CN108786807A - A kind of graphene/WO3The preparation of/Ag composite photocatalysis films - Google Patents
A kind of graphene/WO3The preparation of/Ag composite photocatalysis films Download PDFInfo
- Publication number
- CN108786807A CN108786807A CN201810630159.XA CN201810630159A CN108786807A CN 108786807 A CN108786807 A CN 108786807A CN 201810630159 A CN201810630159 A CN 201810630159A CN 108786807 A CN108786807 A CN 108786807A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- films
- obtains
- film
- 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.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000011521 glass Substances 0.000 claims abstract description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 22
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011889 copper foil Substances 0.000 claims abstract description 18
- 239000011858 nanopowder Substances 0.000 claims abstract description 18
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 12
- 238000004528 spin coating Methods 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 239000003708 ampul Substances 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 60
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of graphene/WO3The preparation of/Ag composite photocatalysis films, copper foil, which is put into, makes to generate a layer graphene film on copper foil in quartz ampoule；Polymethyl methacrylate solution is spin-coated on graphene film surface to be positioned in FeCl3 solution, is placed in acetone again after spin coating PMMA, finally obtains graphene film；Ammonium metatungstate is added in appropriate distilled water and obtains solution A, polyacrylic acid, methylene-bisacrylamide are added into solution A, obtained precursor sol A is placed in dry in drying box and is ground, WO is obtained3Nano-powder；By WO3Nano-powder, which is added in isobutanol, obtains sol B, will obtain sol B and is spun on the ITO electro-conductive glass for being attached with graphene.With graphene/WO3The ITO conductive glass surface spraying adhesives of film, then as anodic deposition electrode, Ag targets are as cathode.Absolute ethyl alcohol is sprayed obtaining film surface, obtains graphene/WO3/ Ag composite photocatalysis films, the present invention need not detach powder, reclaimer operation, more convenient to use.
Description
Technical field
The present invention relates to nano material preparation and multicomponent function film preparing technical field, more particularly to a kind of graphite
Alkene/WO3The preparation of/Ag composite photocatalysis films.
Background technology
With economic continuous development, human society is increasing to the demand of the energy.Currently, although the mankind are in new energy
Source development field has been achieved for certain progress, but over all, has not been achievable large-scale promotion, this limitation is just compeled
Make us that must increase the utilization of the exploitation to non-renewable energy resources such as oil, coals.These traditional energies maintain society well
The daily operating of meeting makes the harmful substances such as its waste water,waste gas and industrial residue generated in use cause serious environment dirty
Dye, therefore the improvement of environmental contaminants is particularly important in today's society.
Environmental pollution treatment method mainly has chemical method, biological degradation method, photocatalytic method at present.Chemical method is to pollutant
Middle input chemical agent is eliminated by chemical reactions such as neutralization, redox and is polluted.This mode is simple, is convenient for recycling, but deposits
The problems such as causing secondary pollution and high cost, so needing to use with caution.Biological degradation method is environmentally protective, but process range has
Limit, there are certain requirements the biochemical degradation ability of pollutant, so its application need to be improved.
Photocatalytic method, is a kind of direct method using sunlight degradable organic pollutant, and cost is relatively low, without secondary dirt
Dye, low energy consumption and easily operated, has broad application prospects.
WO3It is a kind of conductor photocatalysis material that forbidden band can be less than 3.0eV, it can only compared to traditional TiO2, ZnO etc.
The material for carrying out light-catalyzed reaction, WO are excited by ultraviolet light3It can be reacted using visible light, therefore latent with more development
Power.But it there is also some problems, the photon-electron of semi-conducting material-hole-recombination efficiency first is higher, is unfavorable for light and urges
Change the progress of reaction；Secondly single WO3Electron transport ability is limited, and weaker to Adsorption of Organic ability, can not
Effectively improve degradation rate；In addition, existing WO3It is in the majority with powder morphology, it is recycled after use, more not
Just.
Therefore, if by WO3, graphene and metal Ag carry out combined processing, be prepared into a kind of novel multicomponent complex light
Catalytic film can effectively reduce the combined efficiency in photon-electron-hole, improve photocatalytic activity, accelerate organic pollution drop
Solution simplifies subsequent processes.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of graphene/WO3/ Ag is compound
The preparation method of photocatalysis film, with higher sun light utilization efficiency, electron-transport efficiency, adsorption capacity and photocatalysis
Activity.Meanwhile it is different from simple photocatalysis powder material, the present invention is a kind of thin-film material, need not be divided powder
It is more convenient to use from, reclaimer operation.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of graphene/WO3The preparation of/Ag composite photocatalysis films, which is characterized in that include the following steps：
Step 1, the preparation of graphene film：
Thick 25 μm of copper foil is put into quartz ampoule, is vacuumized, is passed through hydrogen and empties air in 5 minutes, be then heated to
1000 DEG C, holding hydrogen flow rate is 2~6sccm, makes air pressure constant in 40mTorr, is kept for a period of time；
After temperature and pressure stabilization, it is passed through 35~40sccm methane, total pressure 500mTorr is kept for a period of time；
After depositing a period of time, stopping is passed through methane and heating, is cooled to room temperature with 50 DEG C/h, one layer of stone is generated on copper foil
Black alkene film；
Polymethyl methacrylate (PMMA) solution of appropriate a concentration of 0.01mol/L is spin-coated on graphene film table
Then copper foil is positioned in FeCl3 solution by face, after 12~15h, pull PMMA/ graphene films out from FeCl3 solution and turn
Move on on ITO electro-conductive glass, then a certain amount of a concentration of 0.01mol/L of spin coating PMMA, then with being positioned in proper amount of acetone, 5
After~8h, final graphene film is obtained；
Step 2, the preparation of tungstic acid (WO3) nano-powder：
The ammonium metatungstate (AMT) of certain mass is added in appropriate distilled water, being stirred continuously makes solid be completely dissolved, and obtains
To solution A, the methylene-bisacrylamide (MBA) that polyacrylic acid (PAA) and mass fraction are 1% is then added into solution A,
Magnetic agitation makes each component be evenly distributed in the solution for a period of time, 3.5h is placed at 80~100 DEG C, later natural cooling
1.5~2h obtains precursor sol A；
Precursor sol A is placed in drying box and is dried, AMT xerogel powders are obtained after grinding, then by AMT xerogel
The ultrasonic wave of powder certain frequency is shatter at tiny powder, and vacuum annealing process is carried out in vacuum annealing furnace：One section of heat preservation
Time 2~3h of postcooling finally obtains dry WO3 nano-powders；
Step 3, graphene/WO3The preparation of film：
By all WO obtained in step 23Nano-powder is added in a certain amount of isobutanol, and 20~30min of stirring makes powder
Body is evenly distributed in a solvent, obtains sol B；
What sol B was uniformly spun to step 1 obtains is attached on the ITO electro-conductive glass of graphene, when one section dry
Between, obtain graphene/WO3Film；
Step 4, graphene/WO3The preparation of/Ag composite photocatalysis films：
Has graphene/WO what step 3 obtained3The ITO conductive glass surfaces of film spray appropriate binder, then
As anodic deposition electrode, the Ag targets of certain mass are placed in parallel in argon gas, are added between two-plate as cathode
The DC voltage of 200~400V maintains 0.5~2h, obtains the graphene/WO for being attached to anode3/ Ag films；
It enables and has graphene/WO3The ITO electro-conductive glass of/Ag films is horizontal positioned, sprays a small amount of anhydrous second in film surface
Alcohol places drying, calcines later, obtain dry graphene/WO3/Ag composite photocatalysis films.
The quartzy bore is 25mm, long 1.5m.
Polyacrylic acid relative molecular mass is 6000~8000 in the step two.
Solution A and the volume ratio of polyacrylic acid, methylene-bisacrylamide (MBA) are 100 in the step two:20:
3。
Precursor sol A is placed in drying box in the step two, and 8~10h, annealing are dried under the conditions of 200~300 DEG C
Processing partial pressure of oxygen is 10Pa, and annealing temperature is 600 DEG C, 60 DEG C/h of heating rate.
In the step three dry 18 at 30 DEG C~for 24 hours.
Argon gas is 40~250Pa in the step four, sprays a small amount of absolute ethyl alcohol in film surface, place dry 4~
6h calcines 6~10h at 450~500 DEG C later.
Beneficial effects of the present invention：
By the present invention in that with sol-gel method, sputtering method and chemical vapour deposition technique, Polymer-supported staying, it is prepared for
Dry graphene/WO3/ Ag composite photocatalysis films, chemical constituent is uniform and defect is few, degradable organic pollutant ability compared with
By force；
Wherein nano metal Ag and WO3In conjunction on the one hand producing Schottky contacts, reduce light induced electron and vacancy
In conjunction with, in addition, nano metal Ag has surface plasma resonance effect, the absorbing properties of composite material are improved, it is effective to increase
The photocatalytic activity of strong material；
The presence of graphene not only contributes to interface electronics and shifts faster, is also optimized with metal nanoparticle collaboration
Level-density parameter structure enhances the adsorption capacity to organic pollution, therefore largely improves photocatalysis efficiency.By graphite
Alkene/WO3Two-dimensional film form is made in/Ag, separation, the recovery processing of powder need not be carried out again, convenient for better in the environment
It uses.
Description of the drawings
Fig. 1 is preparation flow figure of the present invention.
Fig. 2 is monoclinic phase WO3XRD spectra.
Fig. 3 is schematic diagram of the present invention.
Specific implementation mode
With reference to embodiment, invention is further described in detail.
Embodiment 1
Step 1, the preparation of graphene film：
It is 10mm by long and width, thick 25 μm of copper foil puts in quartz ampoule (quartzy bore is 25mm, long 1.5m) into, takes out true
Sky is passed through hydrogen 5min and empties air, is then heated to 1000 DEG C, holding hydrogen flow rate is 2sccm, and air pressure constant is made to exist
40mTorr keeps 20min.
After temperature and pressure stabilization, it is passed through 35sccm methane, total pressure 500mTorr keeps 2h.
Later, stop being passed through methane and heating, room temperature is cooled to 50 DEG C/h, a layer graphene film is generated on copper foil.
By polymethyl methacrylate (PMMA) solution of a concentration of 0.01mol/L of 20mL graphene/copper foil surface with
Then graphene/copper foil is positioned in 100mL 0.05mol/L FeCl3 solution by 2000r/min spin coating 30s, after 12h, from
It pulls PMMA/ graphene films in FeCl3 solution out and is transferred on ITO electro-conductive glass (14*16*1.1mm), then with similarity condition
The PMMA of spin coating and first time equivalent is then placed into 100mL acetone, after 5h, obtains final graphene film.See Fig. 1
In, from raw material CH4 to graphene film flow.Black ball represents graphene layer in Fig. 3.
Step 2, the preparation of tungstic acid (WO3) nano-powder：
3g ammonium metatungstates (AMT) are added in 100mL distilled water, being stirred continuously makes solid be completely dissolved, and obtains solution
A.Then the polyacrylic acid (PAA) that 20mL molecular weight is 6000 and the methylene that 3mL mass fractions are 1% are added into solution A
Bisacrylamide (MBA), magnetic agitation 10min make each component be evenly distributed in the solution, and 3.5h is placed at 80 DEG C, later certainly
So cooling 1.5h, obtains precursor sol A.
Precursor sol A is placed in drying box, 8h is dried under the conditions of 200 DEG C, AMT xerogel powders are obtained after grinding,
Then shatter at tiny powder by the ultrasonication 10min of AMT xerogel powder 20KHz frequencies, in vacuum annealing furnace
Carry out vacuum annealing process (partial pressure of oxygen 10Pa)：Annealing temperature is 600 DEG C, 60 DEG C/h of heating rate, keeps the temperature 5h, cooling 2h.
Finally obtain dry WO3 nano-powders.See in Fig. 1 from raw material A MT to WO3Nano-powder flow.Fig. 2 is the XRD diagram of WO3
Spectrum.
Step 3, graphene/WO3The preparation of film：
1.85g WO3 nano-powders obtained in step 2 are added in 100mL isobutanols, stirring 20min makes powder
It is evenly distributed in a solvent, obtains sol B；
The ITO electro-conductive glass for being attached with graphene that the uniform spin coating of sol B (6000r/min, 30s) to step 1 is obtained
On, dry 18h, obtains graphene/WO at 30 DEG C3Film.Solation and graphene/WO3 film flows in corresponding diagram 1.Fig. 3
Middle grey bead indicates the WO3 nano particles being attached on graphene layer.
Step 4, graphene/WO3The preparation of/Ag composite photocatalysis films：
With graphene/WO3The ITO conductive glass surfaces of film spray 20mL acroleic acid binding agents, are then made
For anodic deposition electrode, using the Ag targets of 100g as cathode.It is placed in parallel in argon gas (150Pa), is added between two-plate
The DC voltage of 200V maintains 0.5h, obtains the graphene/WO for being attached to anode3/ Ag films.In Fig. 3 white globules represent with
The Ag nano particles that graphene layer, WO3 nano particles combine.
It enables and has graphene/WO3The ITO electro-conductive glass of/Ag films is horizontal positioned, sprays the anhydrous second of 5mL in film surface
Alcohol places dry 4h.6h is calcined at 450 DEG C later, obtains dry graphene/WO3/Ag composite photocatalysis films.See Fig. 1
In by addition binder to successfully preparing graphene/WO3/ Ag flows.Fig. 3 is depicted each substance arrangement finally invented, divides
Cloth situation.
Embodiment 2
Step 1, the preparation of graphene film：
It is 10mm by long and width, thick 25 μm of copper foil puts in quartz ampoule (quartzy bore is 25mm, long 1.5m) into, takes out true
Sky is passed through hydrogen and empties air in 5 minutes, is then heated to 1000 DEG C, holding hydrogen flow rate is 4sccm, and air pressure constant is made to exist
40mTorr keeps 20min.
After temperature and pressure stabilization, it is passed through 38sccm methane, total pressure 500mTorr keeps 2h.
After depositing a period of time, stopping is passed through methane and heating, is cooled to room temperature with 50 DEG C/h, one layer of stone is generated on copper foil
Black alkene film.
On the surface of graphene by polymethyl methacrylate (PMMA) the solution spin coating of a concentration of 0.01mol/L of 20mL, so
Copper foil is positioned in 100mL 0.05mol/L FeCl3 solution afterwards, after 12h, pulls PMMA/ graphenes out from FeCl3 solution
Film is simultaneously transferred to ITO electro-conductive glass (14*16*1.1mm)) on, then spin coating 50mL PMMA, then with being positioned over 100mL third
In ketone, after 8h, final graphene film is obtained.
Step 2, the preparation of tungstic acid (WO3) nano-powder：
5g ammonium metatungstates (AMT) are added in 100mL distilled water, being stirred continuously makes solid be completely dissolved, and obtains solution
A.Then the di-2-ethylhexylphosphine oxide that polyacrylic acid (PAA) 3mL mass fractions that addition 20mL molecular weight is 8000 into solution A are 1%
Acrylamide (MBA), magnetic agitation 10min make each component be evenly distributed in the solution, and 3.5h is placed at 80 DEG C, natural later
Cooling 1.5h, obtains precursor sol A.
Precursor sol A is placed in drying box, 10h is dried under the conditions of 200 DEG C, AMT xerogel powders are obtained after grinding,
Then the ultrasonic wave of AMT xerogel powder certain frequencies is shatter at tiny powder, progress vacuum is moved back in vacuum annealing furnace
Fire processing (partial pressure of oxygen 10Pa)：Annealing temperature is 600 DEG C, 60 DEG C/h of heating rate, heat preservation 5h postcoolings 3h.It finally obtains dry
Dry WO3 nano-powders.
Step 3, the preparation of graphene/WO3 films：
All WO3 nano-powders obtained in step 2 are added in 100mL isobutanols, stirring 20min makes powder exist
It is evenly distributed in solvent, obtains sol B；
The ITO electro-conductive glass for being attached with graphene that the uniform spin coating of sol B (6000r/min, 30s) to step 1 is obtained
On, dry 20h, obtains graphene/WO3 films at 30 DEG C.
Step 4, the preparation of graphene/WO3/Ag composite photocatalysis films：
20mL acroleic acid binding agents are sprayed in the ITO conductive glass surfaces with graphene/WO3 films, are then made
For anodic deposition electrode, the Ag targets of 100g are as cathode.It is placed in parallel in argon gas (150Pa), 300V is added between two-plate
DC voltage, maintain 1h, obtain the graphene/WO3/Ag films for being attached to anode.
It enables the ITO electro-conductive glass with graphene/WO3/Ag films horizontal positioned, sprays the anhydrous second of 5mL in film surface
Alcohol places dry 5h.8h is calcined at 450 DEG C later, obtains dry graphene/WO3/Ag composite photocatalysis films.
Embodiment 3
Step 1, the preparation of graphene film：
It is 10mm by long and width, thick 25 μm of copper foil puts in quartz ampoule (quartzy bore is 25mm, long 1.5m) into, takes out true
Sky is passed through hydrogen and empties air in 5 minutes, is then heated to 1000 DEG C, holding hydrogen flow rate is 6sccm, and air pressure constant is made to exist
40mTorr keeps 20min.
After temperature and pressure stabilization, it is passed through 40sccm methane, total pressure 500mTorr keeps 2h.
After depositing a period of time, stopping is passed through methane and heating, is cooled to room temperature with 50 DEG C/h, one layer of stone is generated on copper foil
Black alkene film.
On the surface of graphene by polymethyl methacrylate (PMMA) the solution spin coating of a concentration of 0.01mol/L of 20mL, so
Copper foil is positioned in 100mL 0.05mol/L FeCl3 solution afterwards, after 15h, pulls PMMA/ graphenes out from FeCl3 solution
Film is simultaneously transferred to ITO electro-conductive glass (14*16*1.1mm)) on, then spin coating 50mL PMMA, then with being positioned over 100mL third
In ketone, after 8h, final graphene film is obtained.
Step 2, the preparation of tungstic acid (WO3) nano-powder：
10g ammonium metatungstates (AMT) are added in 100mL distilled water, being stirred continuously makes solid be completely dissolved, and obtains solution
A.Then the di-2-ethylhexylphosphine oxide that polyacrylic acid (PAA) 3mL mass fractions that addition 20mL molecular weight is 8000 into solution A are 1%
Acrylamide (MBA), magnetic agitation 10min make each component be evenly distributed in the solution, and 3.5h is placed at 100 DEG C, later certainly
So cooling 2h, obtains precursor sol A.
Precursor sol A is placed in drying box, 10h is dried under the conditions of 300 DEG C, AMT xerogel powders are obtained after grinding,
Then the ultrasonic wave of AMT xerogel powder certain frequencies is shatter at tiny powder, progress vacuum is moved back in vacuum annealing furnace
Fire processing (partial pressure of oxygen 10Pa)：Annealing temperature is 600 DEG C, 60 DEG C/h of heating rate, heat preservation 5h postcoolings 3h.It finally obtains dry
Dry WO3 nano-powders.
Step 3, the preparation of graphene/WO3 films：
All WO3 nano-powders obtained in step 2 are added in 100mL isobutanols, stirring 20min makes powder exist
It is evenly distributed in solvent, obtains sol B；
The ITO electro-conductive glass for being attached with graphene that the uniform spin coating of sol B (6000r/min, 30s) to step 1 is obtained
On, it is dried for 24 hours at 30 DEG C, obtains graphene/WO3 films.
Step 4, the preparation of graphene/WO3/Ag composite photocatalysis films：
20mL acroleic acid binding agents are sprayed in the ITO conductive glass surfaces with graphene/WO3 films, are then made
For anodic deposition electrode, the Ag targets of 100g are as cathode.It is placed in parallel in argon gas (150Pa), 300V is added between two-plate
DC voltage, maintain 2h, obtain the graphene/WO3/Ag films for being attached to anode.It enables with graphene/WO3/Ag films
ITO electro-conductive glass is horizontal positioned, sprays 5mL absolute ethyl alcohols in film surface, places dry 6h.It is calcined at 500 DEG C later
10h obtains dry graphene/WO3/Ag composite photocatalysis films.
Claims (7)
1. a kind of graphene/WO3The preparation of/Ag composite photocatalysis films, which is characterized in that include the following steps：
Step 1, the preparation of graphene film：
Thick 25 μm of copper foil is put into quartz ampoule, is vacuumized, is passed through hydrogen and empties air in 5 minutes, be then heated to 1000
DEG C, holding hydrogen flow rate is 2~6sccm, makes air pressure constant in 40mTorr, is kept for a period of time；
After temperature and pressure stabilization, it is passed through 35~40sccm methane, total pressure 500mTorr is kept for a period of time；
After depositing a period of time, stopping is passed through methane and heating, is cooled to room temperature with 50 DEG C/h, a layer graphene is generated on copper foil
Film；
Polymethyl methacrylate (PMMA) solution of appropriate a concentration of 0.01mol/L is spin-coated on graphene film surface, so
Copper foil is positioned in FeCl3 solution afterwards, after 12~15h, PMMA/ graphene films is pulled out from FeCl3 solution and is transferred to
On ITO electro-conductive glass, then a certain amount of a concentration of 0.01mol/L of spin coating PMMA, then with being positioned in proper amount of acetone, 5~8h
Afterwards, final graphene film is obtained；
Step 2, the preparation of tungstic acid (WO3) nano-powder：
The ammonium metatungstate (AMT) of certain mass is added in appropriate distilled water, being stirred continuously makes solid be completely dissolved, and obtains molten
Then the methylene-bisacrylamide (MBA) that polyacrylic acid (PAA) and mass fraction are 1%, magnetic force is added in liquid A into solution A
Stirring a period of time so that each component is evenly distributed in the solution, 3.5h is placed at 80~100 DEG C, later natural cooling 1.5~
2h obtains precursor sol A；
Precursor sol A is placed in drying box and is dried, AMT xerogel powders are obtained after grinding, then by AMT xerogel powders
It is shatter at tiny powder with the ultrasonic wave of certain frequency, vacuum annealing process is carried out in vacuum annealing furnace：Heat preservation a period of time
2~3h of postcooling finally obtains dry WO3 nano-powders；
Step 3, graphene/WO3The preparation of film：
By all WO obtained in step 23Nano-powder is added in a certain amount of isobutanol, and 20~30min of stirring makes powder exist
It is evenly distributed in solvent, obtains sol B；
What sol B was uniformly spun to step 1 obtains is attached on the ITO electro-conductive glass of graphene, dry a period of time, obtains
To graphene/WO3Film；
Step 4, graphene/WO3The preparation of/Ag composite photocatalysis films：
Has graphene/WO what step 3 obtained3The ITO conductive glass surfaces of film spray appropriate binder, are then made
Ag targets for anodic deposition electrode, certain mass are placed in parallel in as cathode in argon gas, between two-plate plus 200~
The DC voltage of 400V maintains 0.5~2h, obtains the graphene/WO for being attached to anode3/ Ag films；
It enables and has graphene/WO3The ITO electro-conductive glass of/Ag films is horizontal positioned, sprays a small amount of absolute ethyl alcohol in film surface, puts
Drying is set, is calcined later, dry graphene/WO3/Ag composite photocatalysis films are obtained.
The quartzy bore is 25mm, long 1.5m.
Polyacrylic acid relative molecular mass is 6000~8000 in the step two.
Solution A and the volume ratio of polyacrylic acid, methylene-bisacrylamide (MBA) are 100 in the step two:20:3.
Precursor sol A is placed in drying box in the step two, and 8~10h, annealing are dried under the conditions of 200~300 DEG C
Partial pressure of oxygen is 10Pa, and annealing temperature is 600 DEG C, 60 DEG C/h of heating rate.
In the step three dry 18 at 30 DEG C~for 24 hours.
Argon gas is 40~250Pa in the step four, sprays a small amount of absolute ethyl alcohol in film surface, places dry 4~6h, it
6~10h is calcined at 450~500 DEG C afterwards.
2. a kind of graphene/WO according to claim 13The preparation of/Ag composite photocatalysis films, which is characterized in that described
Quartzy bore be 25mm, long 1.5m.
3. a kind of graphene/WO according to claim 13The preparation of/Ag composite photocatalysis films, which is characterized in that described
The step of two in polyacrylic acid relative molecular mass be 6000~8000.
4. a kind of preparation of graphene/WO3/Ag composite photocatalysis films according to claim 1, which is characterized in that institute
Solution A and the volume ratio of polyacrylic acid, methylene-bisacrylamide (MBA) are 100 in the step of stating two:20:3.
5. a kind of graphene/WO according to claim 13The preparation of/Ag composite photocatalysis films, which is characterized in that described
The step of two in precursor sol A be placed in drying box, under the conditions of 200~300 DEG C dry 8~10h, annealing partial pressure of oxygen be
10Pa, annealing temperature are 600 DEG C, 60 DEG C/h of heating rate.
6. a kind of graphene/WO according to claim 13The preparation of/Ag composite photocatalysis films, which is characterized in that described
The step of three in dry 18 at 30 DEG C~for 24 hours.
7. a kind of graphene/WO according to claim 13The preparation of/Ag composite photocatalysis films, which is characterized in that described
The step of four in argon gas be 40~250Pa, spray a small amount of absolute ethyl alcohol in film surface, dry 4~6h placed, later 450
6~10h is calcined at~500 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810630159.XA CN108786807A (en) | 2018-06-19 | 2018-06-19 | A kind of graphene/WO3The preparation of/Ag composite photocatalysis films |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810630159.XA CN108786807A (en) | 2018-06-19 | 2018-06-19 | A kind of graphene/WO3The preparation of/Ag composite photocatalysis films |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108786807A true CN108786807A (en) | 2018-11-13 |
Family
ID=64083403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810630159.XA Pending CN108786807A (en) | 2018-06-19 | 2018-06-19 | A kind of graphene/WO3The preparation of/Ag composite photocatalysis films |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108786807A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870842A (en) * | 2022-05-19 | 2022-08-09 | 辽宁大学 | Immobilized Z-shaped Fe 2 O 3 /CuFe 2 O 4 I Cu photocatalyst composite membrane and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660740A (en) * | 2012-05-29 | 2012-09-12 | 东南大学 | Graphene and metal nanoparticle composite film preparation method |
| CN103265081A (en) * | 2013-05-27 | 2013-08-28 | 合肥工业大学 | Method for preparing tungsten oxide nano single crystal by sol-gel method |
| CN103427033A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Conductive thin film, preparation method and application thereof |
| CN104056620A (en) * | 2014-06-19 | 2014-09-24 | 东南大学 | Visible-light catalyst and preparation method and application thereof |
| CN105233823A (en) * | 2015-10-19 | 2016-01-13 | 桂林理工大学 | Visible light responsive photocatalyst AgYW2O8 and preparation method thereof |
| CN105551579A (en) * | 2015-12-22 | 2016-05-04 | 电子科技大学 | Electrochromic multi-layered transparent conductive thin film and preparation method therefor |
| CN106140126A (en) * | 2015-05-15 | 2016-11-23 | 蓝石科技(开曼)有限公司 | A kind of powder composite photocatalyst material and preparation method thereof |
| CN107029771A (en) * | 2017-05-12 | 2017-08-11 | 湖南大学 | Silver carbonate/silver/tungstic acid tri compound Z-type photochemical catalyst and its preparation method and application |
| CN107164780A (en) * | 2017-04-17 | 2017-09-15 | 桂林理工大学 | A kind of WO3The preparation method of/graphene quantum dot composite film photo-anode |
-
2018
- 2018-06-19 CN CN201810630159.XA patent/CN108786807A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427033A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Conductive thin film, preparation method and application thereof |
| CN102660740A (en) * | 2012-05-29 | 2012-09-12 | 东南大学 | Graphene and metal nanoparticle composite film preparation method |
| CN103265081A (en) * | 2013-05-27 | 2013-08-28 | 合肥工业大学 | Method for preparing tungsten oxide nano single crystal by sol-gel method |
| CN104056620A (en) * | 2014-06-19 | 2014-09-24 | 东南大学 | Visible-light catalyst and preparation method and application thereof |
| CN106140126A (en) * | 2015-05-15 | 2016-11-23 | 蓝石科技(开曼)有限公司 | A kind of powder composite photocatalyst material and preparation method thereof |
| CN105233823A (en) * | 2015-10-19 | 2016-01-13 | 桂林理工大学 | Visible light responsive photocatalyst AgYW2O8 and preparation method thereof |
| CN105551579A (en) * | 2015-12-22 | 2016-05-04 | 电子科技大学 | Electrochromic multi-layered transparent conductive thin film and preparation method therefor |
| CN107164780A (en) * | 2017-04-17 | 2017-09-15 | 桂林理工大学 | A kind of WO3The preparation method of/graphene quantum dot composite film photo-anode |
| CN107029771A (en) * | 2017-05-12 | 2017-08-11 | 湖南大学 | Silver carbonate/silver/tungstic acid tri compound Z-type photochemical catalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| 李文章等: "石墨烯-氧化钨复合薄膜的制备及界面电子传输特性", 《物理化学学报》 * |
| 李本侠: "金属/WO2.72/rGO纳米复合材料的制备及其吸附、光催化和光电化学性质", 《中国化学会第30届学术年会摘要集》 * |
| 杨晓丽等: "化学气相沉积法可控制备石墨烯薄膜和单晶畴", 《微纳电子技术》 * |
| 董亚博: "Ag/WO3复合薄膜Sol-Gel制备及其变色性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870842A (en) * | 2022-05-19 | 2022-08-09 | 辽宁大学 | Immobilized Z-shaped Fe 2 O 3 /CuFe 2 O 4 I Cu photocatalyst composite membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meng et al. | Temperature dependent photocatalysis of g-C3N4, TiO2 and ZnO: Differences in photoactive mechanism | |
| Yu et al. | Non-noble metal Bi deposition by utilizing Bi2WO6 as the self-sacrificing template for enhancing visible light photocatalytic activity | |
| Zhang et al. | A novel BiOCl thin film prepared by electrochemical method and its application in photocatalysis | |
| CN103990486B (en) | The preparation method of a kind of indium sulfide/carbonitride composite nano materials | |
| CN105056985B (en) | g‑C3N4The visible light-responded catalytic membrane of/graphene oxide/Nanoscale Iron | |
| Wei et al. | One-step electrochemical synthesis of a graphene–ZnO hybrid for improved photocatalytic activity | |
| Tian et al. | SILAR deposition of CuO nanosheets on the TiO2 nanotube arrays for the high performance solar cells and photocatalysts | |
| Chen et al. | Microwave heating assisted synthesis of novel SnSe/g-C3N4 composites for effective photocatalytic H2 production | |
| Zhao et al. | Unique bar-like sulfur-doped C3N4/TiO2 nanocomposite: excellent visible light driven photocatalytic activity and mechanism study | |
| CN108355696A (en) | Black phosphorus/g-C3N4Composite visible light catalysis material and its preparation method and application | |
| Li et al. | Facial synthesis of dandelion-like g-C3N4/Ag with high performance of photocatalytic hydrogen production | |
| Kim et al. | Graphene–titania films by supersonic kinetic spraying for enhanced performance of dye-sensitized solar cells | |
| Liu et al. | A highly efficient reduced graphene oxide/SnO2/TiO2 composite as photoanode for photocathodic protection of 304 stainless steel | |
| Chen et al. | A facile strategy for SnS2/g-C3N4 heterojunction composite and the mechanism in photocatalytic degradation of MO | |
| Pan et al. | In situ construction of g-C3N4/TiO2 heterojunction films with enhanced photocatalytic activity over magnetic-driven rotating frame | |
| CN105562054A (en) | Preparation method of silver-doped two-dimensional graphite phase carbon nitride composite photocatalyst | |
| Ren et al. | In situ synthesis of gC 3 N 4/TiO 2 heterojunction nanocomposites as a highly active photocatalyst for the degradation of Orange II under visible light irradiation | |
| CN104437494A (en) | Fenton-like catalyst of graphene coated ferriferrous oxide (Fe3O4) micro-spheres as well as preparation method and application thereof | |
| Cheng et al. | Synthesis of vis/NIR-driven hybrid photocatalysts by electrostatic assembly of NaYF4: Yb, Tm nanocrystals on g-C3N4 nanosheets | |
| CN109126856A (en) | A kind of preparation method with close-connected visible light catalyst | |
| CN103301828B (en) | A kind of photoelectrocatalysithin thin film, preparation method and application | |
| CN102324502A (en) | Preparation method of flower-like tin dioxide and graphene composite material | |
| CN104437551B (en) | Preparation method and use method of CuS modified immobilized TiO2 nanoribbon photocatalyst | |
| CN103191707A (en) | Method for preparing black titanium dioxide by using dual-temperature area reducing method | |
| CN107731550A (en) | A kind of metal oxide/graphene composite material and its preparation method and application |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181113 |
|
| RJ01 | Rejection of invention patent application after publication |