940099607 manganese chloride Drugs 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- -1 ketone compound Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RUMOYJJNUMEFDD-UHFFFAOYSA-N perillyl aldehyde Chemical compound CC(=C)C1CCC(C=O)=CC1 RUMOYJJNUMEFDD-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical class ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- LDCYZAJDBXYCGN-VIFPVBQESA-N 5-hydroxy-L-tryptophan Chemical compound C1=C(O)C=C2C(C[C@H](N)C(O)=O)=CNC2=C1 LDCYZAJDBXYCGN-VIFPVBQESA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- RYGHNMANMHVMMN-UHFFFAOYSA-N benzene-1,4-diol;terephthalic acid Chemical compound OC1=CC=C(O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 RYGHNMANMHVMMN-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/298—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with manganese derivatives
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The inventionDisclosed is a preparation method of gamma-crystal manganese dioxide, which comprises the step of carrying out alkali treatment on a manganous salt solution before the manganous salt solution and a potassium permanganate aqueous solution are mixed and reacted. The invention also discloses gamma-crystal manganese dioxide prepared by the preparation method of gamma-crystal manganese dioxide and a preparation method of unsaturated aldehyde by using gamma-crystal manganese dioxide prepared by the preparation method of gamma-crystal manganese dioxide. The invention has the advantage that H is reduced when alkali is added+So as to facilitate the combination of manganese positive ions and oxygen negative ions to generate gamma-MnO2. The gamma crystal form manganese dioxide synthesized by the method is used as a catalyst, and the allyl (benzyl) alcohol can be efficiently catalyzed and oxidized into corresponding aldehyde. Compared with the existing literature reports, the invention has the characteristics of cheap and easily available raw materials, clear catalyst crystal form, good selectivity and mild reaction conditions.
Description
Technical Field
The invention relates to the technical field of gamma-crystal manganese dioxide, in particular to a preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide.
Background
Manganese dioxide is black, black brown amorphous powder or crystal, and is insoluble in water, weak acid and weak base; it is insoluble in water, nitric acid and cold sulfuric acid, and is dissolved in hot concentrated hydrochloric acid to produce chlorine gas. Manganese dioxide is an amphoteric oxide that exhibits oxidation in the presence of a reducing agent and reduction in the presence of a strong oxidizing agent. Manganese dioxide has a wide variety of applications and has important applications in the chemical industry, such as a negative electrode in dry cells; the compound is used as an oxidant in organic synthesis reaction, nonferrous metal hydrometallurgy, hydroquinone (terephthalic acid) production and uranium extraction; used as oxidant and glaze color in the production of ceramics and enamel; the glass is used for eliminating impurities and manufacturing decorative glass in glass production; can be used as a catalyst in polymer polymerization reaction. Manganese dioxide is complex in chemical composition, not entirely stoichiometric, and generally contains a small amount of Mn2O3,Mn3O4And water of hydration, usually expressed as MnO in its formulax. Wherein X is an oxygen content, typically X is less than 2[ Wu, N.L. Nanocrystalline oxide supercapacitors [ J ]].Materials Chemistry and Physics,2002,75,6-11]Manganese dioxide crystal structures, roughly classified into 3 categories, namely one-dimensional tunnel structures, two-dimensional layered structures and three-dimensional network structures, exist 5 crystals (three kinds of one-dimensional tunnel structures, namely α, γ, three kinds of crystal forms, 1 kind of two-dimensional tunnel structures, namely δ crystal forms, and 1 kind of three-dimensional tunnel structures, namely λ crystal forms) and more than 30 kinds of paracrystals [ Xixi, crystal structures, preparation and discharge properties (1) of manganese dioxide and related manganese oxides [ J xi, J]Batteries 2004,6(34):411 and 414]. MnO of different crystal forms2Are substantially identical, but differ greatly in their properties due to differences in lattice structure and unit cell parameters, i.e., geometry and size. According to the preparation method, manganese dioxide can be classified into Natural Manganese Dioxide (NMD) and synthetic manganese dioxide, which can be classified into Electrolytic Manganese Dioxide (EMD) and chemically synthetic manganese dioxide (CMD), including activated manganese dioxide.
Manganese dioxide, which is a mild oxidant when used as an oxidant, has excellent selectivity in oxidizing allyl (benzyl) alcohol, and can oxidize allyl (benzyl) alcohol to its corresponding aldehyde or ketone compound, but is difficult to further oxidize, i.e., manganese dioxide can only oxidize allyl (benzyl) alcohol to aldehyde or ketone compounds without oxidizing it to carboxylic acid compounds. Due to its excellent selectivity, the research on the oxidizability of manganese dioxide has been paid attention to the chemist. The earliest use of manganese dioxide as an oxidizing agent was a study published in biochem.J. by Ball S. et al, Liftu university, 1948 [ students on vitamin A:5.The preparation of triptene 1-vitamine aldehyde]Since then, The research of manganese dioxide as an oxidizing agent has been continued, as described in ① The Journal of organic Chemistry,1959,24(8):1051, ② Proc. chem. Soc, 1964, 110, ③ chem. Soc, 1969, 188-194, ④ Angew. chem, 1973, 85: 401-402, ⑤ patent BE804618A,1974, ⑥ patent JP51071299A,1976, ⑦ chem. Commun. 1999,1337, ⑧ tetrahedronSynthesis of perillaldehyde [ J ] by selective oxidation of perillyl alcohol with ron Lett,2003,44,115, ⑨ active manganese dioxide]Synthetic chemistry, 2004, 12: 408; ⑩ Organic Letters,2009,11(6): 1229-1231;Synlett,2010,602;Catal.Sci.Technol.,2017,10,1039.]and so on.
Although manganese dioxide has good selective oxidation capability, the sources and preparation methods of manganese dioxide used in the current research reports are different, and the crystal structure of manganese dioxide is not described in detail, which is collectively called "active manganese dioxide" (as the Sholim Master thesis: the preparation of active manganese dioxide and the research on its selective oxidation capability), but the name "active manganese dioxide" is not strict.
The earliest reference to "active manganese Dioxide (active manganese Dioxide)" was a patent in 1974 with the patent number being BE804618A, entitled "monolithic activated catalytic catalyst-modifying catalyst" and the 1976 with the patent number JP51071299A, entitled "Pre-of activated catalytic catalyst and acid catalytic salt" indicating the manganese Dioxide used in batteries, and the 1984 patent with the patent number JP 599036-A, entitled "oxide catalyst absorbent-modifying catalyst" and the 1984 patent with the patent number JP patent number being JP 599036-A, entitled "active catalyst absorbent-modifying catalyst", the 1984 patent with the patent number being JP patent number A, 1998, emission absorbent catalyst, emission absorbent, emission absorbent, emission absorbent, emission absorbent, emission absorbent, emission absorbent, emission absorbent, emission absorbent, emission.
The preparation of manganese dioxide mainly comprises a sol-gel method, an electrochemical deposition method, a rheological phase reaction method, a micro-emulsion method, a hydrothermal synthesis method, a coprecipitation method, a liquid phase method, a template method, a solid phase synthesis method and the like, wherein the adopted methods of various manganese dioxide crystal forms are different, and the same preparation method can also be used for preparing manganese dioxide with different crystal forms. At present, the prior art still has defects in the yield and accuracy of preparing gamma crystal form manganese dioxide.
Selective oxidation of allylic (benzyl) alcohols to α, β -unsaturated aldehydes has also gained widespread use, in the traditional method, the selective oxidation reaction of allylic (benzyl) alcohols generally used such as rare metal complexes like ruthenium, rhodium and palladium, different valence states chromium oxide, high valence iodide, and these oxidants are relatively expensive, the reaction conditions are also harsh, and the oxidant aftertreatment is relatively troublesome.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and aims to solve one of the prior art: the crystal structure of the gamma-crystal manganese dioxide is not ideal, and the yield of the gamma-crystal manganese dioxide is low; aiming at solving the second problem in the prior art: the preparation yield of the allyl (benzyl) alcohol is low, and the cost is high.
The invention solves one of the technical problems by the following technical means:
the preparation method of gamma-crystal manganese dioxide comprises the step of carrying out alkali treatment on a manganous salt solution before the manganous salt solution and a potassium permanganate aqueous solution are mixed and reacted.
Preferably, the method comprises the following steps:
step one, dripping alkali liquid into a divalent manganese salt solution to obtain a reaction liquid;
step two, under the condition of heating to a certain temperature, adding the potassium permanganate aqueous solution into the reaction solution obtained in the step one to obtain a reaction system, reacting until the color of the reaction system disappears, and stopping the reaction;
and step three, cooling, separating, washing and drying to obtain a product.
Preferably, in the second step, when the temperature of the reaction solution rises to 70 ℃, adding a potassium permanganate aqueous solution into the reaction solution, continuing to heat to 80 ℃, then keeping the temperature for reaction until the color of the reaction system disappears, and stopping the reaction.
Preferably, in the first step, the alkali is dropped into the divalent manganese salt solution, and the solution is stirred for 5min for standby.
The invention also discloses gamma crystal form manganese dioxide prepared by the method.
The invention solves the second technical problem by the following technical means:
a method for preparing unsaturated aldehyde by adopting gamma-crystal manganese dioxide prepared by the preparation method of gamma-crystal manganese dioxide comprises the following steps:
step one, dissolving gamma-crystal manganese dioxide to obtain a gamma-crystal manganese dioxide solution, adding allyl alcohol, and heating for reaction;
step two, after cooling, filtering with a funnel filled with diatomite to remove solids;
step three, drying the organic phase after washing and extracting;
and step four, filtering, rotary steaming to remove the extracting agent, and performing column chromatography separation to obtain the product.
Preferably, the allylic alcohol in the first step is one of p-methylbenzyl alcohol, p-methoxybenzyl alcohol, p-nitrobenzyl alcohol, allyl alcohol, cinnamyl alcohol and perilla alcohol.
Preferably, the solvent for dissolving gamma-crystal manganese dioxide in the first step is one of DMF, DMSO, xylene, and toluene.
Preferably, in the first step, the concentration of gamma-manganese dioxide in the gamma-manganese dioxide solution is 0.1 moL/L.
Preferably, the molar ratio of the gamma-crystal form manganese dioxide to the allylic alcohol is 1-10: 1.
Preferably, the molar ratio of the gamma crystalline manganese dioxide to allylic alcohol is 8: 1.
Preferably, in the first step, the heating temperature of the heating reaction is 70-90 ℃.
Preferably, in the first step, the heating temperature of the heating reaction is 80 ℃.
Preferably, in the first step, the reaction time of the heating reaction is 2-6 h.
Preferably, in the step one, the reaction time of the heating reaction is 4 h.
Preferably, the extractant in the second step is ethyl acetate.
Preferably, the silica gel column chromatography separation in the fourth step adopts petroleum ether and ethyl acetate as mobile phases, and the volume ratio of the petroleum ether to the ethyl acetate is 10: 1.
The invention has the advantages that: the gamma-crystal manganese dioxide is synthesized with high yield under certain conditions by using common divalent manganese salt and heptavalent manganese salt as raw materials. Because bivalent manganese ions and heptavalent manganese ions are easy to generate oxidation-reduction reaction to generate tetravalent manganese ions, the reaction is simultaneously carried out with H+Is formed of Mn4+And O2-Combining to form manganese dioxide, and combining in different modes to form manganese dioxide of different crystal forms, H+The presence of (B) affects Mn4+And O2-In combination, or in a manner not conducive to the combination, the present invention reduces H by adding a base+So as to facilitate the combination of manganese positive ions and oxygen negative ions to generate gamma-MnO2(i.e., gamma-crystalline manganese dioxide).
In addition, the analysis can obtain that the amount of the added alkali is required to cooperate with the process parameters specifically defined by the invention to obtain a better crystal structure. As can be seen from table 1, when potassium hydroxide is not added, the manganese dioxide product is not of the desired gamma type, when the amount of potassium hydroxide added is 3.36g (0.06mol, which is 1.76 times of potassium permanganate), the crystal form of the manganese dioxide produced is gamma type but the content of manganese dioxide in the product is low, when the amount of potassium hydroxide added is 3.81g (0.068mol), which is 2 times of potassium permanganate, the crystal form of the product is gamma type, the content is also good, and when the amount of potassium hydroxide is increased to 5.21g (0.093mol, which is 2.74 times of potassium permanganate), the crystal form of the product is not gamma type, so that it is preferable to select the amount of potassium hydroxide added to be 2 times (molar ratio) of potassium permanganate.
The gamma crystal form manganese dioxide synthesized by the method is used as a catalyst, and the allyl (benzyl) alcohol, namely the allylic alcohol, can be efficiently catalyzed and oxidized into corresponding aldehyde. Compared with the existing literature reports, the invention has the characteristics of cheap and easily available raw materials, clear catalyst crystal form, good selectivity and mild reaction conditions.
Drawings
FIG. 1 is an XRD spectrum of gamma-crystalline manganese dioxide of examples 1, 2, 3,4, 5, 9, 10, 11;
wherein, the curves from bottom to top in fig. 1 are XRD spectra of gamma-crystalline manganese dioxide of examples 1, 2, 3,4, 5, 9, 10, and 11 in sequence;
FIG. 2 is the XRD spectra of the products of examples 6, 7, 8, 12;
wherein, the XRD spectrograms of the products of the examples 6, 7, 8 and 12 are shown in the sequence from bottom to top in the graph of figure 2;
figure 3 is an XRD pattern of α, gamma, delta, quadtype manganese dioxide of the prior art as in example 14.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
It is noted that, in this document, relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Example 1
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, stirring to completely dissolve the manganese sulfate, and preparing into a 0.50mol/L manganese sulfate solution.
2) Weighing 0.068mol of potassium hydroxide, adding deionized water, and preparing into 1.00mol/L potassium hydroxide solution; dropwise adding the potassium hydroxide solution into the manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 2
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese chloride, adding the manganese chloride into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese chloride to prepare a 0.50mol/L manganese chloride solution.
2) Weighing 0.068mol of potassium hydroxide, adding deionized water, and preparing into 1.00mol/L potassium hydroxide solution; dropwise adding the potassium hydroxide solution into the manganese chloride solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 3
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese acetate tetrahydrate, adding the manganese acetate tetrahydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese acetate tetrahydrate to prepare a 0.50mol/L manganese acetate tetrahydrate solution.
2) Weighing 0.068mol of potassium hydroxide, adding deionized water, and preparing into 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese acetate tetrahydrate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 4
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese nitrate, adding the manganese nitrate into a 500mL three-neck flask, and adding deionized water. Stirring to completely dissolve the manganese nitrate to prepare a 0.50mol/L manganese nitrate solution.
2) Weighing 0.068mol of potassium hydroxide, adding deionized water, and preparing into 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese nitrate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 5
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.068mol of sodium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L sodium hydroxide solution; dropwise adding a sodium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the sodium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 6
This example discloses a method for preparing manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
3) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain a product.
Example 7
This example discloses a method for preparing manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.034mol of potassium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 8
This example discloses a method for preparing manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.051mol of potassium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 9
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.060mol of potassium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 10
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.075mol of potassium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 11
This example discloses a method for preparing gamma-crystalline manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.085mol of potassium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
Example 12
This example discloses a method for preparing manganese dioxide
1) Accurately weighing 0.051mol of manganese sulfate monohydrate, adding the manganese sulfate monohydrate into a 500mL three-neck flask, adding deionized water, and stirring to completely dissolve the manganese sulfate to obtain a 0.50mol/L manganese sulfate solution.
2) Weighing 0.093mol of potassium hydroxide, adding deionized water, and preparing to obtain 1.00mol/L potassium hydroxide solution; dropwise adding a potassium hydroxide solution into a manganese sulfate solution, and continuously stirring; and after the potassium hydroxide solution is dripped, stirring for 5min for later use.
3) Stirring and heating the solution, adding a potassium permanganate aqueous solution (0.034mol of potassium permanganate dissolved in 50mL of water) into the reaction solution when the temperature of the reaction solution rises to 70 ℃, continuously heating and stirring until the temperature rises to 80 ℃, keeping the temperature for reaction, stopping the reaction (30min) when the color of the reaction solution disappears, and standing and cooling to room temperature.
4) And (3) performing filter pressing separation by using a filter press, washing the filter cake for multiple times by using deionized water until the filtrate is neutral, taking out the filter cake, drying the filter cake in a drying oven until the water content is less than 5%, stopping drying to obtain black (brown) powder, and grinding by using a ball mill to obtain the target product gamma-crystal manganese dioxide.
The manganese sulfate monohydrate in example 2 was changed to manganese chloride, and other conditions were unchanged;
example 3 is the change from manganese sulfate monohydrate to manganese acetate tetrahydrate of example 1, with the other conditions unchanged;
example 4 was the change from manganese sulfate monohydrate to manganese nitrate in example 1, with the other conditions unchanged;
example 5 was the change from potassium hydroxide to sodium hydroxide in example 1, with the other conditions being unchanged;
example 6 is example 1 without adding potassium hydroxide, other conditions were unchanged;
example 7 is the amount of potassium hydroxide in example 1 was changed to 1.91g (0.034mol) with the other conditions being unchanged;
example 8 the amount of potassium hydroxide in example 1 was changed to 2.86g (0.051mol) and the other conditions were not changed;
example 9 the amount of potassium hydroxide in example 1 was changed to 3.36g (0.060mol) with the other conditions being unchanged;
example 10 example 1 with 4.20g (0.075mol) of potassium hydroxide and no other conditions;
example 11 is the amount of potassium hydroxide in example 1 was changed to 4.76g (0.085mol) with the other conditions being unchanged;
example 12 the amount of potassium hydroxide in example 1 was changed to 5.21g (0.093mol) with the other conditions being unchanged;
the results of the product-related index tests prepared in examples 1 to 12 are shown in table 1.
TABLE 1 related indices of manganese dioxide for each of the examples
MnO2Content, water content, Cl-,SO4 2-The content and pH value detection standards are as follows: QB/T2629-2004; the crystal form detection method is an XRD method; the specific surface area (BET method) detection standard is GB/T19587-; the true density detection standard is GB/T6155-; the oil absorption value detection standard is GB/T3780.2-2007.
Because bivalent manganese ions and heptavalent manganese ions are easy to generate oxidation-reduction reaction to generate tetravalent manganese ions, the reaction is simultaneously carried out with H+Is formed of Mn4+And O2-Combining to form manganese dioxide, and combining in different modes to form manganese dioxide of different crystal forms, H+The presence of (B) affects Mn4+And O2-In combination, or in a manner not conducive to the combination, the present invention reduces H by adding a base+So as to facilitate the combination of manganese positive ions and oxygen negative ions to generate gamma-MnO2. In addition, the analysis can obtain that the amount of the added alkali is required to cooperate with the process parameters specifically defined by the invention to obtain a better crystal structure. As can be seen from Table 1, the product manganese dioxide is not the desired gamma form when potassium hydroxide is not added, the form of manganese dioxide crystal formed when potassium hydroxide is added in an amount of 3.36g (0.06mol, 1.76 times as much as potassium permanganate) is gamma but the content of manganese dioxide in the product is low, and when potassium hydroxide is added in an amount of 1.76 times as much as potassium permanganateWhen 3.81g (0.068mol) is 2 times of potassium permanganate, the crystal form of the product is gamma type, the content is also good, and the amount of potassium hydroxide is continuously increased to 5.21g (0.093mol, 2.74 times of potassium permanganate), the crystal form of the product is not gamma type, so that the addition amount of potassium hydroxide is more suitable to be 2 times (molar ratio) of potassium permanganate.
5) Product characterization
As shown in fig. 1, the crystalline form of the manganese dioxide synthesized in examples 1, 2, 3,4, 5, 9, 10, and 11 was determined to be gamma-form manganese dioxide by comparing the XRD spectrum with manganese dioxide card (JCPDS-14-0644), whereas the product spectrum generated by the methods of examples 6, 7, 8, and 12 was not gamma-form manganese dioxide as shown in fig. 2.
Example 13
This example discloses a process for the preparation of unsaturated aldehydes by weighing 1.0 mmols of gamma-crystalline manganese dioxide prepared in example 3 into a Schlenk reaction tube, adding 10mL of N, N-Dimethylformamide (DMF) as a solvent, adding 1.0mmoL of benzyl alcohol as a substrate under stirring, placing the Schlenk reaction tube in an oil bath, heating to 80 deg.C and reacting for 4 hours while maintaining the temperature. Stopping the reaction, cooling to room temperature, filtering with a funnel filled with diatomite to remove solids, washing the filtrate with deionized water for multiple times, extracting with ethyl acetate, drying the organic phase with anhydrous magnesium sulfate, filtering, performing rotary evaporation to remove ethyl acetate, and separating the product by column chromatography (the mobile phase is petroleum ether/ethyl acetate volume ratio is 10:1) to obtain benzaldehyde.
Example 14
Comparison of reactivity of manganese dioxide of different crystal forms
α, β and gamma crystal forms prepared by the prior art are respectively weighed (the preparation method is shown in the literature: Lexuan et al. different crystal forms manganese dioxide nano-rods catalyze and oxidize chlorobenzene performance research [ J]2351, journal of chemistry, 2012,70(22): 2351; 4 part 4.1 of the experimental part; the XRD spectrogram is shown in figure 3, and the delta crystal form (the preparation method is shown in the literature: Malayaki, and the like; the nano delta-MnO is prepared by a low-temperature normal-pressure liquid phase method2[J]University of wood university newspaper (nature science edition), 2011, 29 (3): 386-391.1, Experimental methods section; the concentration of the hydrochloric acid is 2mol/L, and the molar ratio of the reactant is KMnO4When HCl is 1:8, the reaction temperature is 60 ℃, and the reaction is carried outThe time is 60min, an XRD spectrogram is shown in figure 3) and gamma-crystal form manganese dioxide prepared in the embodiment 3 of the invention are respectively added with 1.0mmoL into a Schlenk reaction tube, 10mL of solvent N, N-Dimethylformamide (DMF) is added, 1.0mmoL of substrate benzyl alcohol is added under stirring, the Schlenk reaction tube is placed in an oil bath, and the temperature is heated to 80 ℃ for heat preservation reaction for 4 hours. Stopping the reaction, cooling to room temperature, filtering with a funnel filled with diatomite to remove solids, washing the filtrate with deionized water for multiple times, extracting with ethyl acetate, drying the organic phase with anhydrous magnesium sulfate, filtering, performing rotary evaporation to remove ethyl acetate, and separating the product by column chromatography (the mobile phase is petroleum ether/ethyl acetate volume ratio is 10:1) to obtain benzaldehyde. The reaction results are shown in Table 2.
TABLE 2 influence of different crystal forms of manganese dioxide on the reaction results
α -crystalline manganese dioxide is in hexagonal close-packed form [ 2X 2 ]]The pores of the tunnel structure are often embedded with cations, and the β crystal form manganese dioxide is [1 x 1 ] surrounded by manganese oxide octahedron and rhombohedron]The pores of the crystal form gamma manganese dioxide are small, and manganese oxide octahedron of the crystal form gamma is enclosed to form [1 x 1 ]]And [ 1X 2 ]]A close-packed hexagonal structure formed by the interactive growth of tunnels, the [ 1X 2 ] structure]The tunnel has larger pores, the delta-manganese dioxide structure is layered, and the layers directly contain K+、Na+、Li+Isocation and H2O molecules, and the like. Due to these structural differences, [ 1X 2 ] is contained in gamma-form manganese dioxide]The tunnel has large pores, so that the contact surface of the tunnel and a reaction substrate is large, and high oxidation reaction activity is shown.
The gamma crystal form manganese dioxide synthesized by the method is used as a catalyst, and the allyl (benzyl) alcohol, namely the allylic alcohol, can be efficiently catalyzed and oxidized into corresponding aldehyde. Compared with the existing literature reports, the invention has the characteristics of cheap and easily available raw materials, clear catalyst crystal form, good selectivity and mild reaction conditions.
Example 15
Effect of catalyst amount on Oxidation reaction results
Compared with example 13, under the same reaction conditions, 2eq, 4eq, 6eq, 8eq and 10eq of gamma-crystal manganese dioxide are taken to carry out oxidation reaction on benzyl alcohol respectively, and the obtained results are shown in table 3.
Adding 2eq of gamma-crystal manganese dioxide, namely 2.0mmoL of manganese dioxide into an inverse schlenk reaction tube, adding 10mL of N, N-Dimethylformamide (DMF), and adding 1.0mmoL of benzyl alcohol under stirring;
adding 4eq of gamma-crystal manganese dioxide, namely 4.0mmoL of manganese dioxide into an inversed schlenk reaction tube, adding 10mL of N, N-Dimethylformamide (DMF), and adding 1.0mmoL of benzyl alcohol under stirring;
adding 6eq gamma crystal form manganese dioxide, namely 6.0mmoL manganese dioxide into an inverse schlenk reaction tube, adding 10mL of N, N-Dimethylformamide (DMF), and adding 1.0mmoL of benzyl alcohol under stirring;
adding 8eq of gamma-crystal manganese dioxide, namely 8.0mmoL of manganese dioxide into an inverse schlenk reaction tube, adding 10mL of N, N-Dimethylformamide (DMF), and adding 1.0mmoL of benzyl alcohol under stirring;
adding 10eq of gamma-crystal manganese dioxide, namely 10.0mmoL of manganese dioxide into an inversed schlenk reaction tube, adding 10mL of N, N-Dimethylformamide (DMF), and adding 1.0mmoL of benzyl alcohol under stirring;
TABLE 3 influence of different equivalent amounts of gamma-form manganese dioxide on the reaction results
Isolation yield:
as seen from Table 3, when manganese dioxide was 8eq, the conversion of benzyl alcohol was 100%.
Example 16
Effect of catalyst amount on Oxidation reaction results
Influence of solvent
Compared with example 13, the catalyst is 8eq, and the effect of the solvent on the reaction is changed under the condition that other conditions are not changed, and the result is shown in table 4.
TABLE 4 influence of the solvent on the reaction results
Isolation yield:
as can be seen from Table 4, DMF is the most preferable solvent for the reaction system.
Example 17
Influence of reaction temperature
The reaction temperature was changed in comparison with example 13 under otherwise unchanged conditions, and the reaction results are shown in Table 5.
TABLE 5 influence of reaction temperature on the reaction results
Isolation yield:
as is apparent from Table 5, the yield of benzaldehyde was 89.5% at 70 ℃ and the yield of benzaldehyde was identical to 80 ℃ at 90 ℃ and the reaction temperature was set to 80 ℃ at the most suitable level.
Example 18
Influence of reaction time on the reaction
The reaction time was varied as compared with example 13 without changing other conditions, and the reaction results are shown in Table 6.
TABLE 6 influence of reaction time on the reaction results
Isolation yield:
as can be seen from Table 6, the yield of benzaldehyde was 100% when the reaction time was longer than 4 hours, and the reaction was not completed when the reaction time was 3 hours, so that the reaction time was preferably set to 4 hours.
Example 19
Influence of the reaction substrate
To examine the adaptability of the reaction conditions, gamma-form manganese dioxide was 8eq, the other conditions were the same as in example 13, and the effects of different substrates on the reaction were examined, and the reaction results are shown in table 7.
TABLE 7 influence of the reaction substrates on the reaction results
It is noted that, in this document, relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of gamma-crystal manganese dioxide is characterized in that a manganous salt solution is subjected to alkali treatment before the manganous salt solution and a potassium permanganate aqueous solution are mixed and reacted.
2. The preparation method of gamma-crystalline manganese dioxide according to claim 1, characterized in that it comprises the following steps:
step one, dripping alkali liquid into a divalent manganese salt solution to obtain a reaction liquid;
step two, under the condition of heating to a certain temperature, adding the potassium permanganate aqueous solution into the reaction solution obtained in the step one to obtain a reaction system, and reacting until the color of the reaction system disappears;
and step three, cooling, separating, washing and drying to obtain a product.
3. The preparation method of gamma-crystal form manganese dioxide according to claim 2, wherein in the second step, when the temperature of the reaction solution rises to 70 ℃, the aqueous solution of potassium permanganate is added into the reaction solution, and after the temperature is raised to 80 ℃, the reaction is kept at a constant temperature until the color of the reaction system disappears, and the reaction is stopped.
4. Gamma-manganese dioxide prepared by the method of preparing gamma-manganese dioxide according to any one of claims 1 to 3.
5. A method for preparing unsaturated aldehydes by using gamma-crystalline manganese dioxide prepared by the method for preparing gamma-crystalline manganese dioxide according to any one of claims 1 to 3, comprising the steps of:
step one, dissolving gamma-crystal manganese dioxide to obtain a gamma-crystal manganese dioxide solution, adding allyl alcohol, and heating for reaction;
step two, after cooling, filtering with a funnel filled with diatomite to remove solids;
step three, drying the organic phase after washing and extracting;
and step four, filtering, rotary steaming to remove the extracting agent, and performing column chromatography separation to obtain the product.
6. The method of claim 5, wherein the allylic alcohol in the first step is one of p-methylbenzyl alcohol, p-methoxybenzyl alcohol, p-nitrobenzyl alcohol, allyl alcohol, cinnamyl alcohol and perillyl alcohol.
7. The method for preparing unsaturated aldehydes according to claim 5, wherein the solvent for dissolving gamma-form manganese dioxide in the first step is one of DMF, DMSO, xylene, and toluene.
8. The method for preparing unsaturated aldehyde according to claim 5, wherein the molar ratio of gamma-crystalline manganese dioxide to allylic alcohol is 1-10: 1.
9. The method according to claim 5, wherein the heating temperature of the heating reaction in the first step is 70 to 90 ℃.
10. The method according to claim 5, wherein the heating reaction is carried out for a reaction time of 2 to 6 hours in the first step.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010158162.3A CN111268738A (en) | 2020-03-09 | 2020-03-09 | Preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010158162.3A CN111268738A (en) | 2020-03-09 | 2020-03-09 | Preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111268738A true CN111268738A (en) | 2020-06-12 |
Family
ID=70995526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010158162.3A Pending CN111268738A (en) | 2020-03-09 | 2020-03-09 | Preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111268738A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114345323A (en) * | 2022-01-19 | 2022-04-15 | 广东工业大学 | Three-dimensional petal-shaped gamma-MnO2Catalyst and preparation method and application thereof in catalytic combustion of toluene |
CN114540873A (en) * | 2022-04-25 | 2022-05-27 | 清华大学 | Palladium/gamma-manganese dioxide/foamed nickel composite electrode and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0769640A (en) * | 1993-09-01 | 1995-03-14 | Mitsui Toatsu Chem Inc | Production of manganese dioxide |
CN101343080A (en) * | 2008-08-25 | 2009-01-14 | 陕西师范大学 | Manganese dioxide mesoporous material and method of preparing the same |
CN102583561A (en) * | 2012-01-12 | 2012-07-18 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
CN103172119A (en) * | 2013-04-17 | 2013-06-26 | 湖南化工研究院 | Preparation method of layered chemical manganese dioxide |
CN109796048A (en) * | 2019-03-27 | 2019-05-24 | 中国人民解放军陆军工程大学 | Controlled synthesis method of manganese dioxide with different crystal forms |
-
2020
- 2020-03-09 CN CN202010158162.3A patent/CN111268738A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0769640A (en) * | 1993-09-01 | 1995-03-14 | Mitsui Toatsu Chem Inc | Production of manganese dioxide |
CN101343080A (en) * | 2008-08-25 | 2009-01-14 | 陕西师范大学 | Manganese dioxide mesoporous material and method of preparing the same |
CN102583561A (en) * | 2012-01-12 | 2012-07-18 | 大连民族学院 | Alpha-phase manganese dioxide nano-rod, and preparation method and application thereof |
CN103172119A (en) * | 2013-04-17 | 2013-06-26 | 湖南化工研究院 | Preparation method of layered chemical manganese dioxide |
CN109796048A (en) * | 2019-03-27 | 2019-05-24 | 中国人民解放军陆军工程大学 | Controlled synthesis method of manganese dioxide with different crystal forms |
Non-Patent Citations (1)
Title |
---|
冯银茂: "("二氧化锰选择性氧化烯丙醇的研究"", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114345323A (en) * | 2022-01-19 | 2022-04-15 | 广东工业大学 | Three-dimensional petal-shaped gamma-MnO2Catalyst and preparation method and application thereof in catalytic combustion of toluene |
CN114345323B (en) * | 2022-01-19 | 2024-03-08 | 广东工业大学 | Three-dimensional petal-shaped gamma-MnO 2 Catalyst, preparation method and application thereof in catalytic combustion of toluene |
CN114540873A (en) * | 2022-04-25 | 2022-05-27 | 清华大学 | Palladium/gamma-manganese dioxide/foamed nickel composite electrode and preparation method and application thereof |
CN114540873B (en) * | 2022-04-25 | 2022-08-12 | 清华大学 | Palladium/gamma-manganese dioxide/foamed nickel composite electrode and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Tantirungrotechai et al. | Biodiesel synthesis over Sr/MgO solid base catalyst | |
Dahl et al. | Composite titanium dioxide nanomaterials | |
Salinas et al. | Study of potassium-supported TiO2 catalysts for the production of biodiesel | |
Xie et al. | Transesterification of soybean oil over WO3 supported on AlPO4 as a solid acid catalyst | |
CN111268738A (en) | Preparation method of gamma-crystal manganese dioxide, gamma-crystal manganese dioxide and application of gamma-crystal manganese dioxide | |
CN105460974B (en) | Defect-rich ultra-thin bismuth oxyiodide nano-sheet preparation method | |
CN105879886B (en) | A kind of preparation method of GO/Sb BiOBr composite photo-catalysts | |
CN104249993A (en) | Method for producing hydrogen and oxygen through solar photocatalysis of water based on metal oxide photocatalyst | |
Jo et al. | Effectively CO2 photoreduction to CH4 by the synergistic effects of Ca and Ti on Ca-loaded TiSiMCM-41 mesoporous photocatalytic systems | |
Jin et al. | ZnO/Sn3O4 amorphous-crystalline heterojunctions for Cr (VI) visible photocatalysis: Simple synthesis with excellent performance | |
Yang et al. | Oxygen activation through β-Bi2O3 and ultrafine CeO2 interactions to promote catalytic soot combustion | |
CN107213904B (en) | Preparation method of monoclinic iron molybdate nanosheet with high activity and exposed crystal face | |
Liu et al. | Metal oxide-containing SBA-15-supported gold catalysts for base-free aerobic homocoupling of phenylboronic acid in water | |
CN104150536A (en) | Preparation method and application of MoO2 powder with favorable photoelectric properties | |
CN109126870A (en) | Multi-metal oxygen cluster is the preparation method that node constructs porous catalyst material | |
Wang et al. | Mesoporous WO3 modified by Mo for enhancing reduction of CO2 to solar fuels under visible light and thermal conditions | |
Khor et al. | Zr-doped silver niobates for photocatalytic degradation of methylene blue and Rhodamine B dyes | |
Khor et al. | Zr, La-dual doped silver niobate for photocatalytic degradation of dyes under visible light irradiation | |
Go et al. | Solid solution precursors to gadolinia-doped ceria prepared via a low-temperature solution route | |
Zhang et al. | One-step conversion of acidified oil to biodiesel by novel bifunctional SrZr1-xFexO3 catalyst | |
CN101294093A (en) | Integrated preparation method for biological diesel oil and isolated plant | |
CN106560230B (en) | Application of the composite catalyst based on iron nitrogen-doped titanium dioxide in nitric oxide photocatalysis | |
CN101700910A (en) | Preparation method of spherical nanoscale niobium pentaoxide powder | |
CN100562361C (en) | A kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier | |
CN113929058B (en) | Catalyst carrier for preparing chlorine by catalytic oxidation of fluorine-containing HCl gas, and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20230406 Address after: No. 1 Tongbanqiao Industrial Park, Zhulin Town, Jintan District, Changzhou City, Jiangsu Province, 213001 Applicant after: JIANGSU KEXIANG ANTICORROSIVE MATERIAL Co.,Ltd. Address before: Tunxi road in Baohe District of Hefei city of Anhui Province, No. 193 230009 Applicant before: Hefei University of Technology |
|
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200612 |