CN110227445A - A kind of WO3-xNano wire and the preparation method and application thereof - Google Patents
A kind of WO3-xNano wire and the preparation method and application thereof Download PDFInfo
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- CN110227445A CN110227445A CN201910575149.5A CN201910575149A CN110227445A CN 110227445 A CN110227445 A CN 110227445A CN 201910575149 A CN201910575149 A CN 201910575149A CN 110227445 A CN110227445 A CN 110227445A
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- dehydrated alcohol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002070 nanowire Substances 0.000 claims abstract description 83
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 25
- 239000010937 tungsten Substances 0.000 claims abstract description 25
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229960004756 ethanol Drugs 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 230000005855 radiation Effects 0.000 claims abstract description 5
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 12
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000003574 free electron Substances 0.000 description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 description 6
- 102000007698 Alcohol dehydrogenase Human genes 0.000 description 5
- 108010021809 Alcohol dehydrogenase Proteins 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000001815 biotherapy Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of WO3‑xNano wire and the preparation method and application thereof belongs to catalysis material preparation technical field.WO of the invention3‑xNano wire is made by method comprising the following steps: tungsten source and dehydrated alcohol being mixed, reaction solution is formed；By reaction solution in 140~180 DEG C of progress 12~20h of solvent thermal reaction, WO is obtained3‑xNano wire.It is 1~3 μm that the present invention, which has obtained length, and diameter is the WO of 5~10nm3‑xNano wire, the WO3‑xNano wire has very strong absorption in Visible-to-Near InfaRed region, has strong plasma effect；Can under conditions of room temperature, ultraviolet light+radiation of visible light catalysis ethanol dehydrogenation reaction.Embodiment statistics indicate that: under nitrogen-oxygen (oxygen volume accounting be 0.4%) mixed atmosphere, the yield highest of acetaldehyde has reached 896.67 μm of ol/ (gh), and selectivity has also reached 91%.
Description
Technical field
The present invention relates to catalysis material preparation technical field more particularly to a kind of WO3-xNano wire and preparation method thereof with answer
With.
Background technique
The local surfaces plasma effect (LSPR) that noble metal nano particles surface occurs can enhance the work of the absorption to light
With.However LSPR effect can also occur on the semiconductor grain surface of some high free carrier density.Due to semiconductor material
The synthetic method of material is simple, cheap, and has many advantages, such as strong LSPR effect, make its photocatalytic water, biological therapy,
The fields such as solar energy conversion have broad application prospects.
Alcohol dehydrogenase is industrially a kind of reaction of important production acetaldehyde, but current some technologies are all to need metal
Efficient conversion is just able to achieve under material and high-temperature and high-pressure conditions, catalytic condition is harsher, limits its application.
Therefore, a kind of catalyst how is provided, it is current for so that it is carried out Dehydrogenating reaction of alcohol under relatively mild conditions
The difficult point of research.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of WO3-xNano wire and the preparation method and application thereof.This hair
The WO of bright offer3-xNano wire has very strong absorption in Visible-to-Near InfaRed region, has strong plasma effect, normal
It can catalysis ethanol dehydrogenation reaction under warm, normal pressure temperate condition.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of WO3-xNano wire is made by method comprising the following steps:
Tungsten source and dehydrated alcohol are mixed, reaction solution is formed；
The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；
The tungsten source includes tungsten carbonyl or tungsten chloride；The temperature of the solvent thermal reaction is 140~180 DEG C, and the time is
12~20h.
Preferably, the WO3-xThe length of nano wire is 1~3 μm, and diameter is 5~10nm.
The present invention also provides the WO described in above-mentioned technical proposal3-xThe preparation method of nano wire, comprising the following steps:
Tungsten source and dehydrated alcohol are mixed, reaction solution is formed；
The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；
The tungsten source includes tungsten carbonyl or tungsten chloride；The temperature of the solvent thermal reaction is 140~180 DEG C, and the time is
12~20h.
It preferably, further include by gained solvent thermal reaction liquid cooled to room temperature, so after the solvent thermal reaction
After be centrifugated, by the solid being centrifugally separating to obtain washing, dry.
The present invention also provides the WO described in above-mentioned technical proposal3-xApplication of the nano wire in catalysis ethanol dehydrogenation reaction.
Preferably, it is described application the following steps are included:
By WO3-xIt after nano wire is mixed with dehydrated alcohol, is coated on carrier, obtains WO3-xNano wire and dehydrated alcohol sample
Product；
By the WO3-xNano wire and dehydrated alcohol sample are in normal pressure, nitrogen-oxygen mix atmosphere, ultraviolet light+visible light
Under irradiation, dehydrogenation reaction is carried out.
Preferably, the WO3-xThe amount ratio of nano wire and dehydrated alcohol is 5mg:0.2mL.
Preferably, volume content of the oxygen in nitrogen-oxygen mix atmosphere is 0~20%.
Preferably, the temperature of the dehydrogenation reaction is room temperature.
The present invention provides a kind of WO3-xNano wire is made by method comprising the following steps: by tungsten source and dehydrated alcohol
Mixing forms reaction solution；The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；The tungsten source includes six carbonyls
Tungsten or tungsten chloride；The temperature of the solvent thermal reaction is 140~180 DEG C, and the time is 12~20h.The present invention with tungsten carbonyl or
Tungsten chloride is tungsten source, and in 140~180 DEG C of progresss 12~20h of solvent thermal reaction, having obtained length is 1~3 μm, diameter for 5~
The WO of 10nm3-xNano wire, the WO3-xNano wire has very strong absorption in Visible-to-Near InfaRed region, has strong plasma
Effect；Can under the conditions of room temperature and relatively mild normal pressure catalysis ethanol dehydrogenation reaction.Embodiment statistics indicate that: in nitrogen
Under gas-oxygen (oxygen volume accounting is 0.4%) mixed atmosphere, the yield highest of acetaldehyde has reached 896.67 μm of ol/ (g
H), selectivity has also reached 91%.
The present invention also provides the WO described in above-mentioned technical proposal3-xThe preparation method of nano wire, preparation provided by the invention
Method is simple, easy to operate, low in cost.
The present invention also provides the WO described in above-mentioned technical proposal3-xApplication of the nano wire in catalysis ethanol dehydrogenation reaction.
WO of the invention3-xNano wire is under the irradiation of the joint of ultraviolet light and visible light, WO3-xIt is produced in nano wire valence band by ultraviolet excitation
Raw free electron can transit to the hot hole on imperfect tape and on imperfect tape carry out it is compound, make on imperfect tape freely electricity
Sub- density is maintained at a stable state；Therefore, WO3-xThis electron transfer processes of nano wire, make WO3-xNano wire can be seen
Do a kind of band structure with Z- type hetero-junctions；To realize high efficiency at room temperature and with high selectivity catalysis ethanol take off
Hydrogen reaction.
Detailed description of the invention
Fig. 1 is WO provided by the invention3-xNanowire catalytic alcohol dehydrogenase process schematic；
Fig. 2 is 1 gained WO of embodiment3-xThe transmission electron microscope image of nano wire；
Fig. 3 is 1 gained WO of embodiment3-xThe absorption spectrum of nano wire；
Fig. 4 is 1 gained WO of embodiment3-xNano wire thermionic transition process schematic diagram under the irradiation of different light；
Fig. 5 is 1 gained WO of embodiment3-xNano wire promotes alcohol dehydrogenase to generate acetaldehyde curve graph；
Fig. 6 is the present embodiment under nitrogen-oxygen (oxygen volume accounting is 0.4%) mixed atmosphere, different wave length irradiation
Gained WO3-xImpact effect figure of the nano wire to Dehydrogenating reaction of alcohol.
Specific embodiment
The present invention provides a kind of WO3-xNano wire is made by method comprising the following steps:
Tungsten source and dehydrated alcohol are mixed, reaction solution is formed；
The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；The tungsten source includes tungsten carbonyl or chlorination
Tungsten；The temperature of the solvent thermal reaction is 140~180 DEG C, and the time is 12~20h.
The present invention will mix tungsten source and dehydrated alcohol, form reaction solution.
In the present invention, the tungsten source is tungsten carbonyl or tungsten chloride, preferably tungsten carbonyl.The present invention is to the tungsten source
It is not specifically limited with the hybrid mode of dehydrated alcohol, using hybrid mode well known to those skilled in the art, specifically
Such as stirring.In addition, the present invention is not specifically limited the amount ratio in the tungsten source and dehydrated alcohol, in specific implementation of the invention
In example, when the tungsten source is tungsten carbonyl, the amount ratio of the tungsten carbonyl and dehydrated alcohol is preferably 50mg:30mL.
After obtaining reaction solution, the reaction solution is carried out solvent thermal reaction by the present invention, obtains WO3-xNano wire.
In the present invention, the temperature of the solvent thermal reaction is 140~180 DEG C, preferably 160 DEG C；Time be 12~
20h, preferably 15~18h.In the present invention, the solvent thermal reaction preferably carries out in polytetrafluoro kettle.
After solvent thermal reaction, the present invention is it is also preferable to include by gained solvent thermal reaction liquid cooled to room temperature, so
After be centrifugated, by the solid being centrifugally separating to obtain washing, dry.
In the present invention, the revolving speed of the centrifuge separation is preferably 8000r/min, and the time is preferably 10min.In the present invention
In, the washing is preferably dehydrated alcohol with reagent, the present invention to the number of the washing without limitation.The present invention is to described dry
Dry temperature and time is also not specifically limited.
WO provided by the invention3-xNano wire has very strong absorption in Visible-to-Near InfaRed region, have it is strong it is equal from
Sub- effect；Under the collective effect of Uv and visible light, it can be transitted in valence band by the free electron that ultraviolet excitation generates
Hot hole progress on imperfect tape and on imperfect tape is compound, and the free electron density on imperfect tape is made to be maintained at a stable shape
State.Therefore, this electron transfer processes under Uv and visible light synergistic effect, make WO3-xNano wire can regard a kind of tool as
There is the band structure of Z- type hetero-junctions.
The present invention also provides the WO described in above-mentioned technical proposal3-xThe preparation method of nano wire, comprising the following steps:
Tungsten source and dehydrated alcohol are mixed, reaction solution is formed；
The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；The tungsten source includes tungsten carbonyl or chlorination
Tungsten；The temperature of the solvent thermal reaction is 140~180 DEG C, and the time is 12~20h.
In the present invention, the WO3-xThe preparation method parameter of nano wire is consistent with the parameter of foregoing description, herein not
It repeats again.
Preparation method of the invention is easy to operate, low in cost, and the WO prepared3-xNano wire have in the near infrared region compared with
Wide and adjustable RESONANCE ABSORPTION band.
The present invention also provides the WO described in above-mentioned technical proposal3-xApplication of the nano wire in catalysis ethanol dehydrogenation reaction.
In the present invention, as the WO3-xWhen nano wire is applied to catalysis ethanol dehydrogenation reaction, it is preferably a step:
By WO3-xIt after nano wire is mixed with dehydrated alcohol, is coated on carrier, obtains WO3-xNano wire and dehydrated alcohol sample
Product；
By the WO3-xNano wire and dehydrated alcohol sample are in normal pressure, nitrogen-oxygen mix atmosphere, ultraviolet light+visible light
Under irradiation, dehydrogenation reaction is carried out.
The present invention is by WO3-xIt after nano wire is mixed with dehydrated alcohol, is coated on carrier, obtains WO3-xNano wire with it is anhydrous
Ethanol sample.
In the present invention, the WO3-xThe amount ratio of nano wire and dehydrated alcohol is preferably 5mg:0.2mL.In the present invention
In, the WO3-xThe hybrid mode of nano wire and dehydrated alcohol is preferably ultrasound；The frequency of the ultrasound is preferably 80~
120kHz, time are preferably 5min.
The present invention is to the WO3-xThe coating method of the mixture of nano wire and dehydrated alcohol is not specifically limited；The painting
Preferred 0.1~the 0.3mm of the thickness of cloth.In the present invention, the carrier is preferably sheet glass.
Obtain WO3-xAfter nano wire and dehydrated alcohol sample, the present invention is by the WO3-xNano wire and ethanol sample are normal
Under pressure, nitrogen-oxygen mix atmosphere, ultraviolet light+radiation of visible light, dehydrogenation reaction is carried out.
In the present invention, volume content of the oxygen in nitrogen-oxygen mix atmosphere is preferably 0~20%, into one
Step preferably 0.4%.In the present invention, the nitrogen-oxygen mix atmosphere preferably obtains by the following method: using nitrogen pair
Reactor is de-gassed, and is then filled with oxygen according to the ratio of oxygen in nitrogen-oxygen mix atmosphere.In the present invention,
The presence of nitrogen in mixed atmosphere makes ethyl alcohol that dehydrogenation reaction occur and generates acetaldehyde, and forms activation hydrogen on tungsten oxide surface；It is mixed
Close atmosphere in oxygen can rapidly and tungsten oxide surface reactive with active hydrogen generation water, go the reactive hydrogen on tungsten oxide surface quickly
It removes, is adsorbed on tungsten oxide for subsequent ethanol and position is provided, promote the progress of dehydrogenation reaction.In addition, if nitrogen-oxygen mix
The content of oxygen is excessive in atmosphere, and the oxygen vacancies of tungsten oxide can be made to reduce, and leads to the reduction of tungsten oxide activity, so by nitrogen-oxygen
The volume content control that gas mixes wherein oxygen is 20% or less.
In the present invention, the intensity of the ultraviolet light+visible light is preferably 30~80W, further preferably 50W.At this
In invention, the light source for providing the ultraviolet light+visible light is preferably xenon lamp；The model of the xenon lamp is preferably PLS-SXE300/
300UV。
In the present invention, the temperature of the dehydrogenation reaction is preferably room temperature.
Fig. 1 WO provided by the invention3-xNanowire catalytic alcohol dehydrogenase process schematic, the Dehydrogenating reaction of alcohol process
In be also accompanied by side reaction dehydration, wherein dehydrogenation reaction accounts for leading, and the accounting of dehydration is only 1% or so.
WO provided by the invention3-xNano wire stabilizes WO by the synergistic effect of ultraviolet-visible light3-xFree electron it is close
Degree, to realize high efficiency at room temperature and the with high selectivity reaction of catalysis ethanol dehydrogenation.
Below with reference to embodiment to WO provided by the invention3-xNano wire and the preparation method and application thereof carries out specifically
It is bright, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
50mg tungsten carbonyl powder is added in 30mL deionized water, yellowly liquid is vigorously stirred, then by it
It is transferred in 50mL polytetrafluoro water heating kettle, keeps the temperature 12h at 160 DEG C, after naturally cooling to room temperature, with the speed of 8000r/min
It is centrifuged 10min, obtained solid is washed with dehydrated alcohol, dries in a vacuum drying oven, obtains WO3-xNano wire.
Fig. 2 is WO obtained by the present embodiment3-xThe transmission electron microscope image of nano wire, figure it is seen that gained
WO3-xThe length of nano wire is 1~3 μm, and diameter is 5~10nm.
Fig. 3 is 1 gained WO of embodiment3-xThe absorption spectrum of nano wire；As can be seen from Figure 3: gained WO3-xNano wire is can
See-near infrared region has very strong absorption, illustrate gained WO3-xNano wire has strong plasma effect.
Take 5mgWO3-x0.2mL dehydrated alcohol is added in nano wire, and ultrasonic 5min obtains uniform dispersion, then by dispersion liquid
It is placed in a sheet glass (4.9cm2) on, then sheet glass is put into 100mL reactor, and with nitrogen deaerate 20min, reinject
A certain amount of oxygen (0mL, 0.2mL, 0.4mL, 0.8mL, 1.2mL and 20mL), then carries out illumination, the gas of generation with xenon lamp
(acetaldehyde, ethylene) is detected with gas-chromatography.
In order to probe into the influence of optical wavelength, using the optical filter of 200~400nm and 400~780nm, make xenon source can
Independent ultraviolet light and visible light are generated, illumination, the gas gas of generation then are carried out to sample in independent ultraviolet light and visible light
Phase chromatography is detected.
Fig. 4 is WO obtained by the present embodiment3-xNano wire thermionic transition process schematic diagram under the irradiation of different light；From Fig. 4
It can be seen that the electronics in valence band, which can excite, to be transitted on conduction band, but can then have one under independent ultraviolet irradiation
On non-radiative decay to imperfect tape, so as to cause a low activity.Electronics under the irradiation of separately visible light, on imperfect tape
Thermoelectron can be excited into due to LSPR effect, and generate hot hole in imperfect tape, but usually thermoelectron can and sample
The adsorbate on surface is reacted, to reduce the density of free electron, reduces activity.However being total in ultraviolet light and visible light
It is empty that by the free electron that ultraviolet excitation generates the heat on imperfect tape and on imperfect tape can be transitted under same-action, in valence band
Cave progress is compound, and the free electron density on imperfect tape is made to be maintained at a stable state.Therefore, this in ultraviolet light and visible
Electron transfer processes under light synergistic effect, make WO3-xA kind of band structure with Z- type hetero-junctions can be regarded as.
Fig. 5 is WO obtained by the present embodiment3-xNano wire promotes alcohol dehydrogenase to generate acetaldehyde curve graph；As can be seen from Figure 5:
The yield of acetaldehyde has very big difference with the difference of oxygen content；Wherein, in nitrogen-oxygen, (oxygen volume accounting is
0.4%) under mixed atmosphere, the yield highest of acetaldehyde has reached 896.67 μm of ol/ (gh), and selectivity has also reached 91%.
Fig. 6 is the present embodiment under nitrogen-oxygen (oxygen volume accounting is 0.4%) mixed atmosphere, different wave length irradiation
Gained WO3-xImpact effect figure of the nano wire to Dehydrogenating reaction of alcohol；As can be seen from Figure 6: WO3-xIn independent ultraviolet light or visible
Under light irradiation, in 3h, the yield of acetaldehyde only has 25.89 and 213.68 μm of ol/g, and under ultraviolet-visible light, acetaldehyde
Yield reached 2690.00 μm of ol, be 74 times under ultraviolet light, it is seen that 12 times under light.
Embodiment 2
Similar to Example 1, difference is only that: tungsten source becomes tungsten chloride.
Gained WO3-xUnder nitrogen-oxygen (oxygen volume accounting is 0.4%) mixed atmosphere, the yield of acetaldehyde is nano wire
784.70 μm of ol/ (gh), have selectively reached 90.2%.
Gained WO3-xNano wire is under independent ultraviolet light or radiation of visible light, and in 3h, the yield of acetaldehyde only has 24.64
With 206.58 μm of ol/g, and under ultraviolet-visible light, the yield of acetaldehyde has reached 2354.09 μm of ol.
Embodiment 3
Similar to Example 1, difference is only that, the temperature of the solvent thermal reaction is 140 DEG C.
Gained WO3-xUnder nitrogen-oxygen (oxygen volume accounting is 0.4%) mixed atmosphere, the yield of acetaldehyde is nano wire
811.75 μm of ol/ (gh), have selectively reached 90.6%.
Gained WO3-xNano wire is under independent ultraviolet light or radiation of visible light, and in 3h, the yield of acetaldehyde only has 25.05
With 210.69 μm of ol/g, and under ultraviolet-visible light, the yield of acetaldehyde has reached 2435.24 μm of ol.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of WO3-xNano wire, which is characterized in that be made by method comprising the following steps:
Tungsten source and dehydrated alcohol are mixed, reaction solution is formed；
The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；
The tungsten source includes tungsten carbonyl or tungsten chloride；The temperature of the solvent thermal reaction be 140~180 DEG C, the time be 12~
20h。
2. WO according to claim 13-xNano wire, which is characterized in that the WO3-xThe length of nano wire is 1~3 μm,
Diameter is 5~10nm.
3. the described in any item WO of claim 1~23-xThe preparation method of nano wire, which comprises the following steps:
Tungsten source and dehydrated alcohol are mixed, reaction solution is formed；
The reaction solution is subjected to solvent thermal reaction, obtains WO3-xNano wire；
The tungsten source includes tungsten carbonyl or tungsten chloride；The temperature of the solvent thermal reaction be 140~180 DEG C, the time be 12~
20h。
4. preparation method according to claim 3, which is characterized in that further include by institute after the solvent thermal reaction
Solvent thermal reaction liquid cooled to room temperature is obtained, is then centrifuged for separating, by the solid being centrifugally separating to obtain washing, drying.
5. the described in any item WO of claim 1~23-xApplication of the nano wire in catalysis ethanol dehydrogenation reaction.
6. application according to claim 5, which comprises the following steps:
By WO3-xIt after nano wire is mixed with dehydrated alcohol, is coated on carrier, obtains WO3-xNano wire and dehydrated alcohol sample；
By the WO3-xNano wire and dehydrated alcohol sample are in normal pressure, nitrogen-oxygen mix atmosphere, ultraviolet light+radiation of visible light
Under, carry out dehydrogenation reaction.
7. application according to claim 6, which is characterized in that the WO3-xThe amount ratio of nano wire and dehydrated alcohol is
5mg:0.2mL.
8. application according to claim 6, which is characterized in that volume of the oxygen in nitrogen-oxygen mix atmosphere
Content is 0~20%.
9. application according to claim 6, which is characterized in that the temperature of the dehydrogenation reaction is room temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111774051A (en) * | 2020-06-02 | 2020-10-16 | 贵州理工学院 | Catalyst for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration and preparation method thereof |
| CN113511682A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | Doping of WO3Nanowire, preparation method thereof and gas sensor |
| CN113511683A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | WO3Nanowire, preparation method thereof and gas sensor |
| CN113856715A (en) * | 2021-12-03 | 2021-12-31 | 东营惠宝新材料科技有限公司 | Photo-thermal-pyroelectric-surface plasma photocatalyst, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511682A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | Doping of WO3Nanowire, preparation method thereof and gas sensor |
| CN113511683A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | WO3Nanowire, preparation method thereof and gas sensor |
| CN113511682B (en) * | 2020-04-10 | 2023-12-22 | 中国石油化工股份有限公司 | Doping WO 3 Nanowire, preparation method thereof and gas sensor |
| CN111774051A (en) * | 2020-06-02 | 2020-10-16 | 贵州理工学院 | Catalyst for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration and preparation method thereof |
| CN113856715A (en) * | 2021-12-03 | 2021-12-31 | 东营惠宝新材料科技有限公司 | Photo-thermal-pyroelectric-surface plasma photocatalyst, preparation method and application |
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