CN111825118B - Molybdenum dioxide nano-microsphere and preparation method and application thereof - Google Patents
Molybdenum dioxide nano-microsphere and preparation method and application thereof Download PDFInfo
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- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000004005 microsphere Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229960002446 octanoic acid Drugs 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 238000009827 uniform distribution Methods 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000002077 nanosphere Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZGHDMISTQPRNRG-UHFFFAOYSA-N dimolybdenum Chemical compound [Mo]#[Mo] ZGHDMISTQPRNRG-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 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
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- 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
- B01J35/39—Photocatalytic properties
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Abstract
The invention relates to the technical field of nano materials, in particular to a molybdenum dioxide nano microsphere and a preparation method and application thereof. The invention discloses a preparation method of molybdenum dioxide nano-microspheres, which is simple to operate, can obtain the nano-microspheres with uniform size, uniform distribution, small particle size and larger specific surface area by using a simple hydrothermal synthesis method, and has high activity and high selectivity; and the yield of the molybdenum dioxide microspheres prepared by the preparation method can reach 90 percent. The molybdenum dioxide nano-microsphere provided by the invention is applied to the field of photocatalysis, and can show high photocatalysis effect.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a molybdenum dioxide nano microsphere and a preparation method and application thereof.
Background
The oxide of molybdenum has two main forms, molybdenum trioxide (MoO) 3 ) And molybdenum dioxide (MoO) 2 ). Wherein MoO 2 Belongs to monoclinic system, has good catalytic performance and is insoluble in most acids. The unique chemical property makes it widely applicable in both traditional catalytic fields (e.g. oxidation of alkanes) and electrochemical fields (e.g. lithium ion batteries, supercapacitors).
Molybdenum dioxide is a relatively special transition metal oxide, since Mo is present therein 4+ Has attracted a great deal of attention because of its high surface area to volume ratio, high density of surface unsaturated atoms and excellent conductivity, so that it exhibits a 1T-like phase MoS 2 Has high capacitance and very low resistivity. Due to MoO 2 Has good conductivity which is not possessed by common oxides, and Mo is 4+ Free electron density in valence band is high and unlike MoO 3 Middle Mo 6+ All valence band electrons are bound by the surrounding oxygen atoms, which enhances the MoO 2 The catalytic activity of (2) makes it widely used in the field of organic catalysis. In addition, due to MoO 2 The high-conductivity molybdenum-molybdenum composite material has the advantages of excellent conductivity, high carrier transfer rate, tunnel-shaped gaps in a lattice structure of the high-conductivity molybdenum composite material, contribution to quick embedding and penetrating of charged particles, high content of molybdenum in a crust and low cost, and can be used for electrochemical application in preparation of anode materials of super capacitors and lithium ion batteries and the like.
Currently, nanostructured MoO is prepared 2 The method mainly comprises an electrochemical deposition method, an electrolytic deposition method, a thermal evaporation method, a magnetron sputtering method, a chemical synthesis method, a chemical vapor deposition method and the like, and the preparation process is relatively complex and the cost is high.
Disclosure of Invention
In view of this, the invention provides a molybdenum dioxide nanoparticle, a preparation method and an application thereof, the molybdenum dioxide nanoparticle is prepared by a hydrothermal method, the preparation method is simple, and the prepared molybdenum dioxide nanoparticle has the advantages of uniform size, uniform distribution, small particle size, large specific surface area, high activity and high selectivity.
The specific technical scheme is as follows:
the invention provides a preparation method of molybdenum dioxide nano microspheres, which comprises the following steps:
step 1: mixing the aqueous solution of molybdate with acid, and filtering to obtain a molybdate precipitate;
step 2: mixing the molybdic acid precipitate with strong acid and reducing acid, and carrying out solvothermal reaction to obtain molybdenum dioxide nano microspheres;
the strong acid is selected from one or at least two of sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid and caprylic acid.
In the present invention, the molybdic acid precipitate is mixed with a strong acid and a reducing acid to undergo a solvothermal reaction, thereby obtaining Mo 6+ Reduction to Mo 4+ And obtaining the molybdenum dioxide nano-microspheres.
At present, common morphologies of molybdenum dioxide nano materials include nanosheets, nano particles and the like, but the molybdenum dioxide nano materials have low yield, uneven size and distribution and low conversion rate and selectivity as photocatalysts, so that the practical application of the molybdenum dioxide nano materials is limited.
The preparation method of the molybdenum dioxide nano-microspheres provided by the invention is simple to operate and high in yield, and the nano-microspheres with uniform size and uniform distribution can be obtained by using a simple hydrothermal synthesis method, and have small particle size and larger specific surface area.
In step 1 of the invention, the aqueous solution of molybdate is obtained by dissolving molybdate in deionized water and performing ultrasonic dispersion, wherein the ultrasonic dispersion time is preferably 10min to 60min, and more preferably 30 min;
the molybdate is selected from sodium molybdate, ammonium molybdate or potassium molybdate;
the acid is one or at least two selected from sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid and caprylic acid;
the molar ratio of said molybdate to said acid is (5-20): 1, preferably 10: 1;
the aqueous molybdate solution is mixed with the acid and preferably filtered with suction to obtain a wet molybdic acid precipitate.
In step 2 of the present invention, the reducing acid is one or at least two selected from lactic acid, oxalic acid and citric acid, and preferably lactic acid.
In step 2 of the present invention, the molybdic acid precipitate is preferably mixed with a strong acid, and after ultrasonic dispersion, a reducing acid is added to perform ultrasonic dispersion, wherein the molar ratio of the strong acid to the molybdic acid precipitate is 1: (2-10); the molar ratio of the reducing acid to the molybdic acid precipitate is 1: (1-15), preferably 1: 8; the concentration of the strong acid is preferably 20M, and the concentration of the reducing acid is preferably 9 mM-18 mM; the ultrasonic dispersion time is 10min to 60min, preferably 30 min;
and then carrying out a solvothermal reaction at the temperature of 120-300 ℃ for 8-48 h, preferably at the temperature of 220 ℃ for 18 h.
The invention also provides a molybdenum dioxide nano microsphere prepared by the preparation method.
The molybdenum dioxide nano-microspheres provided by the invention have the advantages of uniform size, uniform distribution, small particle size and larger specific surface area.
The particle size of the molybdenum dioxide nano-microspheres is 150-300nm, and preferably 200 nm.
The invention also provides the application of the molybdenum dioxide nano-microsphere in photocatalysis.
The molybdenum dioxide nano-microsphere provided by the invention can be used as a photocatalyst and has higher selectivity and activity.
In the invention, taking catalytic cyclohexane as an example, the application of the molybdenum dioxide nano-microsphere in photocatalysis specifically comprises the following steps:
dissolving the molybdenum dioxide nano microspheres in an organic solvent, and then adding cyclohexane and an oxidant to carry out photo-thermal catalytic reaction to obtain hexanol and cyclohexanone.
In the invention, the photo-thermal catalytic reaction is preferably carried out in a photo-thermal catalytic high-pressure reaction kettle; the mass-volume ratio of the molybdenum dioxide microspheres to cyclohexane is (1-5) mg: 1mL, preferably 20 mg: 10 mL; the oxidant is preferably dry air; the reaction pressure is preferably 1.5MPa, the temperature is 60-180 ℃, the temperature is preferably 120 ℃, the light source is preferably a xenon lamp, and the light intensity is 100mW/cm 2 ～2000mW/cm 2 Preferably 1000mw/cm 2 。
According to the technical scheme, the invention has the following advantages:
the invention provides a preparation method of molybdenum dioxide nano microspheres, which is simple to operate, can obtain the nano microspheres with uniform size, uniform distribution, small particle size and larger specific surface area by using a simple hydrothermal synthesis method, and has high activity and high selectivity; and the yield of the molybdenum dioxide microspheres prepared by the preparation method can reach 90 percent. The molybdenum dioxide nano-microsphere provided by the invention is applied to the field of photocatalysis, and can show high photocatalysis effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is an XRD pattern of the molybdenum dioxide nanospheres in example 1 of the present invention;
FIG. 2 is an electron micrograph of a molybdenum dioxide nanosphere in example 1 of the present invention, wherein (a), (b) and (c) are TEM images and (d) is SEM image.
FIG. 3 is an SEM photograph of the molybdenum dioxide nano-microspheres in example 2 of the present invention;
FIG. 4 is an SEM photograph of the molybdenum dioxide nanospheres in example 3 of the present invention;
FIG. 5 is a comparison graph of the selectivity and the conversion rate of cyclohexane oxidation catalyzed by the molybdenum dioxide nano-microspheres obtained in examples 1 to 3 of the present application.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. 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.
Example 1
The embodiment is a preparation method of molybdenum dioxide nano microspheres, which comprises the following specific preparation steps:
1. weighing 1g of sodium molybdate, dissolving in 20mL of deionized water, dispersing for about 30min by using ultrasonic waves, and mixing with 2mL of nitric acid;
2. filtering the mixture to obtain wet molybdic acid precipitate;
3. adding 2mL of 20M acetic acid into the obtained molybdic acid precipitate, and performing ultrasonic dispersion for about 1 h;
4. adding 2mL of 14mM lactic acid into the dispersed molybdic acid mixture, and continuing ultrasonic dispersion for about 1 h;
5. transferring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, placing the kettle in an oven, and carrying out solvothermal reaction for 24h at the temperature of 180 ℃;
6. after the reaction is finished, naturally cooling the product to room temperature, transferring the product into a centrifugal tube, and washing the product with acetone and ethanol for multiple times to obtain molybdenum dioxide nano microspheres;
7. adding 20mL of ethanol for storage.
As shown in fig. 1 and fig. 2, the molybdenum dioxide nano-microsphere was successfully prepared in this example. As shown in FIG. 2, the particle size of the molybdenum dioxide nanoparticle of the present embodiment is about 150-250nm, and the size is uniform and the distribution is uniform.
The yield of the molybdenum dioxide nano-microspheres prepared by the embodiment is about 90%.
Example 2
The embodiment is a preparation method of molybdenum dioxide nano microspheres, which comprises the following specific preparation steps:
1. weighing 0.8g of sodium molybdate, dissolving in 20mL of deionized water, dispersing for about 30min by using ultrasonic waves, and mixing with 2mL of sulfuric acid;
2. filtering the mixture to obtain wet molybdic acid precipitate;
3. adding 2mL of 20M octanoic acid into the obtained molybdic acid precipitate, and ultrasonically dispersing for about 1 h;
4. adding 2mL of 9mM citric acid into the dispersed molybdic acid mixture, and continuing ultrasonic dispersion for about 1 h;
5. transferring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, placing the kettle in an oven, and carrying out solvothermal reaction for 24h at the temperature of 180 ℃;
6. after the reaction is finished, naturally cooling the product to room temperature, transferring the product into a centrifugal tube, and washing the product with acetone and ethanol for multiple times;
7. adding 20mL of ethanol for storage.
As shown in fig. 3, the particle size of the molybdenum dioxide nanoparticle is about 150-300nm, the size is uniform, and the distribution is uniform.
The yield of the molybdenum dioxide nano-microspheres prepared by the embodiment is about 90%.
Example 3
The embodiment is a preparation method of molybdenum dioxide nano microspheres, which comprises the following specific preparation steps:
1. weighing 0.6g of sodium molybdate, dissolving in deionized water, and dispersing for about 30min by using ultrasonic waves to obtain a molybdate solution; mixing with a molybdate solution and 2mL of hydrochloric acid to obtain a mixture;
2. filtering the mixture to obtain wet molybdic acid precipitate;
3. adding 1.5mL of 20M formic acid into the obtained molybdic acid precipitate, and ultrasonically dispersing for about 1 h;
4. adding 2mL of 18mM oxalic acid into the dispersed molybdic acid mixture, and continuing ultrasonic dispersion for about 1 h;
5. transferring the mixture into a 50mL polytetrafluoroethylene high-pressure reaction kettle, placing the kettle in an oven, and carrying out solvothermal reaction for 24h at the temperature of 180 ℃;
6. after the reaction is finished, naturally cooling the product to room temperature, transferring the product into a centrifugal tube, and washing the product with acetone and ethanol for multiple times;
7. adding 20mL of ethanol for storage.
As shown in fig. 4, the particle size of the molybdenum dioxide nanoparticle is about 150-300nm, the size is uniform, and the distribution is uniform.
The yield of the molybdenum dioxide nano-microspheres prepared by the embodiment is about 90%.
Example 4
The embodiment of the application provides a cyclohexane catalytic oxidation experiment of the molybdenum dioxide nano-microsphere prepared by the embodiment, which comprises the following specific steps:
1. the molybdenum dioxide nanospheres (MoO) of examples 1-3 2 ) Respectively weighing 20mg, dissolving in 5mL of acetone, and ultrasonically dispersing for 30min to obtain three parts of mixed solution;
2. respectively adding the mixed solution obtained in the step 1 and 10mL of cyclohexane into a photo-thermal catalytic high-pressure reaction kettle;
3. introducing dry air into the photo-thermal catalytic high-pressure reaction kettle, using the dry air as an oxidant, adjusting the pressure of the photo-thermal catalytic high-pressure reaction kettle to be 1.5MPa, setting the temperature to be 120 ℃, turning on a xenon lamp, and controlling the light intensity to be 1000mw/cm 2 To perform a test and a meterThe results are shown in FIG. 5, which shows the conversion of cyclohexane catalytic oxidation and the selectivity of the catalytic main products cyclohexanol and cyclohexanone (the mixture of the two is called KA oil).
As can be seen from fig. 5, the molybdenum dioxide nanoparticles prepared in examples 1 to 3 can improve the conversion rate of cyclohexane catalytic oxidation while maintaining high selectivity, and have high activity and high selectivity.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; 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 (3)
1. A process for catalyzing cyclohexane to produce hexanol and cyclohexanone, comprising the steps of:
dissolving the molybdenum dioxide nano microspheres in an organic solvent, and then adding cyclohexane and an oxidant to carry out a photo-thermal catalytic reaction to obtain hexanol and cyclohexanone;
the photo-thermal catalytic reaction is carried out in a photo-thermal catalytic high-pressure reaction kettle;
in the photo-thermal catalytic reaction, the mass-to-volume ratio of the molybdenum dioxide nano-microspheres to cyclohexane is 1-5 mg: 1 mL;
the reaction pressure of the photo-thermal catalytic reaction is 1.5MPa, and the temperature is 60-180 ℃;
the preparation method of the molybdenum dioxide nano-microsphere comprises the following steps:
step 1: mixing the aqueous solution of molybdate with acid, and filtering to obtain a molybdate precipitate;
step 2: mixing the molybdic acid precipitate with organic acid and reducing acid, and carrying out solvothermal reaction to obtain molybdenum dioxide nano microspheres;
the acid in the step 1 is one or at least two selected from sulfuric acid, hydrochloric acid and nitric acid;
the organic acid in the step 2 is selected from one or at least two of formic acid, acetic acid and caprylic acid, and the reducing acid is selected from one or at least two of lactic acid, oxalic acid and citric acid;
in step 1, the molar ratio of the molybdate to the acid is (5-20): 1;
the molar ratio of the organic acid to the molybdic acid precipitate is 1: (2-10);
the molar ratio of the reducing acid to the molybdic acid precipitate is 1: (1-15);
the reaction temperature of the solvothermal reaction is 120-300 ℃, and the reaction time is 8-48 h.
2. The process of claim 1, wherein the molybdate is selected from sodium molybdate, ammonium molybdate, and potassium molybdate.
3. The method for catalyzing cyclohexane to generate hexanol and cyclohexanone according to claim 1, wherein the particle size of the molybdenum dioxide nano-microspheres is 150-300 nm.
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