CN106824190A - A kind of WO3‑xNanocatalyst and its preparation, application - Google Patents
A kind of WO3‑xNanocatalyst and its preparation, application Download PDFInfo
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- CN106824190A CN106824190A CN201710124940.5A CN201710124940A CN106824190A CN 106824190 A CN106824190 A CN 106824190A CN 201710124940 A CN201710124940 A CN 201710124940A CN 106824190 A CN106824190 A CN 106824190A
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- nanocatalyst
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- ethyl alcohol
- absolute ethyl
- presoma
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000007547 defect Effects 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000010298 pulverizing process Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000003643 water by type Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of WO3‑xNanocatalyst, with flake structure, wherein x is the quantity of oxygen defect, 0.08≤x≤0.18.The invention also discloses above-mentioned WO3‑xThe preparation method of nanocatalyst.The invention also discloses above-mentioned WO3‑xThe application of nanocatalyst.The present invention is peeled off by liquid phase ultrasound and obtains WO3‑xNanocatalyst, with electrical conductivity high, is conducive to the transmission of catalytic process electronics；With moderate hydrogen adsorption free energy, hydrogen producing catalysis activity can be effectively improved, not only performance is close to current commercial Pt/C catalyst and cheap, while having preferable stability, it is adaptable to commercial applications.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of WO3-xNanocatalyst and its preparation, application.
Background technology
Since nineteen seventies, the mankind begin to think the carrier that hydrogen is energy.Because hydrogen molecule is not
But with highest energy density, and burn within the engine or be converted into electric energy in a fuel cell, its accessory substance is only
There is water to be produced without other harmful substances.Comparatively speaking, carbon containing fossil energy after burning by that can produce water and two
Harmful material such as carbonoxide, greatly harm is caused to environment.It is well known that protium is the abundantest unit in the earth's crust
One of element, but it is most of under the conditions of it be not exist in the form of molecular hydrogen, therefore we must develop efficiently and can hold
Continuous hydrogen producing technology.However, hydrogen most so far is all still obtained by gas renormalizing, during this
Not only need to consume fossil energy, also inevitably result from carbon dioxide.Using regenerative resource (such as solar energy)
Electro-catalysis aquatic products hydrogen is a kind of continuable method of cleaning.Early in 1789, J.R.Deiman just had begun to begin one's study
Electro-catalysis water decomposition.The conventional commercial catalyst that electro-catalysis aquatic products hydrogen is used is Pt/C, although this catalyst
Performance is high, but its platinum element earth reserves is few, it is big with synthesis difficulty to extract.This causes this kind of catalyst expensive, seriously
Limit its large-scale application.
And the total class of transition metal oxide element is abundant, earth reserves are plump, can be less expensive as catalyst；It is two-dimentional brilliant
The chip sample of body structure, than larger, the defect on surface is relatively more, and exposed avtive spot is relatively more, favorably for its specific surface area
In the absorption of hydrogen atom.Oxygen defect is conducive to improving the density of states of the sample near fermi level, improves the conduction of oxide
Property, this is conducive to the electric transmission during electro-catalysis.Oxygen defect provides the hydrogen adsorption free energy of appropriateness for catalyst, accelerates
The generation of catalytic reaction.
The content of the invention
Based on the technical problem that background technology is present, the present invention proposes a kind of WO3-xNanocatalyst and its preparation, should
With, its specific surface area is more than larger, defect, and exposed avtive spot is more, effectively raises the utilization rate of atom, and oxygen defect
Result in electric conductivity of the invention increases, and accelerates the electro transfer of electro-catalysis process and is adsorbed freely there is provided appropriate hydrogen
Can, electro-catalysis efficiency is beneficially improved, so as to play its catalysis advantage in the reaction of electrolysis water hydrogen producing, concurrently excavate more
Wide application potential.
A kind of WO proposed by the present invention3-xNanocatalyst, it has flake structure, and wherein x is the quantity of oxygen defect.
Preferably, 0.08≤x≤0.18.
Preferably, sheet thickness is 5~6nm.
The above-mentioned WO that the present invention is also proposed3-xThe preparation method of nanocatalyst, comprises the following steps：By W18O49Presoma
Add in the mixed solution of absolute ethyl alcohol and deionized water, then carry out Ultrasonic Pulverization stripping, then clean, freeze-drying is obtained
WO3-xNanocatalyst.
Preferably, the volume ratio of absolute ethyl alcohol and deionized water is 0.8~1.2：0.8~1.2, W18O49Presoma with it is mixed
The mass volume ratio (g/L) for closing solution is 0.8~1.2：0.8~1.2.
Preferably, the time that Ultrasonic Pulverization is peeled off is 4~6h.
Preferably, the temperature of freeze-drying is -38~-40 DEG C, and sublimation drying is 22~26h.
Preferably, the concrete operations of cleaning are as follows：Material after Ultrasonic Pulverization is peeled off is centrifuged, then will be from
Heart products therefrom carries out supersound washing with polar solvent.
Preferably, the concrete operations of cleaning are as follows：Material after Ultrasonic Pulverization is peeled off with the rotating speed of 2000 turns/min from
18~20min of the heart, 1~2min of supersound washing, add deionized water, are then centrifuged with the rotating speed of 11000~13000 turns/min
8~10min.
Preferably, W18O49Presoma is prepared using following technique：Tungsten hexachloride is added to ethanol solution under normal temperature
In stir, then carry out hydro-thermal reaction, after being subsequently cooled to room temperature, cleaning, vacuum drying obtain W18O49Presoma.
Preferably, the mass volume ratio (mg/mL) of tungsten hexachloride and absolute ethyl alcohol is 18~22：0.8~1.2.
Preferably, the temperature of hydro-thermal reaction is 160~180 DEG C, and the time of hydro-thermal reaction is 20~24h.
Preferably, the concrete operations of cleaning are as follows：Material is centrifuged 8 with the rotating speed of 11000~13000 turns/min after cooling down
~10min, then carries out supersound washing with absolute ethyl alcohol, then be centrifuged with the rotating speed of 11000~13000 turns/min by centrifugation product
8~10min, then carries out supersound washing by centrifugation product with absolute ethyl alcohol.
Preferably, vacuum drying temperature is 50~60 DEG C.
The above-mentioned WO that the present invention is also proposed3-xNanocatalyst is applied in the reaction of electrolysis water hydrogen producing.
The present invention obtains WO using liquid phase Ultrasonic Pulverization stripping method3-xNanocatalyst, its flake structure improves and was catalyzed
Atom utilization in journey, oxygen defect improves the electric conductivity of catalyst, and there is provided the hydrogen adsorption free energy of appropriateness, is conducive to
The catalytic efficiency of electro-catalysis process.The present invention is compared with conventional crystal material synthesis method, and mild condition, program is simple, synthesis
Cost is greatly lowered, and more environmentally friendly in building-up process.The present invention has in terms of electro catalytic electrode reaction and has great advantage, its work
Property is close to commercial Pt/C catalyst, the good stability of catalyst.
By present invention gained WO3-xNanocatalyst is contrasted with the Pt/C catalyst of commercialization, and the present invention is in electrolysis aquatic products
Hydrogen process, generation current density is 10mA/cm2When required overpotential be 38.8mV, under square one, commercial urges
Overpotential needed for agent Pt/C is 23.1mV, and this shows electrocatalysis characteristic of the invention close to commercial catalyst.And
By the cyclic voltammetry scan of 1000 circles, the performance of catalyst does not decay significantly substantially, further demonstrates that this catalyst is steady
It is qualitative fine.
Brief description of the drawings
Fig. 1 is the gained W of the embodiment of the present invention 518O49The transmission electron microscope picture of presoma.
Fig. 2 is the gained WO of the embodiment of the present invention 53-xThe transmission electron microscope picture of nanocatalyst.
Fig. 3 is the gained WO of the embodiment of the present invention 53-xThe X-ray image K-M of nanocatalyst.
Fig. 4 is the gained WO of the embodiment of the present invention 53-xThe scanning transmission electron microscope angle of elevation annular dark field of nanocatalyst
Picture.
Fig. 5 is the gained WO of the embodiment of the present invention 53-xThe atomic force scan image of nanocatalyst.
Fig. 6 is the gained WO of this hair embodiment 53-xThe image that the resistivity of nanocatalyst is varied with temperature.
Fig. 7 is the gained WO of the embodiment of the present invention 53-xThe linear sweep voltammetry image of nanocatalyst and Pt/C catalyst.
Fig. 8 is the gained WO of the embodiment of the present invention 53-xThe image of nanocatalyst electro-catalysis stability.
Specific embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
Above-mentioned WO proposed by the present invention3-xThe preparation method of nanocatalyst, comprises the following steps：By W18O49Presoma adds
Enter in the mixed solution of absolute ethyl alcohol and deionized water, then carry out Ultrasonic Pulverization stripping, then clean, freeze-drying is obtained
WO3-xNanocatalyst.
Embodiment 2
Above-mentioned WO proposed by the present invention3-xThe preparation method of nanocatalyst, comprises the following steps：By W18O49Presoma adds
Enter in the mixed solution of absolute ethyl alcohol and deionized water, the volume ratio of absolute ethyl alcohol and deionized water is 1：1, W18O49Presoma
It is 1 with the mass volume ratio (g/L) of mixed solution：1, Ultrasonic Pulverization stripping is then carried out, then to clean, freeze-drying is obtained
WO3-xNanocatalyst.
W18O49Presoma is prepared using following technique：Tungsten hexachloride is added in ethanol solution under normal temperature is stirred
Uniformly, hydro-thermal reaction is then carried out, after being subsequently cooled to room temperature, cleaning, vacuum drying obtains W18O49Presoma.
Embodiment 3
Above-mentioned WO proposed by the present invention3-xThe preparation method of nanocatalyst, comprises the following steps：By W18O49Presoma adds
Enter in the mixed solution of absolute ethyl alcohol and deionized water, the volume ratio of absolute ethyl alcohol and deionized water is 1：1, W18O49Presoma
It is 1 with the mass volume ratio (g/L) of mixed solution：1, then carry out Ultrasonic Pulverization and peel off 6h, after then Ultrasonic Pulverization is peeled off
Material 18min, supersound washing 1min are centrifuged with the rotating speed of 2000 turns/min, add deionized water, then with 11000 turns/
The rotating speed centrifugation 10min of min, -40 DEG C of freeze-dryings obtain WO3-xNanocatalyst.
W18O49Presoma is prepared using following technique：Tungsten hexachloride is added in ethanol solution under normal temperature is stirred
Uniformly, the mass volume ratio (mg/mL) of tungsten hexachloride and absolute ethyl alcohol is 20：1, then carry out hydro-thermal reaction, hydro-thermal reaction temperature
It is 180 DEG C to spend, and the hydro-thermal reaction time is 20h, after being subsequently cooled to room temperature, by material after cooling with the rotating speed of 11000 turns/min
Centrifugation 10min, then carries out supersound washing 1min with absolute ethyl alcohol, then be centrifuged with the rotating speed of 11000 turns/min by centrifugation product
10min, then carries out supersound washing with absolute ethyl alcohol by centrifugation product, and 60 DEG C of vacuum drying obtain W18O49Presoma.
Embodiment 4
Above-mentioned WO proposed by the present invention3-xThe preparation method of nanocatalyst, comprises the following steps：By W18O49Presoma adds
Enter in the mixed solution of absolute ethyl alcohol and deionized water, the volume ratio of absolute ethyl alcohol and deionized water is 1：1, W18O49Presoma
It is 1 with the mass volume ratio (g/L) of mixed solution：1, then carry out Ultrasonic Pulverization and peel off 5h, after then Ultrasonic Pulverization is peeled off
Material 19min, supersound washing 2min are centrifuged with the rotating speed of 2000 turns/min, add deionized water, then with 12000 turns/
The rotating speed centrifugation 9min of min, -40 DEG C of freeze-dryings obtain WO3-xNanocatalyst.
W18O49Presoma is prepared using following technique：Tungsten hexachloride is added in ethanol solution under normal temperature is stirred
Uniformly, the mass volume ratio (mg/mL) of tungsten hexachloride and absolute ethyl alcohol is 20：1, then carry out hydro-thermal reaction, hydro-thermal reaction temperature
It is 190 DEG C to spend, and the hydro-thermal reaction time is 22h, after being subsequently cooled to room temperature, by material after cooling with the rotating speed of 12000 turns/min
Centrifugation 9min, then carries out supersound washing 1.5min with absolute ethyl alcohol, then be centrifuged with the rotating speed of 12000 turns/min by centrifugation product
9min, then carries out supersound washing with absolute ethyl alcohol by centrifugation product, and 55 DEG C of vacuum drying obtain W18O49Presoma.
Embodiment 5
Above-mentioned WO proposed by the present invention3-xThe preparation method of nanocatalyst, comprises the following steps：
Tungsten hexachloride is added in ethanol solution under normal temperature is stirred, the quality of tungsten hexachloride and absolute ethyl alcohol
Volume ratio (mg/mL) is 20：1, hydro-thermal reaction is then carried out, hydrothermal temperature is 160 DEG C, and the hydro-thermal reaction time is 24h, so
After be cooled to room temperature after, material after cooling is centrifuged 8min with the rotating speed of 13000 turns/min, the anhydrous second of product will be then centrifuged
Alcohol carries out supersound washing 2min, then 8min is centrifuged with the rotating speed of 13000 turns/min, and then centrifugation product is carried out with absolute ethyl alcohol
Supersound washing, 50 DEG C of vacuum drying obtain W18O49Presoma；
By 20mgW18O49Presoma is added in the mixed solution of 10mL absolute ethyl alcohols and 10mL deionized waters, absolute ethyl alcohol
It is 1 with the volume ratio of deionized water：1, W18O49Presoma is 1 with the mass volume ratio (g/L) of mixed solution：1, then carry out
Ultrasonic Pulverization peels off 5h, and the material after then Ultrasonic Pulverization is peeled off is centrifuged 20min, supersound washing with the rotating speed of 2000 turns/min
2min, adds deionized water, and 8min then is centrifuged with the rotating speed of 13000 turns/min, and -40 DEG C of freeze-drying 24h obtain WO3-x
Nanocatalyst.
After testing, the present embodiment gained WO3-xTungsten, the stoichiometric proportion of oxygen are 1 in nanocatalyst：2.82, its thin slice knot
The thickness of structure is 5nm.
Experimental example 6
By the gained WO of 5mg embodiments 53-xNanocatalyst is added to the deionized water of the absolute ethyl alcohol of 0.5mL, 0.46mL
In the perfluorinated sulfonic acid mixed solution of 0.04mL, then ultrasonic 0.5h instills the solution of 10 μ L to the glass-carbon electrode of a diameter of 5mm
On, as working electrode and in the H of 0.5mol/L after drying2SO4Its activity as electrolysis water hydrogen producing is determined in solution.
The speed of potential scan is 2mV/s, and the rotating speed of electrode is 1600 turns/min, and the linear scan curve of gained is for shown in Fig. 7.Its
Current density is 10mA/cm during hydrogen producing2When required overpotential be 38.8mV, and as the catalyst Pt/C of commercialization
Required overpotential is 23.1mV under square one, shows WO of the invention3-xNanocatalyst performance is already close to business
With catalyst.In addition, WO of the invention3-xNanocatalyst is by after the cyclic voltammetry scan of 1000 circles, its current density is
10mA/cm2When required overpotential be 40.2mV, the activity of the catalyst of explanation does not substantially decay, i.e., catalyst is steady
It is qualitative good.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of WO3-xNanocatalyst, it is characterised in that it has flake structure, wherein x is the quantity of oxygen defect.
2. WO according to claim 13-xNanocatalyst, it is characterised in that 0.08≤x≤0.18.
3. WO according to claim 1 or claim 23-xNanocatalyst, it is characterised in that sheet thickness is 5~6nm.
4. one kind as described in claim 1-3 WO3-xThe preparation method of nanocatalyst, it is characterised in that comprise the following steps：
By W18O49Presoma is added in the mixed solution of absolute ethyl alcohol and deionized water, then carries out Ultrasonic Pulverization stripping, Ran Houqing
Wash, freeze-drying obtains WO3-xNanocatalyst.
5. WO according to claim 43-xThe preparation method of nanocatalyst, it is characterised in that absolute ethyl alcohol and deionized water
Volume ratio be 0.8~1.2：0.8~1.2, W18O49Presoma is 0.8~1.2 with the mass volume ratio (g/L) of mixed solution：
0.8~1.2.
6. the WO according to claim 4 or 53-xThe preparation method of nanocatalyst, it is characterised in that what Ultrasonic Pulverization was peeled off
Time is 4~6h；Preferably, the temperature of freeze-drying is -38~-40 DEG C, and sublimation drying is 22~26h.
7. the WO according to claim any one of 4-63-xThe preparation method of nanocatalyst, it is characterised in that cleaning it is specific
Operation is as follows：Material after Ultrasonic Pulverization is peeled off is centrifuged, and then centrifugation products therefrom is carried out with polar solvent
Supersound washing；Preferably, the concrete operations of cleaning are as follows：Material after Ultrasonic Pulverization is peeled off with the rotating speed of 2000 turns/min from
18~20min of the heart, 1~2min of supersound washing, add deionized water, are then centrifuged with the rotating speed of 11000~13000 turns/min
8~10min.
8. the WO according to claim any one of 4-63-xThe preparation method of nanocatalyst, it is characterised in that W18O49Presoma
Prepared using following technique：Tungsten hexachloride is added in ethanol solution under normal temperature is stirred, then carry out hydro-thermal anti-
Should, after being subsequently cooled to room temperature, cleaning, vacuum drying obtains W18O49Presoma.
9. WO according to claim 83-xThe preparation method of nanocatalyst, it is characterised in that tungsten hexachloride and absolute ethyl alcohol
Mass volume ratio (mg/mL) be 18~22：0.8~1.2；Preferably, the temperature of hydro-thermal reaction is 160~180 DEG C, and hydro-thermal is anti-
The time answered is 20~24h；Preferably, the concrete operations of cleaning are as follows：Material is with 11000~13000 turns/min after cooling down
Rotating speed 8~10min is centrifuged, centrifugation product is then carried out into supersound washing with absolute ethyl alcohol, then with 11000~13000 turns/
The rotating speed of min is centrifuged 8~10min, and centrifugation product then is carried out into supersound washing with absolute ethyl alcohol；Preferably, it is vacuum drying
Temperature is 50~60 DEG C.
10. one kind as described in claim any one of 1-3 WO3-xNanocatalyst is applied in the reaction of electrolysis water hydrogen producing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710124940.5A CN106824190B (en) | 2017-03-03 | 2017-03-03 | WO (WO) 3-x Nanometer catalyst and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710124940.5A CN106824190B (en) | 2017-03-03 | 2017-03-03 | WO (WO) 3-x Nanometer catalyst and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106824190A true CN106824190A (en) | 2017-06-13 |
| CN106824190B CN106824190B (en) | 2023-12-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710124940.5A Active CN106824190B (en) | 2017-03-03 | 2017-03-03 | WO (WO) 3-x Nanometer catalyst and its preparation and application |
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| CN107715863A (en) * | 2017-09-30 | 2018-02-23 | 五邑大学 | A kind of preparation method of anoxic state tungsten oxide photcatalyst |
| CN110237838A (en) * | 2019-05-06 | 2019-09-17 | 张红 | A kind of preparation method of oxygen defect enhancing light absorption type tungsten oxide material |
| US20200048107A1 (en) * | 2017-04-27 | 2020-02-13 | Kabushiki Kaisha Toshiba | Nano metal compound particles, coating material and film using the same, method for producing film, and method of producing nano metal compound particles |
| CN112812375A (en) * | 2020-12-31 | 2021-05-18 | 宁波能之光新材料科技股份有限公司 | Preparation method of high-dispersion-stability photo-thermal conversion functional nano material |
| CN115448367A (en) * | 2022-08-31 | 2022-12-09 | 浙江大学 | Preparation method of fulvic acid catalyst and application of fulvic acid catalyst in piezoelectric catalytic hydrogen peroxide |
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| US20200048107A1 (en) * | 2017-04-27 | 2020-02-13 | Kabushiki Kaisha Toshiba | Nano metal compound particles, coating material and film using the same, method for producing film, and method of producing nano metal compound particles |
| CN107715863A (en) * | 2017-09-30 | 2018-02-23 | 五邑大学 | A kind of preparation method of anoxic state tungsten oxide photcatalyst |
| CN107715863B (en) * | 2017-09-30 | 2020-04-28 | 五邑大学 | Preparation method of anoxic tungsten oxide photocatalyst |
| CN110237838A (en) * | 2019-05-06 | 2019-09-17 | 张红 | A kind of preparation method of oxygen defect enhancing light absorption type tungsten oxide material |
| CN112812375A (en) * | 2020-12-31 | 2021-05-18 | 宁波能之光新材料科技股份有限公司 | Preparation method of high-dispersion-stability photo-thermal conversion functional nano material |
| CN112812375B (en) * | 2020-12-31 | 2022-03-25 | 宁波能之光新材料科技股份有限公司 | Preparation method of high-dispersion-stability photo-thermal conversion functional nano material |
| CN115448367A (en) * | 2022-08-31 | 2022-12-09 | 浙江大学 | Preparation method of fulvic acid catalyst and application of fulvic acid catalyst in piezoelectric catalytic hydrogen peroxide |
| CN115448367B (en) * | 2022-08-31 | 2024-01-05 | 浙江大学 | Preparation method of yellow-tungstic acid catalyst and application of yellow-tungstic acid catalyst in piezocatalysis of hydrogen peroxide |
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