CN106824190B - WO (WO) 3-x Nanometer catalyst and its preparation and application - Google Patents
WO (WO) 3-x Nanometer catalyst and its preparation and application Download PDFInfo
- Publication number
- CN106824190B CN106824190B CN201710124940.5A CN201710124940A CN106824190B CN 106824190 B CN106824190 B CN 106824190B CN 201710124940 A CN201710124940 A CN 201710124940A CN 106824190 B CN106824190 B CN 106824190B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- minutes
- rpm
- precursor
- carrying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 title abstract description 26
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound 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
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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a WO 3‑x The nano catalyst has a flake structure, wherein x is the number of oxygen defects, and x is more than or equal to 0.08 and less than or equal to 0.18. The invention also discloses the WO 3‑x A preparation method of a nano catalyst. The invention also discloses the WO 3‑x Application of the nano catalyst. The invention obtains WO by liquid phase ultrasonic stripping 3‑x The nanometer catalyst is used for preparing the nanometer catalyst,the high conductivity is good for the transmission of electrons in the catalytic process; the catalyst has moderate free energy of hydrogen adsorption, can effectively improve the catalytic activity of hydrogen production, has the performance close to that of the current commercial Pt/C catalyst, is low in price, has better stability, and is suitable for commercial application.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a WO (WO) 3-x Nano catalyst, its preparation and application.
Background
Since the seventies of the twentieth century, humans began to consider hydrogen as a carrier of energy. Since hydrogen molecules not only have the highest energy density, but also burn in the engine or are converted into electric energy in the fuel cell, by-products thereof are produced only with water and no other harmful substances. In contrast, fossil energy containing carbon generates harmful substances such as water and carbon dioxide after combustion, which causes great harm to the environment. It is well known that hydrogen is one of the most abundant elements in the crust, but under most conditions it does not exist in the form of molecular hydrogen, so we have to develop efficient and sustainable hydrogen production technology. However, most of the hydrogen has been obtained by reforming natural gas so far, and this process is not only required to consume fossil energy, but also inevitably generates carbon dioxide gas. Electrocatalytic production of hydrogen using renewable energy sources (e.g., solar energy) is a clean and sustainable method. As early as 1789, j.r.deiman has begun to study electrocatalytic water decomposition. The traditional commercial catalyst used for electrocatalytic aquatic hydrogen is Pt/C, and the catalyst has high catalytic performance, but the platinum element has little earth reserves and great extraction and synthesis difficulty. This results in an expensive catalyst, which severely limits its large-scale use.
The transition metal oxide elements are rich in total class, and the earth reserves are rich, can be used as a catalyst and is cheaper; the sheet sample with the two-dimensional crystal structure has larger specific surface area, more surface defects and more exposed active sites, and is favorable for the adsorption of hydrogen atoms. Oxygen defects are beneficial to increase the density of states of the sample near the fermi level, the conductivity of the oxide is improved, which facilitates electron transport during electrocatalysis. The oxygen defect provides proper free energy for hydrogen adsorption for the catalyst, and accelerates the catalytic reaction.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a WO 3-x The nano catalyst has larger specific surface area, more defects and more exposed active sites, effectively improves the utilization rate of atoms, increases the conductivity due to oxygen defects, accelerates the electron transfer in the electrocatalytic process, provides moderate free energy of hydrogen adsorption, and favorably improves the electrocatalytic efficiency, thereby exerting the catalytic advantage of the nano catalyst in the electrolytic aquatic hydrogen reaction and developing wider application potential.
The invention provides a WO 3-x A nanocatalyst having a sheet structure wherein x is the number of oxygen defects.
Preferably, 0.08.ltoreq.x.ltoreq.0.18.
Preferably, the flake thickness is 5 to 6nm.
The invention also proposes the above WO 3-x The preparation method of the nano catalyst comprises the following steps: will W 18 O 49 Adding the precursor into a mixed solution of absolute ethyl alcohol and deionized water, then carrying out ultrasonic crushing and peeling, then cleaning, and freeze-drying to obtain WO 3-x A nano catalyst.
Preferably, the volume ratio of the absolute ethyl alcohol to the deionized water is 0.8-1.2: 0.8 to 1.2, W 18 O 49 The mass volume ratio (g/L) of the precursor to the mixed solution is 0.8-1.2: 0.8 to 1.2.
Preferably, the ultrasonic pulverization and peeling time is 4 to 6 hours.
Preferably, the freeze-drying temperature is-38 to-40 ℃ and the freeze-drying time is 22 to 26 hours.
Preferably, the specific operation of the washing is as follows: and (3) centrifugally separating the materials after ultrasonic crushing and stripping, and then ultrasonically washing the product obtained by centrifugation by using a polar solvent.
Preferably, the method comprises the steps of, the specific operation of cleaning is as follows: centrifuging the materials after ultrasonic crushing and stripping for 18-20 min at a rotation speed of 2000 rpm, ultrasonically washing for 1-2 min, adding deionized water, and centrifuging for 8-10 min at a rotation speed of 11000-13000 rpm.
Preferably, W 18 O 49 The precursor is prepared by the following process: adding tungsten hexachloride into absolute ethanol solution at normal temperature, stirring uniformly, performing hydrothermal reaction, cooling to room temperature, cleaning, and vacuum drying to obtain W 18 O 49 A precursor.
Preferably, the method comprises the steps of, the mass volume ratio (mg/mL) of the tungsten hexachloride to the absolute ethyl alcohol is 18-22: 0.8 to 1.2.
Preferably, the temperature of the hydrothermal reaction is 160-180 ℃, and the time of the hydrothermal reaction is 20-24 hours.
Preferably, the specific operation of the washing is as follows: centrifuging the cooled material at a rotation speed of 11000-13000 r/min for 8-10 min, then ultrasonically washing the centrifugate with absolute ethyl alcohol, centrifuging at a rotation speed of 11000-13000 r/min for 8-10 min, and then ultrasonically washing the centrifugate with absolute ethyl alcohol.
Preferably, the temperature of the vacuum drying is 50 to 60 ℃.
The invention also proposes the above WO 3-x The nano catalyst is applied to the reaction of hydrogen production by electrolysis of water.
The invention adopts a liquid phase ultrasonic crushing and stripping method to obtain WO 3-x The nano catalyst has the advantages that the thin sheet structure improves the atom utilization rate in the catalytic process, the oxygen defect improves the electrical conductivity of the catalyst, and moderate free energy of hydrogen adsorption is provided, so that the catalytic efficiency of the electrocatalytic process is facilitated. Compared with the traditional crystal material synthesis method, the method has the advantages of mild condition, simple procedure, greatly reduced synthesis cost and environmental protection in the synthesis process. The invention has great advantages in the aspect of electrocatalytic electrode reaction, and the activity of the invention is close to that of commercial PtAnd (3) the catalyst is good in stability.
WO obtained by the invention 3-x The nano catalyst is compared with a commercial Pt/C catalyst, and the current density of the nano catalyst is 10mA/cm in the process of electrolyzing aquatic hydrogen 2 The overpotential required was 38.8mV, and in equivalent cases, 23.1mV for a commercial catalyst Pt/C, indicating that the electrocatalytic performance of the present invention is close to that of a commercial catalyst. And after 1000 circles of cyclic voltammetry scanning, the performance of the catalyst is basically free from obvious attenuation, and further shows that the catalyst has good stability.
Drawings
FIG. 1 is a diagram of W obtained in example 5 of the present invention 18 O 49 Transmission electron microscopy of the precursor.
FIG. 2 shows WO obtained in example 5 of the present invention 3-x Transmission electron microscopy of nanocatalysts.
FIG. 3 is a diagram of WO obtained in example 5 of the present invention 3-x X-ray electron diffraction image of nanocatalyst.
FIG. 4 shows WO obtained in example 5 of the present invention 3-x The scanning transmission electron microscope of the nano catalyst is provided with a high-angle annular dark field image.
FIG. 5 is a diagram of WO obtained in example 5 of the present invention 3-x Of nano-catalysts an atomic force scan image.
FIG. 6 shows WO obtained in example 5 of the present invention 3-x Image of the resistivity of the nanocatalyst as a function of temperature.
FIG. 7 shows the present invention WO obtained in example 5 3-x Linear sweep voltammetric images of nanocatalysts and Pt/C catalysts.
FIG. 8 shows WO obtained in example 5 of the present invention 3-x Image of electrocatalyst electrocatalytic stability.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
The invention proposes the above WO of 3-x The preparation method of the nano catalyst comprises the following steps: will W 18 O 49 Adding the precursor into a mixed solution of absolute ethyl alcohol and deionized water, then carrying out ultrasonic crushing and peeling, then cleaning, and freeze-drying to obtain WO 3-x Nanometer scale a catalyst.
Example 2
The invention proposes the above WO 3-x The preparation method of the nano catalyst comprises the following steps: will W 18 O 49 The precursor is added into a mixed solution of absolute ethyl alcohol and deionized water, and the volume ratio of the absolute ethyl alcohol to deionized water is 1:1, W 18 O 49 The mass volume ratio (g/L) of the precursor to the mixed solution is 1:1, then ultrasonic crushing and peeling, then cleaning, freeze drying to obtain WO 3-x A nano catalyst.
W 18 O 49 The precursor is prepared by the following process: adding tungsten hexachloride into absolute ethanol solution at normal temperature, stirring uniformly, performing hydrothermal reaction, cooling to room temperature, cleaning, and vacuum drying to obtain W 18 O 49 A precursor.
Implementation of the embodiments example 3
The invention proposes the above WO 3-x The preparation method of the nano catalyst comprises the following steps: will W 18 O 49 The precursor is added into a mixed solution of absolute ethyl alcohol and deionized water, and the volume ratio of the absolute ethyl alcohol to deionized water is 1:1, W 18 O 49 The mass volume ratio (g/L) of the precursor to the mixed solution is 1:1, then carrying out ultrasonic crushing and stripping for 6 hours, centrifuging the material after ultrasonic crushing and stripping for 18 minutes at a rotation speed of 2000 rpm, ultrasonically washing for 1 minute, adding deionized water, centrifuging for 10 minutes at a rotation speed of 11000 rpm, and freeze-drying at-40 ℃ to obtain WO 3-x A nano catalyst.
W 18 O 49 The precursor is prepared by the following process: adding tungsten hexachloride into absolute ethyl alcohol solution at normal temperature, and uniformly stirring, wherein the mass volume ratio (mg/mL) of the tungsten hexachloride to the absolute ethyl alcohol is 20:1, then carrying out a hydrothermal reaction at 180 ℃ for 20 hours, cooling to room temperature, centrifuging the cooled material at 11000 rpm for 10min, and then using the centrifuged productUltrasonic washing with absolute ethanol for 1min, centrifuging at 11000 rpm for 10min, ultrasonic washing the centrifugate with absolute ethanol, and vacuum drying at 60deg.C to obtain W 18 O 49 A precursor.
Example 4
The invention proposes the above WO 3-x The preparation method of the nano catalyst comprises the following steps: will W 18 O 49 The precursor is added into a mixed solution of absolute ethyl alcohol and deionized water, and the volume ratio of the absolute ethyl alcohol to deionized water is 1:1, W 18 O 49 The mass volume ratio (g/L) of the precursor to the mixed solution is 1:1, then carrying out ultrasonic crushing and stripping for 5 hours, centrifuging the material after ultrasonic crushing and stripping for 19 minutes at a rotation speed of 2000 rpm, ultrasonically washing for 2 minutes, adding deionized water, centrifuging for 9 minutes at a rotation speed of 12000 rpm, and freeze-drying at-40 ℃ to obtain WO 3-x A nano catalyst.
W 18 O 49 The precursor is prepared by the following process: adding tungsten hexachloride into absolute ethyl alcohol solution at normal temperature, and uniformly stirring, wherein the mass volume ratio (mg/mL) of the tungsten hexachloride to the absolute ethyl alcohol is 20:1, then carrying out hydrothermal reaction at 190 ℃ for 22 hours, cooling to room temperature, centrifuging the cooled material at 12000 rpm for 9min, then carrying out ultrasonic washing on the centrifuged product with absolute ethyl alcohol for 1.5min, centrifuging at 12000 rpm for 9min, then carrying out ultrasonic washing on the centrifuged product with absolute ethyl alcohol, and carrying out vacuum drying at 55 ℃ to obtain W 18 O 49 A precursor.
Example 5
The invention proposes the above WO 3-x The preparation method of the nano catalyst comprises the following steps:
adding tungsten hexachloride into absolute ethyl alcohol solution at normal temperature, and uniformly stirring, wherein the mass volume ratio (mg/mL) of the tungsten hexachloride to the absolute ethyl alcohol is 20:1, then carrying out a hydrothermal reaction at 160 ℃ for 24 hours, cooling to room temperature, centrifuging the cooled material at 13000 rpm for 8min, and then carrying out ultrasonic washing on the centrifuged product with absolute ethanol for 2min, centrifuging at 13000 rpm for 8min, ultrasonic washing the centrifugate with absolute ethanol, and vacuum drying at 50deg.C to obtain W 18 O 49 A precursor;
will be 20mgW 18 O 49 The precursor is added into a mixed solution of 10mL of absolute ethyl alcohol and 10mL of deionized water, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1, W 18 O 49 The mass volume ratio (g/L) of the precursor to the mixed solution is 1:1, then carrying out ultrasonic crushing and stripping for 5 hours, centrifuging the material after ultrasonic crushing and stripping for 20 minutes at a rotation speed of 2000 rpm, ultrasonically washing for 2 minutes, adding deionized water, centrifuging for 8 minutes at a rotation speed of 13000 rpm, and freeze-drying at-40 ℃ for 24 hours to obtain WO 3-x Nanometer scale catalytic reaction and (3) an agent.
According to the detection, WO obtained in this example 3-x The stoichiometric ratio of tungsten to oxygen in the nano catalyst is 1:2.82, the thickness of the lamellar structure is 5nm.
Experimental example 6
5mg of WO obtained in example 5 3-x Adding the nano catalyst into a mixed solution of 0.5mL of absolute ethyl alcohol, 0.46mL of deionized water and 0.04mL of perfluorosulfonic acid, carrying out ultrasonic treatment for 0.5H, then dripping 10 mu L of the solution onto a glassy carbon electrode with the diameter of 5mm, drying, and taking the solution as a working electrode and adding 0.5mol/L H 2 SO 4 The activity of the catalyst as hydrogen for electrolysis of water was measured in the solution. The potential sweep speed was 2mV/s, the electrode rotation speed was 1600 rpm, the resulting linear scan curve is shown in fig. 7. The current density in the hydrogen production process is 10mA/cm 2 The overpotential required was 38.8mV, whereas the overpotential required for Pt/C as a commercial catalyst was 23.1mV in the same case, indicating the WO of the invention 3-x Nanocatalyst performance has been approximated to commercial catalysts. In addition, WO of the invention 3-x After 1000 circles of cyclic voltammetry scanning, the current density of the nano catalyst is 10mA/cm 2 The overpotential required is 40.2mV, which indicates that the activity of the catalyst is not obviously attenuated, i.e. the stability of the catalyst is good.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (2)
1. WO (WO) 3-x A nanocatalyst, characterized in that it has a flake structure, wherein x is the number of oxygen defects;
the thickness of the flake is 5nm;
the oxygen defect provides a moderate free energy of hydrogen adsorption;
3-x=2.82；
said WO 3-x The preparation method of the nano catalyst comprises the following steps:
adding tungsten hexachloride into absolute ethanol solution at normal temperature, stirring uniformly, wherein the mass of tungsten hexachloride is 20mg, the volume of absolute ethanol is 1 mL, then carrying out hydrothermal reaction, the hydrothermal reaction temperature is 160 ℃, the hydrothermal reaction time is 24 hours, cooling to room temperature, centrifuging the cooled material at 13000 rpm for 8 minutes, then carrying out ultrasonic washing on the centrifuged product for 2 minutes by using absolute ethanol, centrifuging at 13000 rpm for 8 minutes, carrying out ultrasonic washing on the centrifuged product by using absolute ethanol, and carrying out vacuum drying at 50 ℃ to obtain W 18 O 49 Precursor(s) a body;
will be 20mgW 18 O 49 The precursor is added into a mixed solution of 10mL of absolute ethyl alcohol and 10mL of deionized water, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1, W 18 O 49 Precursor quality is 1 g, the volume of the mixed solution is 1L, ultrasonic crushing and stripping are carried out for 5 hours, then ultrasonic crushing and stripping materials are centrifuged for 20 minutes at a rotation speed of 2000 rpm, ultrasonic washing is carried out for 2 minutes, deionized water is added, centrifugal separation is carried out for 8 minutes at a rotation speed of 13000 rpm, and freeze drying is carried out for 24 hours at-40 ℃ to obtain WO 3-x A nano catalyst.
2. A WO as claimed in claim 1 3-x The nano catalyst is applied to the reaction of hydrogen production by electrolysis of water.
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 CN106824190A (en) | 2017-06-13 |
| CN106824190B true CN106824190B (en) | 2023-12-29 |
Family
ID=59138567
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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106824190B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3617151A4 (en) * | 2017-04-27 | 2021-02-17 | Kabushiki Kaisha Toshiba | Metal compound nanoparticles, coating and film using same, method for manufacturing film, and method for manufacturing metal compound nanoparticles |
| 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 |
| 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 |
| 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 |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805023A (en) * | 2010-04-01 | 2010-08-18 | 中国科学院宁波材料技术与工程研究所 | Method for preparing tungstic oxide nano-sheets |
| CN102921006A (en) * | 2012-11-13 | 2013-02-13 | 东华大学 | Application of tungsten oxide matrix nanometer materials in preparation of near-infrared light heat treatment drugs |
| CN103570070A (en) * | 2013-11-07 | 2014-02-12 | 东华大学 | Preparation method of self-assembly W18049 nanostructure |
| CN103692763A (en) * | 2013-12-06 | 2014-04-02 | 深圳先进技术研究院 | Peeling method of two-dimensional layered nano material |
| CN104071847A (en) * | 2014-07-02 | 2014-10-01 | 中国地质大学（北京） | Preparation method of high-yield high-density hypoxic type tungsten oxide nanometer-micrometer structural positive-impedance moisture-sensitive material |
| KR101493937B1 (en) * | 2013-09-06 | 2015-02-17 | 한국전기연구원 | Two dimensional nanosheets fabricated by using ultrasonic wave and manufacturing method thereby |
| CN104401948A (en) * | 2014-11-17 | 2015-03-11 | 长安大学 | Preparation method for single-layer graphite-type carbon nitride nanosheet solution |
| CN104874389A (en) * | 2015-05-05 | 2015-09-02 | 上海应用技术学院 | Mesoporous WO[3-x] visible-light-driven photocatalyst with oxygen vacancy as well as preparation method and application thereof |
| CN105067579A (en) * | 2015-07-28 | 2015-11-18 | 华南师范大学 | Preparation and application of single-layer g-C3N4 fluorescence sensor |
| CN105271421A (en) * | 2015-11-02 | 2016-01-27 | 哈尔滨工业大学 | Preparation method of tungsten-based nanosphere particle powder |
| CN105271420A (en) * | 2015-10-27 | 2016-01-27 | 陕西科技大学 | Method for preparing nanoscale granular W18O49 material |
| CN105498748A (en) * | 2015-11-25 | 2016-04-20 | 南阳师范学院 | Tungsten oxide nanosheets, preparation method and catalysis application thereof |
| CN105749912A (en) * | 2016-03-14 | 2016-07-13 | 中国海洋大学 | Multi-morphology metal-doped W18O49 electrocatalyst and application thereof to hydrogen production by water electrolysis |
| CN106082344A (en) * | 2016-06-15 | 2016-11-09 | 中国科学技术大学 | A kind of preparation method of the defect state Tungstic anhydride. for photocatalysis aerobic coupling |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI518037B (en) * | 2013-09-17 | 2016-01-21 | 國立清華大學 | W18O49-type tungsten oxide nanomaterial and applications thereof in light sensor, mosfet and solar cell |
-
2017
- 2017-03-03 CN CN201710124940.5A patent/CN106824190B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805023A (en) * | 2010-04-01 | 2010-08-18 | 中国科学院宁波材料技术与工程研究所 | Method for preparing tungstic oxide nano-sheets |
| CN102921006A (en) * | 2012-11-13 | 2013-02-13 | 东华大学 | Application of tungsten oxide matrix nanometer materials in preparation of near-infrared light heat treatment drugs |
| KR101493937B1 (en) * | 2013-09-06 | 2015-02-17 | 한국전기연구원 | Two dimensional nanosheets fabricated by using ultrasonic wave and manufacturing method thereby |
| CN103570070A (en) * | 2013-11-07 | 2014-02-12 | 东华大学 | Preparation method of self-assembly W18049 nanostructure |
| CN103692763A (en) * | 2013-12-06 | 2014-04-02 | 深圳先进技术研究院 | Peeling method of two-dimensional layered nano material |
| CN104071847A (en) * | 2014-07-02 | 2014-10-01 | 中国地质大学（北京） | Preparation method of high-yield high-density hypoxic type tungsten oxide nanometer-micrometer structural positive-impedance moisture-sensitive material |
| CN104401948A (en) * | 2014-11-17 | 2015-03-11 | 长安大学 | Preparation method for single-layer graphite-type carbon nitride nanosheet solution |
| CN104874389A (en) * | 2015-05-05 | 2015-09-02 | 上海应用技术学院 | Mesoporous WO[3-x] visible-light-driven photocatalyst with oxygen vacancy as well as preparation method and application thereof |
| CN105067579A (en) * | 2015-07-28 | 2015-11-18 | 华南师范大学 | Preparation and application of single-layer g-C3N4 fluorescence sensor |
| CN105271420A (en) * | 2015-10-27 | 2016-01-27 | 陕西科技大学 | Method for preparing nanoscale granular W18O49 material |
| CN105271421A (en) * | 2015-11-02 | 2016-01-27 | 哈尔滨工业大学 | Preparation method of tungsten-based nanosphere particle powder |
| CN105498748A (en) * | 2015-11-25 | 2016-04-20 | 南阳师范学院 | Tungsten oxide nanosheets, preparation method and catalysis application thereof |
| CN105749912A (en) * | 2016-03-14 | 2016-07-13 | 中国海洋大学 | Multi-morphology metal-doped W18O49 electrocatalyst and application thereof to hydrogen production by water electrolysis |
| CN106082344A (en) * | 2016-06-15 | 2016-11-09 | 中国科学技术大学 | A kind of preparation method of the defect state Tungstic anhydride. for photocatalysis aerobic coupling |
Non-Patent Citations (8)
| Title |
|---|
| Nanostructure Architectures of Tungsten Carbide for Methanol Electrooxidation Catalyst;Yekun Jiang et al;《Chin. J. Chem.》;20161231;第34卷;第624-630页 * |
| Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials;et al. Jonathan N. Coleman;《science》;20110204;第331卷;第568-572页 * |
| 水热法制备微纳结构氧化钨;高小青等;《化学进展》;20130124;第24卷(第01期);全文 * |
| 溶剂热法制备W_(18)O_(49)纳米粉体及其光催化性能研究;介燕妮;海国娟;黄剑锋;曹丽云;吴建鹏;张飞飞;马鼎;;陕西科技大学学报(自然科学版)(第02期);全文 * |
| 溶剂热法制备W_(18)O_(49)纳米粉体及其光催化性能研究;介燕妮等;《陕西科技大学学报(自然科学版)》;20160425;第34卷(第02期);全文 * |
| 缺氧型钨氧化物纳/微米结构的制备及其光催化性能;钱静雯等;《稀有金属材料与工程》;20151115;第44卷;全文 * |
| 钨丝上原位加热生长的WO_(3-x)纳米棒的结构与缺陷研究;张怀若等;《电子显微学报》;20040825(第04期);全文 * |
| 钨氧化合物的合成与性能研究进展;刘盛楠等;《材料导报》;20130525;第27卷;第164页左栏引言部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106824190A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106824190B (en) | WO (WO) 3-x Nanometer catalyst and its preparation and application | |
| CN109046408B (en) | Composite hydrogen evolution electro-catalytic material and preparation method and application thereof | |
| CN108242549B (en) | Catalyst with dispersed VIII group single atoms and preparation method thereof | |
| CN106925771B (en) | Ultra-fine PtRh nano wire and its method for preparing catalyst, application | |
| CN109103474B (en) | Preparation method of high-performance nitrogen-doped porous carbon-loaded PtNi alloy particle methanol fuel cell catalyst | |
| CN111111707B (en) | Selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and preparation method and application thereof | |
| CN109778225A (en) | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation | |
| CN110721713B (en) | Mo 2 C catalytic material and preparation method and application thereof | |
| CN109295476B (en) | Flake Co2Synthesis method and application of P-carbon cloth composite material | |
| JP2012518532A (en) | Carbon-supported CoSe2 nanoparticles for oxygen reduction and hydrogen generation in acidic environment | |
| CN113522327A (en) | Ternary composite photocatalyst, preparation method and application thereof | |
| CN109647464A (en) | A kind of electrocatalysis material converting nitrogen to ammonia | |
| CN110504456B (en) | Oxygen reduction electrode based on nitrogen-oxygen doped ball/sheet porous carbon material and preparation method and application thereof | |
| CN111286752B (en) | Nitrogen-doped graphite phase carbon nitride nanosheet/molybdenum disulfide composite material and preparation method thereof | |
| CN111682222B (en) | Preparation method and catalytic application of Pt-CdS-nitrogen doped graphene quantum dot composite material | |
| CN109759120A (en) | A kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation method and application | |
| CN111883367A (en) | Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof | |
| CN110975912A (en) | Preparation and application of cobalt-nitrogen doped catalyst derived from bimetallic MOFs (metal-organic frameworks) | |
| CN107754840A (en) | One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol | |
| CN114457374A (en) | Nanotube array structure material assembled by V-doped cuprous selenide nanosheets, preparation method and application thereof | |
| Habibi et al. | Ni@ Pt core-shell nanoparticles as an improved electrocatalyst for ethanol electrooxidation in alkaline media | |
| JP2016081584A (en) | Conductive particle and carrier material comprising the same, and fuel cell device and water electrolytic device | |
| Hong et al. | Boosting the Performance of Nitrogen‐Doped Mesoporous Carbon Oxygen Electrode with Ultrathin 2D Iron/Cobalt Selenides | |
| CN109763139B (en) | α-Co(OH)2/PPy/GO nanosheet and OER electrocatalytic modified electrode based on same | |
| CN110707331A (en) | Copper-based nano catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |