CN106693985A - Preparation method of sheet spinel structure cobalt-manganese composite oxide - Google Patents
Preparation method of sheet spinel structure cobalt-manganese composite oxide Download PDFInfo
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- CN106693985A CN106693985A CN201611053408.0A CN201611053408A CN106693985A CN 106693985 A CN106693985 A CN 106693985A CN 201611053408 A CN201611053408 A CN 201611053408A CN 106693985 A CN106693985 A CN 106693985A
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- manganese composite
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 33
- 239000011029 spinel Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 238000000967 suction filtration Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 45
- 239000000047 product Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000005303 weighing Methods 0.000 abstract 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 125000005909 ethyl alcohol group Chemical group 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YLYPAGJDBMPYKO-UHFFFAOYSA-N [Mn].[Mn].[Co].[Co] Chemical compound [Mn].[Mn].[Co].[Co] YLYPAGJDBMPYKO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a sheet spinel structure cobalt-manganese composite oxide. The preparation method comprises the following steps: 1, weighing an aqueous solution of cobalt nitrate hexahydrate and manganous nitrate, dissolving in absolute ethyl alcohol, stirring and dissolving to obtain a solution A; additionally weighing excessive oxalic acid dihydrate, dissolving in the absolute ethyl alcohol, stirring and dissolving to obtain a solution B; 2, adding the solution B dropwise into the solution A while stirring, and continuing to stir to obtain a mixed solution; 3, after completing stirring, conducting suction filtration on the mixed solution, and drying a precipitate obtained through suction filtration in an air circulation oven; 4, roasting the dried solid in a muffle furnace to obtain the sheet spinel structure cobalt-manganese composite oxide. According to the preparation method, other metal cations except the necessary metal salts are not introduced, the preparation method has the advantages of cheap raw materials, simple operation, washing-free, even distribution of products, and high purity, and the obtained product shows very high activity on the complete oxidation reaction of benzene.
Description
Technical field
The present invention relates to a kind of preparation method of cobalt manganese composite oxide, category material is prepared and environmental technology field, specifically
Ground say, be related to a kind of preparation method of sheet spinel structure cobalt manganese composite oxide Co2MnOx.
Background technology
Cobalt manganese composite oxide is a kind of new material with extensive use, due to its contain two kinds of different metals from
Son and with special spinel type crystal structure, therefore magnetics, electronics, catalysis, energy conversion and storage etc. aspect
Suffer from great application prospect.As the various laws and regulations for being directed to VOCs (volatile organic matter) improvement in recent years go out
Platform, application of the cobalt manganese composite oxide in VOCs improvement receives much concern.
Activity and its specific surface area, active component decentralization, component that cobalt Mn complex oxide catalyst is removed to VOCs
Interphase interaction etc. it is relevant；Wherein, these factors are directly related with preparation method.Existing for cobalt manganese composite oxide
Preparation method in, have coprecipitation method, collosol and gel etc..And thus obtained cobalt and manganese oxide is based on graininess, typically
Have the shortcomings that impurity content is high, particle diameter is big, skewness.Often show relatively low catalytic performance.
Catalysis material is prepared into laminated structure and is greatly improved material property；Through retrieval：Patent CN105597769A, adopts
Sheet-like morphology nano composite metal oxide catalyst CeO2-Co3O4 is synthesized with hydro-thermal method, due to the CeO2-Co3O4 for preparing
The sheet microscopic appearance of active crystal face is exposed with more advantages, it has more high activity and CO catalytic selectivities；Patent
CN102303900A, using hydro-thermal method synthesizing flaky pattern indium trisulfide, with good Visible Light Induced Photocatalytic ability；Patent
CN103011188A, using the nanometer SAPO-34 molecular sieves of microwave heating method synthesizing flaky pattern, in methyl alcohol ethene, propylene
Had outstanding performance in reaction Deng low-carbon alkene.In prepared by the material of above sheet-like morphology, hydro-thermal method often needs HTHP, and needs
Reaction time that will be more long.Heating using microwave is also required to carry out at a higher temperature, therefore above method inevitably increases
Addition sheet, it is more difficult to realize large-scale production.
Existing document report is bar-shaped, floriform appearance structure cobalt manganese composite oxide synthesis, but does not find with sheet-shaped
The relevant report of looks cobalt manganese composite oxide.
The content of the invention
For problem above, it is an object of the invention to provide a kind of preparation of the cobalt manganese composite oxide with laminated structure
Method, it has the advantages that, and raw material sources are abundant, preparation method is simple, suitable for large-scale production.Cobalt manganese prepared by the present invention
Composite oxides be sheet spinel structure, with reactivity it is high the characteristics of, can at low temperature be catalyzed burning benzene.XRD results
Cobalt manganese composite oxide obtained by showing is spinel structure；SEM shows that cobalt manganese composite oxide is sheet-like morphology.
The present invention is achieved by the following technical solutions：
A kind of preparation method of sheet spinel structure cobalt manganese composite oxide, the described method comprises the following steps：
The first step, weigh cabaltous nitrate hexahydrate and manganese nitrate aqueous solution is dissolved in absolute ethyl alcohol, after stirring and dissolving solution
A；Another excessively two oxalic acid hydrates that weigh are dissolved in absolute ethyl alcohol, and solution B is obtained after stirring and dissolving；
Under second step, stirring, solution B is dropwise instilled in solution A, continue to stir, obtain mixed liquor；
After the completion of 3rd step, stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in convection oven
Middle drying；
4th step, the solid after drying is placed in Muffle furnace roasting obtains described sheet spinel structure cobalt manganese composite oxygen
Compound.
Preferably, in the first step：The manganese nitrate aqueous solution mass fraction is 50%.
Preferably, in the solution A liquid total mole number of cobalt and manganese and two oxalic acid hydrates in the B solution molal quantity it
Than being 1:1.2, the molar concentration of oxalic acid solution is 0.72mol/L.Because spinel structure formula is A2BO4, A is often+trivalent gold
Category ion, B is often+divalent metal ion.Optimum condition of the present invention is the mol ratio 2 of Co/Mn:1, it is obtained in that with perfect point
The Co2MnOx of spinel structure.And the oxalic acid amount of skipping over is then to ensure cobalt salt with manganese salt according to theoretical addition amount (2:1) precipitate completely,
And consumption of oxalic acid will excessively cause the sheet-like morphology of cobalt manganese cobalt manganese composite oxide to cave in.
Preferably, second step, continuation mixing time is 4~6h.
Preferably, in the 3rd step：The temperature that the convection oven sets is 70~80 DEG C.Using the temperature range to suction filtration
The influence volatilization completely that is smaller and being conducive to absolute ethyl alcohol of the sediment for obtaining.It is preferred that in convection oven drying time be 10~
12h。
Preferably, in the 4th step：The temperature of the roasting is 300-500 DEG C.Be conducive to obtaining good using the sintering temperature
Good crystal phase structure, cobalt manganese composite oxide pattern, and and then raising material property.At the temperature (300~500 DEG C) of selection
Roasting can obtain the sheet cobalt manganese composite oxide with perfect spinel structure, and the catalysis burning of benzene be shown optimal
Performance.
Preferably, in the 4th step：The time of roasting is 3~5h, and heating rate is 2 DEG C/min.
The present invention is using conditions such as suitable temperature and heating rates for obtaining having perfect spinel structure
Co2MnOx has material impact.First, to obtain good spinel structure and control the sheet-shaped of cobalt manganese composite oxide
Looks, sintering temperature of the invention, when temperature is too low, it is impossible to obtain good spinel crystal phase structure, temperature is too high, can destroy
The sheet-like morphology of cobalt manganese composite oxide.Secondly present invention selection oxalic acid is precipitating reagent, because the oxalate precursor for being formed exists
In decomposable process, CO or CO can be produced2Gas, and drying temperature, heating rate, sintering temperature and time etc. can influence CO or
Person CO2The generation and release of gas, and then influence the crystal phase structure and microscopic appearance of product.Heating rate can influence crystal knot
Crystalline substance, and temperature and time can then influence crystal grain to grow up, and further the microscopic appearance on product produces influence.Further, by
It is of different sizes in the atom of cobalt and manganese, when crystal grain is grown up, easily make deformation of crystal structure, on the one hand may promote carrying for performance
Height, on the other hand can but influence the microscopic appearance and crystal phase structure of product.
The present invention, with ethanol as dispersant, adds grass without introducing other metal cations in addition to indispensable slaine
Acid co-precipitation, without washing, obtained cobalt manganese composite oxide is the cobalt-manganese spinel structure of sheet.The preparation method has
Raw material is cheap, simple to operate, without washing, the advantage that product is evenly distributed, purity is high, products therefrom is anti-to the complete oxidation of benzene
Activity very high should be shown.
Compared with prior art, the present invention has advantages below：
(1) raw material used by the present invention is simple, with low cost.
(2) preparation process is simple of the present invention, without washing, it is adaptable to the extensive preparation in extensive actual condition.
(3) the obtained material of the present invention shows preferable reactivity worth to benzene combustion reaction.
Brief description of the drawings
The detailed description made to non-limiting example with reference to the following drawings by reading, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the XRD of the cobalt manganese composite oxide described in embodiment of the present invention 1-3；
Fig. 2 is the SEM figures of the cobalt manganese composite oxide described in the embodiment of the present invention 1；
Fig. 3 schemes for the SEM of cobalt manganese composite oxide described in the embodiment of the present invention 2；
Fig. 4 schemes for the SEM of cobalt manganese composite oxide described in the embodiment of the present invention 3.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1：
Weigh 4.656g cabaltous nitrate hexahydrates and 2.860g manganese nitrate solutions (mass fraction is 50%) are placed in 500mL beakers
In, 200mL absolute ethyl alcohols are added, solution A is obtained after stirring and dissolving；The oxalic acid hydrates of 3.620g bis- are weighed to be placed in 100mL beakers,
50mL absolute ethyl alcohols are added, stirring and dissolving obtains solution B；Under stirring, solution B is dropwise instilled into solution A, be further continued for stirring 4-6h；
After the completion of stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in 70~80 DEG C of convection ovens dry
12h, drying；Solid after drying is placed in Muffle kiln roasting, sintering temperature is 300 DEG C, and roasting time is 4h, heating rate
2 DEG C/min, obtain sheet cobalt manganese composite oxide.
As shown in SEM results in Fig. 2, the thickness of piece is 0.03 μm.The XRD result of embodiment 1 shows the oxidation in Fig. 1
Thing is spinel structure.
Embodiment 2：
Weigh 4.656g cabaltous nitrate hexahydrates and 2.860g manganese nitrate solutions (mass fraction is 50%) are placed in 500mL beakers
In, 200mL absolute ethyl alcohols are added, solution A is obtained after stirring and dissolving；The oxalic acid hydrates of 3.620g bis- are weighed to be placed in 100mL beakers,
50mL absolute ethyl alcohols are added, stirring and dissolving obtains solution B；Under stirring, solution B is dropwise instilled into solution A, be further continued for stirring 4-
6h；After the completion of stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in 70~80 DEG C of convection ovens dry
Dry 12h, drying；Solid after drying is placed in Muffle kiln roasting, sintering temperature is 400 DEG C, and roasting time is 4h, heat up speed
2 DEG C/min of rate, obtains sheet cobalt manganese composite oxide.
As shown in SEM results in Fig. 3, the thickness of piece is 0.02 μm.The XRD results of embodiment 2 show the oxide in Fig. 1
It is spinel structure.
Embodiment 3：
Weigh 4.656g cabaltous nitrate hexahydrates and 2.860g manganese nitrate solutions (mass fraction is 50%) are placed in 500mL beakers
In, 200mL absolute ethyl alcohols are added, solution A is obtained after stirring and dissolving；The oxalic acid hydrates of 3.620g bis- are weighed to be placed in 100mL beakers,
50mL absolute ethyl alcohols are added, stirring and dissolving obtains solution B；Under stirring, solution B is dropwise instilled into solution A, be further continued for stirring 4-
6h；After the completion of stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in 70~80 DEG C of convection ovens dry
Dry 12h, drying；Solid after drying is placed in Muffle kiln roasting, sintering temperature is 500 DEG C, and roasting time is 4h, heat up speed
2 DEG C/min of rate, that is, obtain sheet cobalt manganese composite oxide.
As shown in SEM results in Fig. 4, the thickness of piece is 0.03 μm.The XRD results of embodiment 3 show the oxide in Fig. 1
It is spinel structure.
Comparative example 1：
4.656g cabaltous nitrate hexahydrates are weighed first and 2.860g manganese nitrate solutions (mass fraction is 50%) are placed in 500mL
In beaker, 200mL absolute ethyl alcohols are added, solution A is obtained after stirring and dissolving；Weigh the oxalic acid hydrates of 3.620g bis- and be placed in 100mL burnings
In cup, 50mL absolute ethyl alcohols are added, stirring and dissolving obtains solution B；
Under stirring, solution B is dropwise instilled into solution A, be further continued for stirring 4-6h；
After the completion of stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in 70~80 DEG C of air blast bakings
12h is dried in case, is dried；
Solid after drying is placed in Muffle kiln roasting, sintering temperature is 600 DEG C, and roasting time is 4h, heating rate 2
DEG C/min, obtain graininess cobalt manganese composite oxide.
Comparative example 2：
4.656g cabaltous nitrate hexahydrates are weighed first and 2.860g manganese nitrate solutions (mass fraction is 50%) are placed in 500mL
In beaker, 200mL absolute ethyl alcohols are added, solution A is obtained after stirring and dissolving；The oxalic acid hydrates of 3.620g bis- are weighed, 100mL burnings are placed in
In cup, 50mL absolute ethyl alcohols are added, stirring and dissolving obtains solution B；
Under stirring, solution B is dropwise instilled into solution A, be further continued for stirring 4-6h；
After the completion of stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in 70~80 DEG C of air blast bakings
12h is dried in case, is dried；
By the solid after drying, Muffle kiln roasting is placed in, sintering temperature is 700 DEG C, and roasting time is 4h, heating rate
2 DEG C/min, obtain graininess cobalt manganese composite oxide.
Application effect appraisal：
Cobalt manganese composite oxide reactivity of the present invention is high, good stability, can under cryogenic be catalyzed burning benzene
And prolonged stability can be kept.The XRD of cobalt manganese composite oxide shows cobalt manganese composite oxygen described in different embodiments in Fig. 1
The spinel structure of compound.The SEM figures of Fig. 2~4 then show the laminated structure of cobalt manganese composite oxide.
Catalytically active assessment：Cobalt manganese composite oxide described in embodiment 1-3 and comparative example 1-2 is placed on continuous stream
Benzene vapor is passed through in dynamic fixed bed device and the gaseous mixture of air is reacted；Reaction pressure is normal pressure~1atm, reaction velocity
It is 30000mL/ (gh) that in the gaseous mixture of air and benzene vapor, the concentration of benzene is 1000ppm.
Result shows that cobalt manganese composite oxide described in embodiment 1 is 140 DEG C for the initiation temperature of benzene combustion reaction,
Complete conversion temperature is 235 DEG C.Cobalt manganese composite oxide described in embodiment 2 is 145 for the initiation temperature of benzene combustion reaction
DEG C, complete conversion temperature is 245 DEG C.Cobalt manganese composite oxide is for the initiation temperature of benzene combustion reaction described in embodiment 3
155 DEG C, complete conversion temperature is 245 DEG C.
Cobalt manganese composite oxide is respectively 175 DEG C for the initiation temperature of benzene combustion reaction described in comparative example 1-2
With 180 DEG C；And conversion temperature is then respectively 265 DEG C and 305 DEG C completely.
Cobalt manganese composite oxide described in embodiment of the present invention 1-3 is sheet spinel structure, and even particle distribution is fired to benzene
The initiation temperature and complete conversion temperature for burning reaction are low, and optimal cobalt manganese composite oxide can realize that concentration is at 235 DEG C
The conversion completely of the benzene of 1000ppm.The cobalt manganese composite oxide obtained in comparative example be graininess, skewness, instead
Should be active lower than the cobalt manganese composite oxide obtained in embodiment, with initiation temperature and complete conversion temperature higher, and
Easy in inactivation, anti-caking power is poor.
Specific embodiment of the invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can within the scope of the claims make various deformations or amendments, this not shadow
Sound substance of the invention.
Claims (10)
1. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide, it is characterised in that methods described includes following
Step：
The first step, weigh cabaltous nitrate hexahydrate and manganese nitrate aqueous solution is dissolved in absolute ethyl alcohol, after stirring and dissolving solution A；Separately
Weigh excessive two oxalic acid hydrates and be dissolved in absolute ethyl alcohol, solution B is obtained after stirring and dissolving；
Under second step, stirring, solution B is dropwise instilled in solution A, continue to stir, obtain mixed liquor；
After the completion of 3rd step, stirring, by gained mixed liquor suction filtration, then the sediment obtained after suction filtration is placed in baking in convection oven
It is dry；
4th step, the solid after drying is placed in Muffle furnace roasting obtains described sheet spinel structure cobalt manganese combined oxidation
Thing.
2. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 1, its feature exists
In, the first step, in the solution A, cobalt is 2 with the mol ratio of manganese:1, the total mol concentration of cobalt and manganese is 0.12mol/L.
3. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 2, its feature exists
In the manganese nitrate aqueous solution mass fraction is 50%.
4. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 1, its feature exists
In the ratio between the total mole number of cobalt and manganese and molal quantity of two oxalic acid hydrates in the B solution are 1 in the solution A liquid:1.2, grass
The molar concentration of acid solution is 0.72mol/L.
5. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 1, its feature exists
In second step, continuation mixing time is 4~6h.
6. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 1, its feature exists
In in the 3rd step, the temperature of convection oven is 70~80 DEG C.
7. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 6, its feature exists
In in the 3rd step, drying time is 10~12h in convection oven.
8. the preparation method of a kind of sheet spinel structure cobalt manganese composite oxide according to claim any one of 1-7,
Characterized in that, in the 4th step, the temperature of the roasting is 300-500 DEG C.
9. a kind of preparation method of sheet spinel structure cobalt manganese composite oxide according to claim 8, its feature exists
In in the 4th step, the time of the roasting is 3~5h, and heating rate is 2 DEG C/min.
10. it is a kind of according to claim any one of 1-9 method prepare sheet spinel structure cobalt manganese composite oxide.
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| CN109939693B (en) * | 2019-03-29 | 2021-09-28 | 扬州大学 | CoMn2O4Bimetallic oxide catalyst, preparation method and application |
| CN118341460A (en) * | 2024-06-18 | 2024-07-16 | 浙江工业大学 | Cobalt carbide-based catalyst containing electron auxiliary agent and having specific exposed crystal face, and preparation method and application thereof |
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