CN114308009A - Micro-nano vanadium-molybdenum composite oxide and preparation method and application thereof - Google Patents
Micro-nano vanadium-molybdenum composite oxide and preparation method and application thereof Download PDFInfo
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- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 aromatic nitrile Chemical class 0.000 claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004729 solvothermal method Methods 0.000 claims description 5
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 claims description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003681 vanadium Chemical class 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 229910015667 MoO4 Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FAQSSRBQWPBYQC-VGKOASNMSA-N dioxomolybdenum;(z)-4-hydroxypent-3-en-2-one Chemical compound O=[Mo]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FAQSSRBQWPBYQC-VGKOASNMSA-N 0.000 claims description 3
- 150000002751 molybdenum Chemical class 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 2
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 claims description 2
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- 229960004217 benzyl alcohol Drugs 0.000 claims description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 claims description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000003613 toluenes Chemical class 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 4
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 3
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- 229910016040 MoV2O8 Inorganic materials 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a micro-nano vanadium-molybdenum composite oxide, which is macroscopically in a rectangular block shape, and has the length of 200-2000 nm; the thickness is 50-500nm, and the microscopic structure is a layered structure of one-dimensional nano-sheet self-assembly stacking. The invention also discloses a preparation method and application of the micro-nano vanadium-molybdenum composite oxide. The method for preparing the micro-nano vanadium-molybdenum composite oxide is simple, the raw materials are easy to obtain, the cost is low, and the method is suitable for large-scale preparation; when the method is used for preparing aromatic nitrile through ammoxidation of methyl aromatic hydrocarbon, the ammoxidation temperature is 300-430 ℃.
Description
Technical Field
The invention belongs to the technical field of materials and heterogeneous catalysis, and particularly relates to a micro-nano vanadium-molybdenum composite oxide and a preparation method and application thereof.
Background
Vanadium molybdenum compositeMolybdenum vanadate (MoV) oxide2O8) The lithium ion composite material is an important inorganic functional material, and can be widely applied to the fields of heterogeneous catalysis, electrode materials, sensors and the like, for example, the lithium ion composite material can be used as a lithium ion negative electrode material in the electrode materials, and can be used as an oxidative dehydrogenation catalyst in the heterogeneous catalysis. There are several methods for synthesizing NH by molybdenum vanadate, Shahid, etc4VO3And molybdenum water are used as raw materials, and a spin coating method is adopted to prepare high-quality orthorhombic MoV2O8The nanowire of (ShahidM, Liu J, Ali Z, et al. journal of Power Sources,2013,230: 277-. Zhiging Yin et al [ MoO2(acac)2]And [ VO (acac)2]Adopts a solvothermal method to prepare orthorhombic MoV serving as a raw material under an acidic condition2O8The nanorod of (1) (Zhuangyin, Ying Xiao, XiaWang, Wei Wang, Di Zhuo, Minhua Cao. nanoscale,2015,8(1): 508-. The molybdenum vanadate prepared by the methods has good application in the fields of electrode materials and batteries, but reports on catalytic ammoxidation are not found. All prepared by the method are orthorhombic MoV2O8For monoclinic form V2MoO8Is relatively less prepared.
Disclosure of Invention
The invention aims to provide a micro-nano vanadium-molybdenum composite oxide, namely a vanadium-molybdenum composite oxide which is microscopically nano-sheets and macroscopically is a micron-sized block particle assembled by stacking the nano-sheets.
The invention also aims to provide a preparation method of the micro-nano vanadium-molybdenum composite oxide, which can self-assemble the vanadium-molybdenum composite oxide which is microscopically a nano-sheet into micron-sized blocky particles.
The third purpose of the invention is to provide the application of the micro-nano vanadium-molybdenum composite oxide.
In order to realize the first purpose, the micro-nano vanadium-molybdenum composite oxide provided by the invention is macroscopically in a rectangular block shape, and the length of the micro-nano vanadium-molybdenum composite oxide is 200-2000 nm; the thickness is 50-500nm, and the microscopic structure is a layered structure of one-dimensional nano-sheet self-assembly stacking.
In order to achieve the second object, the method for preparing the micro-nano vanadium-molybdenum composite oxide provided by the invention comprises the following steps:
mixing a vanadium source and a molybdenum source according to a metal atom molar ratio of 2:1, placing the mixture in a pressure container, adding a solvent, uniformly mixing, sealing, heating to 120-300 ℃, carrying out solvothermal reaction for 2-200 hours, and filtering, washing and vacuum-drying a product to obtain a precursor;
calcining the precursor at the temperature of 300-800 ℃ for 0.1-10 hours, and cooling to room temperature to obtain the micro-nano vanadium-molybdenum composite oxide.
The vanadium source is vanadium oxide or vanadium salt, and the molybdenum source is molybdenum oxide or molybdenum salt.
The vanadium oxides include, but are not limited to, V2O5、V2O4Or V2O3Said vanadium salt including but not limited to NH4VO3、VOSO4、VOCl2Etc.; the molybdenum oxide includes, but is not limited to MoO3、MoO2Etc., including but not limited to (NH)4)2MoO4、(NH4)6Mo7O24、Na2MoO4Or MoO2(acac)2. The solvent of the solvothermal reaction is alcohol or an aqueous solution thereof.
The alcohol includes, but is not limited to, polyvinyl alcohol or monohydric, polyhydric alcohols from C1 to C20.
The pressure vessel is an autoclave or a pressure-resistant reactor.
The micro-nano vanadium-molybdenum composite oxide provided by the invention can be used for catalyzing methyl aromatic ammoxidation to prepare aromatic nitrile.
The methyl aromatic hydrocarbon comprises toluene, halogenated toluene, methoxytoluene, hydroxytoluene, nitrotoluene, cyanotoluene, aminotoluene, xylene, methylpyridine, methylpyrazine or methylpyrimidine.
The method for preparing the micro-nano vanadium-molybdenum composite oxide is simple, the raw materials are easy to obtain, the cost is low, and the method is suitable for large-scale preparation; when the method is used for preparing aromatic nitrile through ammoxidation of methyl aromatic hydrocarbon, the ammoxidation temperature is 300-430 ℃.
Drawings
Fig. 1 is a scanning electron microscope image of the bulk micro-nano vanadium-molybdenum composite oxide obtained in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the bulk micro-nano vanadium-molybdenum composite oxide obtained in example 2 of the present invention.
Fig. 3 is a scanning electron microscope image of the bulk micro-nano vanadium-molybdenum composite oxide obtained in embodiment 3 of the present invention.
Fig. 4 is a scanning electron microscope image of the bulk micro-nano vanadium-molybdenum composite oxide obtained in embodiment 4 of the present invention.
FIG. 5 is a transmission electron microscope image of the layered micro-nano vanadium-molybdenum composite oxide obtained by the invention.
Fig. 6 is an XRD (X-ray diffraction) pattern of the micro-nano vanadium-molybdenum composite oxide obtained by the invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples.
As can be seen from FIGS. 1-4, the product prepared in the examples is substantially in the shape of rectangular block, with a thickness of 50-500nm and a length of 500-2000 nm; as can be seen from fig. 5, the product is a layered structure formed by self-assembly of one-dimensional nanosheets; as can be seen from FIG. 6, the product of the layered stacking structure obtained by the invention is a micro-nano vanadium-molybdenum composite oxide.
Example 1
Weighing V with the total mass of 2.0g according to the molar ratio of vanadium to molybdenum of 2:12O5And (NH)4)6Mo7O24Placing the mixture into a 100ml hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding 80ml of absolute ethyl alcohol, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 180 ℃, carrying out thermostatic hydrothermal treatment for 48 hours, and naturally cooling to room temperature. And filtering the product in the reaction kettle, repeatedly washing the product with distilled water and ethanol respectively, and then drying the product at 80 ℃ in vacuum for 8 hours to obtain a vanadium-molybdenum composite oxide precursor, calcining the precursor in a resistance furnace at 550 ℃ for 3 hours to obtain the blocky micro-nano vanadium-molybdenum composite oxide, wherein a scanning electron microscope is shown in figure 1, a transmission electron microscope is shown in figure 5, and XRD is shown in figure 6.
Example 2
According to the following steps:1 vanadium molybdenum molar ratio V with a total mass of 2.0g is weighed2O4And MoO380ml of polyvinyl alcohol aqueous solution is added and stirred and mixed evenly. And then placing the mixed solution into a 100ml hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, placing the reaction kettle into a resistance furnace, heating to 200 ℃, reacting at constant temperature for 60 hours, and naturally cooling to room temperature. And filtering the product in the reaction kettle, repeatedly washing the product with distilled water and ethanol respectively, and then drying the product in vacuum at 80 ℃ for 8 hours to obtain a vanadium-molybdenum composite oxide precursor, calcining the precursor in a resistance furnace at 500 ℃ for 5 hours to obtain the blocky micro-nano vanadium-molybdenum composite oxide, wherein a scanning electron microscope is shown in figure 2.
Example 3
According to the following steps: 1 molar ratio of vanadium to molybdenum NH of 2.5g in total mass is weighed4VO3And Na2MoO4First, NH is added4VO3Adding glycerol 80ml, stirring for 1 hr until the solution turns brick red, adding Na2MoO4Stirring for 20 min; and then placing the mixed solution into a 100ml hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, placing the reaction kettle into a resistance furnace, heating to 160 ℃, reacting at constant temperature for 72 hours, and naturally cooling to room temperature. And filtering the product in the reaction kettle, repeatedly washing the product with distilled water and ethanol respectively, and then drying the product in vacuum at 80 ℃ for 8 hours to obtain a precursor of the vanadium-molybdenum composite oxide, calcining the precursor in a resistance furnace at 600 ℃ for 2 hours to obtain the blocky micro-nano vanadium-molybdenum composite oxide, wherein a scanning electron microscope is shown in figure 3.
Example 4
According to the following steps: 1 vanadium molybdenum molar ratio VOSO with the total mass of 2.0g4And (NH)4)2MoO4Placing the mixture into a 100ml hydrothermal reaction kettle, adding 60ml of ethylene glycol and 20ml of deionized water, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 220 ℃, reacting at constant temperature for 36 hours, and naturally cooling to room temperature. Filtering the product in the reaction kettle, respectively washing with distilled water and ethanol repeatedly, vacuum drying at 80 deg.C for 8h to obtain vanadium-molybdenum composite oxide precursor, calcining the precursor at 450 deg.C in a resistance furnace for 8h to obtain block-shaped micro-nano vanadium-molybdenum composite oxide, scanningThe electron microscope is shown in FIG. 4.
Example 5
According to the following steps: 1 vanadium molybdenum molar ratio V with a total mass of 2.0g is weighed2O3And MoO2(acac)2Placing the mixture into a 100ml hydrothermal reaction kettle, adding 80ml of methanol, fully stirring and uniformly mixing, sealing, placing the mixture into a resistance furnace, heating to 190 ℃, reacting at constant temperature for 50 hours, and naturally cooling to room temperature. And filtering the product, respectively washing the product with distilled water and ethanol repeatedly, drying the product at 80 ℃ for 8h in vacuum to obtain a vanadium-molybdenum composite oxide precursor, and calcining the precursor in a resistance furnace at 500 ℃ for 6h to obtain the micro-nano vanadium-molybdenum composite oxide.
Example 6
This example is a comparative example. Preparation of nano MoV by coprecipitation method2O8A material. Weighing 2.0g of NH according to the vanadium-molybdenum molar ratio of 2:14VO3And (NH)4)6Mo7O24Adding the mixture into a 100ml three-neck flask, then adding 60ml absolute ethyl alcohol, refluxing for 48h, naturally cooling to room temperature, filtering the product, repeatedly washing with deionized water and absolute ethyl alcohol respectively, and drying the product at 80 ℃ for 8h in vacuum to obtain the vanadium molybdate precursor. Calcining the precursor in a resistance furnace at 550 ℃ for 3h to obtain the irregular-shaped nano vanadium-molybdenum composite oxide particles with different sizes.
Example 7
10g of the micro-nano vanadium-molybdenum composite oxide prepared in the example 1 is filled in a quartz tube fixed bed reactor with the inner diameter of 30mm, the raw material, ammonia gas and air are preheated and mixed according to the molar ratio of 1:3:20 and then react through a catalyst bed layer, and the reaction temperature is 400 ℃. After 5 hours of reaction, the conversion rate of p-chlorotoluene was 99.5%, and the molar yield of p-chlorobenzonitrile was 83.5%;
a performance test was conducted using the catalyst obtained in example 6, and the conversion of p-chlorotoluene was 85.6% and the molar yield of p-chlorobenzonitrile was 64.3% at 400 ℃; the conversion of p-chlorotoluene at 440 ℃ was 92.2% and the molar yield of p-chlorobenzonitrile was 73.4%. With nano Cr2V4O13The material (the preparation method is shown in CN202110464630.4, the same below) The performance test was carried out, and the conversion of p-chlorotoluene was 86.8% and the molar yield of p-chlorobenzonitrile was 66.3% at 350 ℃ (optimum temperature).
Example 8
10g of the micro-nano vanadium-molybdenum composite oxide prepared in the example 2 is filled in a quartz tube fixed bed reactor with the inner diameter of 30mm, the raw material, ammonia gas and air are preheated and mixed according to the molar ratio of 1:8:40 and then react through a catalyst bed layer, and the reaction temperature is 420 ℃. After 5 hours of reaction time, the conversion of m-xylene was 98.7% and the molar yield of m-phthalonitrile was 80.9%.
Using the catalyst obtained in example 6, performance tests were carried out, and the conversion of xylene was 95.4% at a temperature of 460 ℃ and the molar yield of isophthalonitrile was 71.2%. With nano Cr2V4O13The material is subjected to a performance test, the conversion rate of the dimethylbenzene is 85.2 percent at the temperature of 350 ℃, and the molar yield of the m-dicyanobenzene is 70.4 percent.
Example 9
12g of the micro-nano vanadium-molybdenum composite oxide prepared in the example 3 is filled in a quartz tube fixed bed reactor with the inner diameter of 30mm, the raw material, ammonia gas and air are preheated and mixed according to the molar ratio of 1:7:30 and then react through a catalyst bed layer, and the reaction temperature is 390 ℃. After 5 hours of reaction, the conversion of 2, 4-dichlorotoluene was 97.6% and the molar yield of 2, 4-dichlorobenzonitrile was 84.4%.
Using the catalyst obtained in example 6, performance test was conducted, and the conversion of 2, 4-dichlorotoluene was 89.8% and the molar yield of 2, 4-dichlorobenzonitrile was 68.3% at a temperature of 440 ℃. With nano Cr2V4O13The material was subjected to a performance test, and the conversion of 2, 4-dichlorotoluene was 88.5% and the molar yield of 2, 4-dichlorobenzonitrile was 69.0% at a temperature of 350 ℃ (optimum temperature).
Example 10
12g of the micro-nano vanadium-molybdenum composite oxide prepared in the example 5 is filled in a quartz tube fixed bed reactor with the inner diameter of 30mm, the raw material, ammonia gas and air are preheated and mixed according to the molar ratio of 1:8:25 and then react through a catalyst bed layer, and the reaction temperature is 380 ℃. After 5 hours of reaction time, the conversion of p-methoxytoluene was 88.6% and the molar yield of Anisotropic nitrile was 74.7%.
A performance test was conducted on the catalyst obtained in example 6, and the conversion of p-methoxytoluene was 73.1% and the molar yield of anisole was 48.9% at a temperature of 420 ℃. With nano Cr2V4O13The material is subjected to performance test, the conversion rate of p-methoxytoluene at 350 ℃ is 85.6%, and the molar yield of the anisyl nitrile is 73.7%.
Claims (9)
1. A micro-nano vanadium molybdenum composite oxide is characterized in that: the micro-nano vanadium-molybdenum composite oxide is macroscopically in a rectangular block shape, and the length of the micro-nano vanadium-molybdenum composite oxide is 200-2000 nm; the thickness is 50-500nm, and the microscopic structure is a layered structure of one-dimensional nano-sheet self-assembly stacking.
2. The preparation method of the micro-nano vanadium-molybdenum composite oxide of claim 1, which is characterized by comprising the following steps:
mixing a vanadium source and a molybdenum source according to a metal atom molar ratio of 2:1, placing the mixture in a pressure container, adding a solvent, uniformly mixing, sealing, heating to 120-300 ℃, carrying out solvothermal reaction for 2-200 hours, and filtering, washing and vacuum-drying a product to obtain a precursor;
calcining the precursor at the temperature of 300-800 ℃ for 0.1-10 hours, and cooling to room temperature to obtain the micro-nano vanadium-molybdenum composite oxide.
3. The preparation method of the micro-nano vanadium-molybdenum composite oxide according to claim 2, characterized by comprising the following steps: the vanadium source is vanadium oxide or vanadium salt, and the molybdenum source is molybdenum oxide or molybdenum salt.
4. The preparation method of the micro-nano vanadium-molybdenum composite oxide according to claim 2 or 3, characterized by comprising the following steps: the vanadium oxides include, but are not limited to, V2O5、V2O4Or V2O3Said vanadium salt including but not limited to NH4VO3、VOSO4、VOCl2(ii) a Oxidation of the molybdenumSubstances include, but are not limited to MoO3、MoO2The molybdenum salt includes but is not limited to (NH)4)2MoO4、(NH4)6Mo7O24、Na2MoO4Or MoO2(acac)2。
5. The preparation method of the micro-nano vanadium-molybdenum composite oxide according to claim 2 or 3, characterized by comprising the following steps: the solvent of the solvothermal reaction is alcohol or an aqueous solution thereof.
6. The preparation method of the micro-nano vanadium-molybdenum composite oxide according to claim 5, characterized by comprising the following steps: the alcohol includes, but is not limited to, polyvinyl alcohol or monohydric, polyhydric alcohols from C1 to C20.
7. The preparation method of the micro-nano vanadium-molybdenum composite oxide according to claim 2 or 3, characterized by comprising the following steps: the pressure vessel is an autoclave or a pressure-resistant reactor.
8. The application of the micro-nano vanadium-molybdenum composite oxide disclosed by claim 1 in preparing aromatic nitrile by catalyzing methyl aromatic ammoxidation.
9. Use according to claim 8, characterized in that: the methyl aromatic hydrocarbon comprises toluene, halogenated toluene, methoxytoluene, hydroxytoluene, nitrotoluene, cyanotoluene, aminotoluene, xylene, methylpyridine, methylpyrazine or methylpyrimidine.
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| CN113277561A (en) * | 2021-04-26 | 2021-08-20 | 中南民族大学 | Nano Cr2V4O13Material, preparation method and application thereof |
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