CN106540678B - Vanadium trioxide nano particle and preparation method - Google Patents
Vanadium trioxide nano particle and preparation method Download PDFInfo
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- CN106540678B CN106540678B CN201610935755.XA CN201610935755A CN106540678B CN 106540678 B CN106540678 B CN 106540678B CN 201610935755 A CN201610935755 A CN 201610935755A CN 106540678 B CN106540678 B CN 106540678B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 67
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000012790 confirmation Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 2
- 230000005611 electricity Effects 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 241000257465 Echinoidea Species 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- 241000736199 Paeonia Species 0.000 description 4
- 235000006484 Paeonia officinalis Nutrition 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to Material Fields, are related to a kind of vanadium trioxide nano particle, and for the vanadium trioxide nano particle in spherical, particle size range is 50-100 nanometer, and specific surface area is 120.4 ± 0.1 square metres every gram.The present invention also provides the preparation method of vanadium trioxide nano particle, method includes: that commercially available vanadic anhydride is added in ethylene glycol, is uniformly mixed, and forms suspending liquid A；Hydrochloric acid is added to suspending liquid A, forms the suspension B that pH is about 1；Suspension B is heated, cooling is stored at room temperature, obtains the product containing dark blue precipitate；The mixed solution of product containing dark blue precipitate is centrifugated, washs and dries, obtain spherical nano particle.Barium oxide nano particle of the invention has very high specific surface area, and stronger structural stability facilitates its raising as electricity material and catalyst performance.
Description
Technical field
The invention belongs to Material Fields, are related to a kind of vanadium trioxide nano particle, more particularly to a kind of spherical three oxygen
Change two vanadium nano particles and preparation method.
Background technique
Vanadium trioxide is known as traditional catalyst.In recent years, with the research to its nanostructure
Gradually deeply, people not only focus on the performance of traditional catalyst field, and it is in emerging electrode material of lithium battery side
The excellent performance in face, gradually by people's extensive concern.Vanadium trioxide is a kind of with the mutual conversion character of conductor insulation
Material.At a certain temperature, electric conductivity has qualitative leap to substance with this property, i.e., is converted to insulation from conductor
Body is converted to conductor from insulator, and this process is reversible.It is well known that the property and application performance of nano material are very
The morphology and size of its particle is depended in big degree.And the morphology and size of particle often have with synthetic method and path it is close
The connection cut.Uniform spherical nanoparticle, structure is simple, facilitates and be self-assembled into device and formation fixed bed catalyst.
And for catalyst, the secondary cleaning of catalyst and recycling and reusing are convenient for without dead angle in spheric granules surface.In addition by ball
The three-dimensional structure that shape particle (self assembly) accumulation is formed is capable of providing more reaction positions, thus preferably mutual with reactant
Contact, is conducive to the raising of its catalytic performance.About spherical vanadium trioxide, there are some reports at present.Method is concentrated mainly on
Vanadyl acetylacetonate: (1) being dissolved in 20 milliliters of ethyl alcohol by following two, and 30 milliliters of hydrogen peroxide are added afterwards.The above mixed liquor is put
It sets and is heated 24 hours in 150 DEG C of autoclaves.It will calcine 2 hours, can be obtained under 400 DEG C of nitrogen after the drying of obtained precipitation and separation
To the pattern vanadium trioxide particle.(2) ammonium metavanadate is dissolved in 50 ml deionized waters, using nitric acid by system pH tune
To 2, and at 50 DEG C stirring until there is orange precipitating.The above solution is added in 20 ml methanols, stands 24 hours at room temperature.
Precipitating becomes to be isolated washing when darkorange.Darkorange precipitating is the vanadium oxide particles of spherical looks.Later, one
Determine at temperature (such as 600 DEG C) under reducing atmosphere (such as hydrogen) and calcine the particle, three vanadium oxides of similar pattern can be obtained.
The pattern and above-mentioned vanadium trioxide particle of other method synthesis have apparent difference, such as sea urchin shape vanadium trioxide micron
Particle.
Above method cost of material is higher, and method is complicated, is unfavorable for being mass produced, to subsequent use bring it is huge not
Just.In view of this, the present invention is specifically proposed.
Summary of the invention
In order to solve the above technical problems in background technology, the purpose of the present invention is to provide a kind of operation letters
Single, safety and environmental protection and low-cost spherical vanadium trioxide nano particle and preparation method.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of vanadium trioxide nano particle, it is characterised in that: the vanadium trioxide nano particle is described in spherical
The particle size range of vanadium trioxide nano particle is 50-100 nanometers, and the specific surface area of the vanadium trioxide nano particle is
120.4 ± 0.1 square metres every gram.
Above-mentioned vanadium trioxide nano particle purity is not less than 99.5%.
A method of being used to prepare foregoing vanadium trioxide nano particle, it is characterised in that: the method packet
Include following steps:
1) vanadic anhydride is added in ethylene glycol, is uniformly mixed, form suspending liquid A；Five oxygen in the suspending liquid A
Changing two vanadium relative to the molar concentration of ethylene glycol is 0.1-0.3mM；
2) pH to pH=1 for adjusting suspending liquid A, obtains suspension B；
3) 200-280 DEG C is gradually heated to suspension B in autoclave, and at this temperature after holding 36-48 hours,
25 ± 1 DEG C of standing coolings, obtain the mixed solution C containing dark blue precipitate；
4) the obtained mixed solution C containing dark blue precipitate of step 3) is centrifuged under the conditions of 2000-3000rpm and is divided
From, respectively using ethyl alcohol and deionized water washing until supernatant it is colorless and transparent, under conditions of 50-80 DEG C dry after obtain class
Spherical vanadium trioxide nano particle.
The above method is after step 4) further include:
5) pattern for the vanadium trioxide nano particle that step 4) is obtained by SEM scanning electron microscope and XRD detection and
Composition characteristics carry out observation confirmation.
Above-mentioned steps 1) in stirring be to be carried out in 50-70 DEG C of water-bath.
Above-mentioned steps 2) it is the pH that suspending liquid A is adjusted using hydrochloric acid；The mass concentration of the hydrochloric acid is 23-36%；It is described
The additional amount of hydrochloric acid is that 1-4mL hydrochloric acid is added in every 16ml suspending liquid A.
The invention has the advantages that
The present invention provides a kind of vanadium trioxide nano particles in spherical, and particle size range is 50-100 nanometers, than
Surface area is 120.4 ± 0.1 square metres every gram.The present invention by by vanadic anhydride be added ethylene glycol in, be uniformly mixed,
Form suspending liquid A；Acidification is carried out to suspending liquid A, makes its pH=1, is gradually heated up the solution after acidification in autoclave,
It is stored at room temperature after cooling to mixed solution centrifuge separation is obtained, respectively using ethyl alcohol and deionized water washing until supernatant is colourless
It is transparent, spherical vanadium trioxide nano particle is obtained after drying.Three oxidations two that method provided by the present invention is prepared
Vanadium nano particle has very high specific surface area, whole spherical in shape, has stronger structural stability, this facilitates it as battery
The raising of material and catalyst performance.Uniform spherical nano particle, structure is simple, facilitates and carries out being self-assembled into device and shape
At fixed bed catalyst.And for catalyst, the secondary cleaning of catalyst and recycling are convenient for without dead angle in spheric granules surface
It recycles.By the three-dimensional structure that accumulation (self assembly) is formed, more reaction positions are capable of providing, are formed preferably with reactant
Contact, is conducive to the raising of catalytic performance.The preparation method of spherical nano particle provided by the present invention is easy to operate, cost
Possibility that is cheap, having mass production has a wide range of applications in new energy (lithium battery), catalytic field.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is preparation manipulation scheme schematic diagram of the invention；
Fig. 2 is the stereoscan photograph of spherical vanadium trioxide nano particle prepared by the embodiment of the present invention 1；
Fig. 3 is the X ray diffracting spectrum of spherical vanadium trioxide nano particle prepared by the embodiment of the present invention 1, is used
In the obtained particulate component of confirmation be vanadium trioxide；
Fig. 4 is vanadium trioxide particle (such as spherical vanadium trioxide of different-shape prepared by the embodiment of the present invention 1
Nano particle, flower-shaped three vanadium oxides nano particle and three vanadium oxide nano particle of sea urchin shape) as carbon monoxide hydrogenation
The CO conversion of catalyst at different temperatures.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Referring to Fig. 1, Fig. 2 and Fig. 3, the present invention provides a kind of vanadium trioxide nano particle, which is received
Rice grain is in spherical, and the particle size range of vanadium trioxide nano particle is 50-100 nanometers, vanadium trioxide nano particle
Specific surface area is 120.4 ± 0.1 square metres every gram, and the purity of vanadium trioxide nano particle is not less than 99.5%.
Referring to Fig. 1, the method such as preceding vanadium trioxide nano particle, this method are used to prepare the present invention provides a kind of
The following steps are included:
1) vanadic anhydride is added in ethylene glycol, in 50-70 DEG C of stirred in water bath and is uniformly mixed, form suspension
A；Vanadic anhydride is 0.1-0.3mM relative to the molar concentration of ethylene glycol in suspending liquid A；Wherein, vanadic anhydride is in this hair
Play the role of very important in bright, it is excessive that the excessive concentration of vanadic anhydride will cause the nano particle formed in subsequent reactions
And it is uneven, and when its concentration is too low, then will lead to can not form particle.Vanadic anhydride and ethylene glycol are all made of commercially available examination
Agent, safety and environmental protection, source are easy to get, are low in cost；
2) pH for adjusting suspending liquid A using hydrochloric acid obtains suspension B to pH=1 ± 0.2；The mass concentration of hydrochloric acid is 23-
36%；The additional amount of hydrochloric acid is that 1-4mL hydrochloric acid is added in every 16ml suspending liquid A；Hydrochloric acid is added and is designed to provide an acidity
Environment, hydrogen ion are the catalyst and reaction initiator of this synthetic reaction, and reaction is caused by hydrogen ion, can accelerate precipitated product
It generates；
3) 200-280 DEG C is gradually heated to suspension B in autoclave, and at this temperature after holding 36-48 hours,
25 ± 1 DEG C of standing coolings, obtain the mixed solution C containing dark blue precipitate；High temperature and pressure heats suspension B, so that five oxidations
Two vanadium can be dissolved in ethylene glycol and chemically react with ethylene glycol, generate the precipitating of vanadium trioxide；
4) the obtained mixed solution C containing dark blue precipitate of step 3) is centrifuged under the conditions of 2000-3000rpm and is divided
From, respectively using ethyl alcohol and deionized water washing until supernatant it is colorless and transparent, under conditions of 50-80 DEG C dry after obtain class
Spherical vanadium trioxide nano particle.
5) pattern for the vanadium trioxide nano particle that step 4) is obtained by SEM scanning electron microscope and XRD detection and
Composition characteristics carry out observation confirmation, are vanadium trioxide by the particulate component that X ray diffracting spectrum confirms referring to Fig. 3.
Vanadium trioxide nano particle provided by the present invention and preparation method are carried out below by specific embodiment
It is described in detail:
Embodiment 1
Vanadium trioxide nano particle is prepared according to the following steps:
1) commercially available vanadic anhydride is added in ethylene glycol solution, is stirred strongly 2 hours in bath in 50 DEG C of water, keep it mixed
It closes uniformly, forms suspending liquid A；The molar concentration of vanadic anhydride is 0.1M in suspending liquid A；
2) 1mL hydrochloric acid is added into suspending liquid A, the color of suspending liquid A is made to become peony from brown color, forms suspension
B, wherein the mass concentration of hydrochloric acid is 23%；
3) suspension B is put into autoclave and is heated, heating temperature is 200 DEG C, and heating time is 36 hours, is stored at room temperature
It can arrive after cooling containing dark blue precipitate mixed solution；
4) step 3) is formed by the centrifuge separation of the mixed solution containing dark blue precipitate, centrifugal rotational speed 2000-
3000rpm, respectively with ethyl alcohol and deionized water wash until supernatant it is colourless, dried at 50 DEG C.Obtain spherical three oxidation
Vanadium nano particle.
Embodiment 2
Nano particle is prepared according to the following steps:
1) commercial vanadic anhydride is added in ethylene glycol solution, is stirred strongly 2 hours in bath in 70 DEG C of water, keep it mixed
It closes uniformly, forms suspending liquid A；The molar concentration of vanadic anhydride is 0.2mM in suspending liquid A；
2) 3mL hydrochloric acid is added into suspending liquid A, the color of suspending liquid A is made to become peony from brown color, forms suspension
B, wherein the mass concentration of hydrochloric acid is 23%；
3) suspension B is put into autoclave and is heated, heating temperature is 240 DEG C, and heating time is 40 hours, is stored at room temperature
The mixed solution containing dark blue precipitate can be arrived after cooling；
4) step 3) is formed by the centrifuge separation of the mixed solution containing dark blue precipitate, centrifugal rotational speed 2000-
3000rpm, respectively with ethyl alcohol and deionized water wash until supernatant it is colorless and transparent, dried at 70 DEG C.Obtain spherical three
V 2 O nano particle.
Embodiment 3
Nano particle is prepared according to the following steps:
1) commercial vanadic anhydride is added in ethylene glycol solution, is stirred strongly 2 hours in bath in 60 DEG C of water, keep it mixed
It closes uniformly, forms suspending liquid A；The molar concentration of vanadic anhydride is 0.25mM in suspending liquid A；
2) 4mL hydrochloric acid is added into suspending liquid A, the color of suspending liquid A is made to become peony from brown color, forms suspension
B, wherein the mass concentration of hydrochloric acid is 36%；
3) suspension B is put into autoclave and is heated, heating temperature is 260 DEG C, and heating time is 44 hours, is stored at room temperature
The mixed solution containing dark blue precipitate can be arrived after cooling；
4) step 3) is formed by the centrifuge separation of the mixed solution containing dark blue precipitate, centrifugal rotational speed 2000-
3000rpm, respectively with ethyl alcohol and deionized water wash until supernatant it is colorless and transparent, dried at 60 DEG C.Obtain spherical three
V 2 O nano particle.
Embodiment 4
Nano particle is prepared according to the following steps:
1) commercial vanadic anhydride is added in ethylene glycol solution, is stirred strongly 2 hours in bath in 60 DEG C of water, keep it mixed
It closes uniformly, forms suspending liquid A；The molar concentration of vanadic anhydride is 0.3mM in suspending liquid A；
2) 4mL hydrochloric acid is added into suspending liquid A, the color of suspending liquid A is made to become peony from brown color, forms suspension
B, wherein the mass concentration of hydrochloric acid is 36%；
3) suspension B is put into autoclave and is heated, heating temperature is 280 DEG C, and heating time is 48 hours, is stored at room temperature
The mixed solution containing dark blue precipitate can be arrived after cooling；
4) step 3) is formed by the centrifuge separation of the mixed solution containing dark blue precipitate, centrifugal rotational speed 2000-
3000rpm, respectively with ethyl alcohol and deionized water wash until supernatant it is colorless and transparent, dried at 60 DEG C.Obtain spherical three
V 2 O nano particle.
Comparative experiments
The spherical vanadium trioxide nano particle of synthesis is evaluated using carbon monoxide (CO) hydrogenation reaction as catalysis
The catalytic performance of agent is prepared using sea urchin shape vanadium trioxide nano particle, flower-shaped vanadium trioxide nano particle and the present invention
Obtained spherical vanadium trioxide nano particle compares (comparative experimental data is shown in Fig. 4).The Hydrogenation Experiment of carbon monoxide
It is carried out in tubular flow reactor, pressure is 1 atmospheric pressure, and carbon monoxide and hydrogen molar ratio are 1:3, and flow velocity is 3.0 vertical
Square centimetre of every gram of catalyst is per minute.Product analysis utilizes the gas-chromatography (Shimadzu GC-8A) with thermal conductivity detector (TCD) to divide online
Analysis.Chromatogram column length is 2 meters, and for helium as carrier gas, flow velocity is 30 cubic centimetres per minutes.Fig. 4 shows three of the above catalyst
(sea urchin shape vanadium trioxide nano particle, flower-shaped vanadium trioxide nano particle and spherical vanadium trioxide nano particle) exists
The CO conversion of the co hydrogenation experiment carried out under different catalytic temperatures.For spherical three vanadium oxides nanometer
Grain, corresponding CO conversion is respectively when catalytic temperature is 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C
6.2%, 11.3%, 19.2%, 30.5%, 40.3%, 34.1%.Shown in the figure, spherical vanadium trioxide nano particle is made
For carbon monoxide hydrogenation agent CO conversion than sea urchin shape vanadium trioxide nano particle and it is flower-shaped three oxidation two
Vanadium nano particle is high, shows to the reaction, the spherical vanadium trioxide nano particle catalytic performance that the present invention synthesizes compares sea urchin
Shape vanadium trioxide nano particle and flower-shaped vanadium trioxide nano particle are high.Main cause can be attributed to the spherical particle
Relatively high specific surface area is capable of providing and more reacts position with carbon monoxide.In addition, being said from crystallography angle, three oxygen
Changing two vanadium nano particles is polycrystalline structure, i.e. individual particle is made of many monocrystalline, can expose more crystal faces in this way, so that
Increase with the reactivity of carbon monoxide.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (4)
1. a kind of preparation method of vanadium trioxide nano particle, the vanadium trioxide nano particle is in spherical, described three
The particle size range of V 2 O nano particle is 50-100 nanometers, and the specific surface area of the vanadium trioxide nano particle is
120.4 ± 0.1 square metres every gram；The vanadium trioxide nano particle purity is not less than 99.5%, it is characterised in that: the side
Method the following steps are included:
1) vanadic anhydride is added in ethylene glycol, is uniformly mixed, form suspending liquid A；Five oxidation two in the suspending liquid A
Vanadium is 0.1-0.3mM relative to the molar concentration of ethylene glycol；
2) pH to pH=1 for adjusting suspending liquid A, obtains suspension B；
3) 200-280 DEG C is gradually heated to suspension B in autoclave, and at this temperature after holding 36-48 hours, 25 ±
1 DEG C of standing cooling, obtains the mixed solution C containing dark blue precipitate；
4) the obtained mixed solution C containing dark blue precipitate of step 3) is centrifugated under the conditions of 2000-3000rpm,
Respectively using ethyl alcohol and deionized water washing until supernatant it is colorless and transparent, under conditions of 50-80 DEG C dry after obtain class ball
Shape vanadium trioxide nano particle.
2. according to the method described in claim 1, it is characterized by: the method is after step 4) further include:
5) pattern and ingredient for the vanadium trioxide nano particle that step 4) is obtained by SEM scanning electron microscope and XRD detection
Feature carries out observation confirmation.
3. method according to claim 1 or 2, it is characterised in that: the stirring in the step 1) is the water at 50-70 DEG C
It is carried out in bath.
4. according to the method described in claim 3, it is characterized by: the step 2) is the pH for adjusting suspending liquid A using hydrochloric acid；
The mass concentration of the hydrochloric acid is 23-36%；The additional amount of the hydrochloric acid is that 1-4mL hydrochloric acid is added in every 16ml suspending liquid A.
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| CN1724385A (en) * | 2005-06-03 | 2006-01-25 | 武汉大学 | Process for preparing crystal vanadium trioxide |
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| CN1724385A (en) * | 2005-06-03 | 2006-01-25 | 武汉大学 | Process for preparing crystal vanadium trioxide |
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