CN103014752B - A kind of TiO 2nano-tube array load is containing the preparation method of ruthenium coating catalyzer - Google Patents
A kind of TiO 2nano-tube array load is containing the preparation method of ruthenium coating catalyzer Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000002071 nanotube Substances 0.000 claims abstract description 64
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 30
- 230000000873 masking effect Effects 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 abstract description 29
- 239000000460 chlorine Substances 0.000 abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 abstract description 27
- 239000010936 titanium Substances 0.000 abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- QXNDHEDXHAAPMR-UHFFFAOYSA-N [Sn]=O.[Sb].[Ti] Chemical compound [Sn]=O.[Sb].[Ti] QXNDHEDXHAAPMR-UHFFFAOYSA-N 0.000 abstract description 4
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- YTJIRARJCQGWQI-UHFFFAOYSA-N [Sb].[Sn].[Ti].[Ru] Chemical compound [Sb].[Sn].[Ti].[Ru] YTJIRARJCQGWQI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 241000894007 species Species 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- IANUMTRPEYONHL-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) titanium(4+) Chemical compound [O-2].[Ti+4].[Ru+3] IANUMTRPEYONHL-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention provides a kind of TiO
2nano-tube array load, containing the preparation method of ruthenium coating catalyzer, belongs to technical field of chlor-alkali industry.First the present invention adopts anonizing to form orderly TiO in Ti substrate
2nano-tube array, increases the specific surface area of carrier, reduces the transmission route of electric charge in electrode materials, improves the catalytic performance of anode coating, reduces chlorine oxygen potential difference; Then by sintering method by ionic radius and RuO
2close titanium tin-antimony oxide is doped to RuO
2in coating, utilize the strong interaction between ruthenium titanium tin antimony solid solution, oxide and substrate, improve the stability of electrode.The inventive method is simple, operational safety, low production cost, and the anode coating catalyzer of preparation has the electro catalytic activity better suppressing to analyse oxygen, promote to analyse chlorine reaction, can be used widely in chlorine industry field.<!-- 2 -->
Description
Technical field
The invention belongs to technical field of chlor-alkali industry, particularly a kind of TiO
2nano-tube array load is containing the preparation method of ruthenium coating catalyzer.
Background technology
Chlorine industry is important Essential Chemistry industry, relates to the every field of national economy and people's lives, its product NaOH, Cl
2and H
2be all important Chemical Manufacture raw material, multiple Chemicals can be processed into further.Current industrial widely used DSA dimensional stable anode applies RuO on titanium plate
2, there is main reaction and analyse chlorine and side reaction and analyse that the potential difference of oxygen is less, high current density stability inferior is poor, electrode price is more expensive and produce the shortcomings such as chlorine efficiency is low in the ruthenium titanium oxide of content >30at.%.In addition, after electrode uses certain hour, due to RuO
2coatingsurface active sites is occupied by the impurity in indissoluble species or electrolytic solution, and the souring of the gas produced in electrolytic process to coating makes the true area of electrode constantly decline, analyse chlorine overpotential to increase, chlorine oxygen potential difference reduces further, and then causes the chlorine selectivity of analysing of electrode to decline.And along with analysing the carrying out of oxygen side reaction, between Ti matrix and coating interface, form TiO
2passive film, causes coating resistance to raise, makes RuO further
2coating activity reduces.Therefore, how to increase the potential difference analysing chlorine reaction and oxygen evolution reaction, reduce and analyse the reacted current potential of chlorine, improve oxygen evolution reaction overpotential, the stability of intensifier electrode is the key realizing efficient, energy-conservation chlorine industry.
Binary or ternary mixed oxide is formed mainly for adulterate in ruthenium titanium oxide coating other elements and oxide compound in current research, composition and the pattern of coating is changed by the content, preparation condition etc. changing dopant species, or add middle layer, change electrode structure, improve its catalytic performance thus.Chinese invention patent CN102505127A discloses " preparation method of noble metal modified titanium anode materials ", although Ni―Ti anode excellent electrochemical performance prepared by this invention, long service life, but adopt precious metal organic coordination compound to be presoma, organic solvent is dimethyl sulfoxide (DMSO), cost is higher, and toxic solvent, easily cause environmental pollution.Chinese invention patent CN102268688A discloses " the ruthenium palladium cobalt coated titanium electrode of tin-antimony interlayer ", and coated titanium electrode prepared by this invention is relative to traditional RuO
2/ Ti, has longer work-ing life, but chlorine oxygen potential difference is less, and the selectivity of electrode is poor.In recent years, TiO
2nanotube is owing to having larger specific surface and high quantum effect and being subject to the extensive concern of researcher in fields such as photochemical catalysis, sensing, solar cells.Chinese invention patent CN102658130A discloses " preparation method of ruthenium-palladium bimetal carried titanium dioxide nano pipe light catalyst and application thereof ", and this invention adopts electrochemical production TiO
2nano-tube array, and through 500 DEG C of anneal, then by ruthenium-palladium galvanic deposit to TiO
2on nano-tube array, thus change the electronic energy level structure of system, improve TiO
2surface properties, and then improve its photocatalysis performance.WangYong-gang etc. utilize hydrothermal method to prepare powder-type TiO
2nanotube, then load RuO
2xH
2o obtains RuO
2/ TiO
2nanotube complex is as electrochemical capacitor.Author selects powder-type TiO
2nanotube is in order to increasing specific surface area as carrier, so that dispersed activity species RuO
2, thus reach the object improving ratio capacitance.As can be seen here, the TiO of high-ratio surface is selected
2nano-tube array contributes to as substrate the catalytic performance improving Catalytic Layer.But, up to the present, have not been reported TiO
2nano-tube array is applied in chlorine industry electrolysis as substrate.
Summary of the invention
What the present invention is directed to the existence of existing DSA dimensional stable anode analyses the shortcomings such as chlorine reaction is little with the potential difference between oxygen evolution reaction, poor stability, provides a kind of TiO
2nano-tube array load is containing the preparation method of ruthenium coating catalyzer.First in Ti substrate, orderly TiO is formed by anonizing
2nano-tube array, does not carry out anneal, is therefore to exist with amorphous form.The TiO of high-specific surface area
2nano-tube array contributes to the dispersity improving catalyzer, reduces the transmission route of electric charge in electrode materials, improves the catalytic performance of anode coating, increases the potential difference analysed chlorine reaction and analyse between oxygen side reaction; Then by sintering method by ionic radius and RuO
2close titanium tin-antimony oxide is doped to RuO
2in coating, form ruthenium titanium tin antimony solid solution, oxide, increase the stability of coating; Meanwhile, the TiO in coating
2with substrate TiO
2nano-tube array character is identical, and then strengthens the bonding force between coating and substrate.
A kind of TiO provided by the invention
2nano-tube array load is containing the preparation method of ruthenium coating catalyzer, and its concrete grammar step comprises:
(1), TiO
2the preparation of nano-tube array
First the oxide compound on Ti sheet surface is removed by mechanical grinding, then successively in acetone and ethanol ultrasonic 15 minutes respectively, then with chemical brightening solution process 30 seconds, wherein polishing fluid was the mixed aqueous solution of concentrated nitric acid and hydrofluoric acid, and volume ratio is HF ︰ HNO
3︰ H
2o=1 ︰ 4 ︰ 5, finally totally stand-by with ultrapure water; Adopting two electrode systems, is to electrode with Ni sheet, and Ti sheet is working electrode, massfraction be 0.5% hydrofluoric acid aqueous solution be electrolyte solution, under room temperature condition, working electrode and to electrode between apply the voltage process 40 minutes of 20V, clean with ultrapure water, dry, obtained TiO
2nano-tube array, TiO
2nano-tube array does not carry out the pretreatment of high temperature anneal, is therefore to exist with amorphous form;
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.10 ~ 0.30mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0 ~ 0.30mol/L, the volumetric molar concentration of tin tetrachloride is 0 ~ 0.30mol/L, and the volumetric molar concentration of butter of antimony is 0 ~ 0.04mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.05 ~ 0.2 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 10 ~ 20 times and preparing
2on nano-tube array, wherein the 1st time to 9th ~ 19 times, all first dry under infrared lamp after each coating, then 400 ~ 500 DEG C of thermooxidizings 10 ~ 15 minutes are proceeded in retort furnace, at 400 ~ 500 DEG C, 1 ~ 2 hour is incubated after last oven dry, room temperature is cooled to furnace temperature, obtained containing ruthenium coating catalyzer.
After the present invention adopts technique scheme, mainly contain following advantage:
(1) TiO
2nano-tube array is owing to having ordered structure, and specific surface area is comparatively large, is conducive to the dispersiveness improving active specy, and perpendicular to electrode surface, thus reduce the transmission route of electric charge in electrode materials to greatest extent, improve the catalytic performance of anode coating.
(2) as unbodied TiO
2the while of nano-tube array and catalyst coat during anneal, by ionic radius and RuO
2close titanium tin-antimony oxide is doped to RuO
2in coating, be conducive to making the obvious refinement of the crystal grain of catalyzer, and form sosoloid, meanwhile, the TiO in coating
2with substrate TiO
2nano-tube array character is identical, further enhancing the reactive force between coating and substrate, extends the life-span of electrode.
The inventive method is simple, operational safety, adopts TiO prepared by the present invention
2nano-tube array load has better suppression containing ruthenium coating catalyzer and analyses oxygen side reaction, and promote the catalytic activity analysing chlorine reaction, what can be used as chlorine industry analyses chlorine anode.
Accompanying drawing explanation
Fig. 1, Fig. 2, Fig. 3 are the scanning electron microscopic picture of electrode prepared by embodiment 1 and 2 and contrast experiment.
In figure: Fig. 1 is TiO prepared by embodiment 1
2nano-tube array load is containing the scanning electron microscopic picture of ruthenium coating catalysis electrode;
Fig. 2 is TiO prepared by embodiment 2
2nano-tube array load is containing the scanning electron microscopic picture of ruthenium coating catalysis electrode;
Fig. 3 is the scanning electron microscopic picture of the Ti load prepared of contrast experiment containing ruthenium coating catalysis electrode.
The linear time base sweep curve of the electrode that Fig. 4 is embodiment 1, prepared by embodiment 2, embodiment 3, embodiment 4 and contrast experiment.
In figure: curve A and a are the TiO executing example 1 preparation
2nano-tube array load is working electrode containing ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and Pt/Ti sheet is the NaNO of supporting electrode, NaCl and 5mol/L of 5mol/L
3the aqueous solution is electrolyte solution, and probe temperature is 40 DEG C, and scanning speed is the linear time base sweep curve under 5mV/s condition.Its center line A analyses chlorine linear time base sweep curve, and line a analyses oxygen linear time base sweep curve.
Curve B and b are the TiO executing example 2 preparation
2nano-tube array load is working electrode containing ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and Pt/Ti sheet is the NaNO of supporting electrode, NaCl and 5mol/L of 5mol/L
3the aqueous solution is electrolyte solution, and probe temperature is 40 DEG C, and scanning speed is the linear time base sweep curve under 5mV/s condition.Its center line B analyses chlorine linear time base sweep curve, and line b analyses oxygen linear time base sweep curve.
Curve C and c are the TiO executing example 3 preparation
2nano-tube array load is working electrode containing ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and Pt/Ti sheet is the NaNO of supporting electrode, NaCl and 5mol/L of 5mol/L
3the aqueous solution is electrolyte solution, and probe temperature is 40 DEG C, and scanning speed is the linear time base sweep curve under 5mV/s condition.Its center line C analyses chlorine linear time base sweep curve, and line c analyses oxygen linear time base sweep curve.
Curve D and d are the TiO executing example 1 preparation
2nano-tube array load is working electrode containing ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and Pt/Ti sheet is the NaNO of supporting electrode, NaCl and 5mol/L of 5mol/L
3the aqueous solution is electrolyte solution, and probe temperature is 40 DEG C, and scanning speed is the linear time base sweep curve under 5mV/s condition.Its center line D analyses chlorine linear time base sweep curve, and line d analyses oxygen linear time base sweep curve.
Curve E and e is Ti load prepared by contrast experiment is working electrode containing ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and Pt/Ti sheet is the NaNO of supporting electrode, NaCl and 5mol/L of 5mol/L
3the aqueous solution is electrolyte solution, and probe temperature is 40 DEG C, and scanning speed is the linear time base sweep curve under 5mV/s condition.Its center line E analyses chlorine linear time base sweep curve, and line e analyses oxygen linear time base sweep curve.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
(1), TiO
2the preparation of nano-tube array
First the oxide compound on Ti sheet surface is removed by mechanical grinding, then successively in acetone and ethanol ultrasonic 15 minutes respectively, then with chemical brightening solution process 30 seconds, wherein polishing fluid was the mixed aqueous solution of concentrated nitric acid and hydrofluoric acid, and volume ratio is HF ︰ HNO
3︰ H
2o=1 ︰ 4 ︰ 5, finally totally stand-by with ultrapure water; Adopting two electrode systems, is to electrode with Ni sheet, and Ti sheet is working electrode, massfraction be 0.5% hydrofluoric acid aqueous solution be electrolyte solution, under room temperature condition, working electrode and to electrode between apply the voltage process 40 minutes of 20V, clean with ultrapure water, dry, obtained TiO
2nano-tube array, TiO
2nano-tube array does not carry out the pretreatment of high temperature anneal, is therefore to exist with amorphous form;
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.10mol/L, and the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.23mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.10 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 10 times and preparing
2on nano-tube array, wherein the 1st time to the 9th time, all first dry under infrared lamp after each coating, then 450 DEG C of thermooxidizings 10 minutes are proceeded in retort furnace, at 450 DEG C, be incubated 1 hour after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
(4), containing sign and the performance test of ruthenium coating catalysis electrode
Scanning electron microscope (SEM) photo obtained containing ruthenium coating catalysis electrode sem test in Fig. 1 prepared.
Adopt three-electrode system, with the NaNO of NaCl and 5mol/L of 5mol/L
3the aqueous solution is as electrolyte solution, in step (3), preparation is working electrode containing ruthenium coating catalysis electrode, saturated calomel electrode is reference electrode, Pt/Ti sheet is supporting electrode, on electrochemical workstation, (CHI660D, Shanghai Chen Hua instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve, and probe temperature is 40 DEG C, scanning speed is 5mV/s, curve A, a in test result corresponding diagram 4.
Embodiment 2
Step (1) is with step (1) in embodiment 1
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.20mol/L; The volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.22mol/L; The volumetric molar concentration of tin tetrachloride is 0.20mol/L; The volumetric molar concentration of butter of antimony is 0.04mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.05 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 20 times and preparing
2on nano-tube array, wherein the 1st time to the 19th time, all first dry under infrared lamp after each coating, then 500 DEG C of thermooxidizings 10 minutes are proceeded in retort furnace, at 500 DEG C, be incubated 1 hour after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
(4), containing sign and the performance test of ruthenium coating catalysis electrode
Scanning electron microscope (SEM) photo obtained containing ruthenium coating catalysis electrode sem test in Fig. 2 prepared.
Adopt three-electrode system, with the NaNO of NaCl and 5mol/L of 5mol/L
3the aqueous solution is as electrolyte solution, in step (3), preparation is working electrode containing ruthenium coating catalysis electrode, saturated calomel electrode is reference electrode, Pt/Ti sheet is supporting electrode, on electrochemical workstation, (CHI660D, Shanghai Chen Hua instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve, and probe temperature is 40 DEG C, scanning speed is 5mV/s, curve B, b in test result corresponding diagram 4.
Embodiment 3
Step (1) is with step (1) in embodiment 1
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.10mol/L, and the volumetric molar concentration of tin tetrachloride is 0.20mol/L, and the volumetric molar concentration of butter of antimony is 0.03mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.2 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 10 times and preparing
2on nano-tube array, wherein the 1st time to the 9th time, all first dry under infrared lamp after each coating, then 400 DEG C of thermooxidizings 15 minutes are proceeded in retort furnace, at 400 DEG C, be incubated 2 hours after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
(4), containing the performance test of ruthenium coating catalysis electrode
Adopt three-electrode system, with the NaNO of NaCl and 5mol/L of 5mol/L
3the aqueous solution is as electrolyte solution, in step (3), preparation is working electrode containing ruthenium coating catalysis electrode, saturated calomel electrode is reference electrode, Pt/Ti sheet is supporting electrode, on electrochemical workstation, (CHI660D, Shanghai Chen Hua instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve, and probe temperature is 40 DEG C, scanning speed is 5mV/s, curve C, c in test result corresponding diagram 4.
Embodiment 4
Step (1) is with step (1) in embodiment 1
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.30mol/L; The volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.30mol/L; The volumetric molar concentration of tin tetrachloride is 0.30mol/L; The volumetric molar concentration of butter of antimony is 0.04mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.05 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 15 times and preparing
2on nano-tube array, wherein the 1st time to the 14th time, all first dry under infrared lamp after each coating, then 450 DEG C of thermooxidizings 10 minutes are proceeded in retort furnace, at 450 DEG C, be incubated 1.5 hours after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
(4), containing the performance test of ruthenium coating catalysis electrode
Adopt three-electrode system, with the NaNO of NaCl and 5mol/L of 5mol/L
3the aqueous solution is as electrolyte solution, in step (3), preparation is working electrode containing ruthenium coating catalysis electrode, saturated calomel electrode is reference electrode, Pt/Ti sheet is supporting electrode, on electrochemical workstation, (CHI660D, Shanghai Chen Hua instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve, and probe temperature is 40 DEG C, scanning speed is 5mV/s, curve D, d in test result corresponding diagram 4.
Contrast experiment
First the oxide compound on Ti sheet surface is removed by mechanical grinding, then successively in acetone and ethanol ultrasonic 15 minutes respectively, then put into the oxalic acid solution 90 DEG C etching 1.5 hours that massfraction is 10wt%, then totally stand-by with ultrapure water.Containing the preparation of ruthenium coating catalyzer with step (3) in embodiment 1, obtained Ti load is containing ruthenium coating catalysis electrode, and scanning electron microscope (SEM) picture is as Fig. 3; Its catalytic performance is tested with step (4) in embodiment 1, curve E, e in test result corresponding diagram 4.
Test-results of the present invention:
As can be seen from Fig. 1 and Fig. 2, with amorphous TiO
2nano-tube array is that carrier loaded containing ruthenium coating catalyst surface almost leakless, crystal grain is tiny, is uniformly dispersed, and segmentation crack in various degree appears in coated electrode surface prepared by the conventional Ti sheet of Fig. 3 display, and in " dry pureed " pattern, this shows TiO
2nano-tube array can improve the dispersiveness of active specy, changes the surface topography of coating, inhibits catalyst coat to be got off by the air scour produced in reaction process.
As can be seen from Figure 4, compared with the coated electrode prepared with conventional Ti sheet, with TiO
2nano-tube array be carrier loaded containing ruthenium coating there is better catalytic activity and Geng Gao analyse chlorine selectivity, it is analysed chlorine reaction and obviously increases with the potential difference between oxygen evolution reaction, and this shows the TiO with bigger serface
2nano-tube array is conducive to the dispersiveness improving active specy, by sintering method by ionic radius and RuO
2close titanium tin-antimony oxide is doped to RuO
2in coating, be conducive to forming sosoloid, and make the obvious refinement of catalyzer crystal grain, thus improve the catalytic performance of anode coating.
Claims (5)
1. a TiO
2nano-tube array load is containing the preparation method of ruthenium coating catalyzer, and its concrete grammar step comprises (1), TiO
2the preparation of nano-tube array
First the oxide compound on Ti sheet surface is removed by mechanical grinding, then successively in acetone and ethanol ultrasonic 15 minutes respectively, then with chemical brightening solution process 30 seconds, wherein polishing fluid was the mixed aqueous solution of concentrated nitric acid and hydrofluoric acid, and volume ratio is HF ︰ HNO
3︰ H
2o=1 ︰ 4 ︰ 5, finally totally stand-by with ultrapure water; Adopting two electrode systems, is to electrode with Ni sheet, and Ti sheet is working electrode, massfraction be 0.5% hydrofluoric acid aqueous solution be electrolyte solution, under room temperature condition, working electrode and to electrode between apply the voltage process 40 minutes of 20V, clean with ultrapure water, dry, obtained TiO
2nano-tube array, TiO
2nano-tube array does not carry out the pretreatment of high temperature anneal, is therefore to exist with amorphous form;
It is characterized in that:
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.10 ~ 0.30mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0 ~ 0.30mol/L, the volumetric molar concentration of tin tetrachloride is 0 ~ 0.30mol/L, and the volumetric molar concentration of butter of antimony is 0 ~ 0.04mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.05 ~ 0.2 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 10 ~ 20 times and preparing
2on nano-tube array, wherein the 1st time to 9th ~ 19 times, all first dry under infrared lamp after each coating, then 400 ~ 500 DEG C of thermooxidizings 10 ~ 15 minutes are proceeded in retort furnace, at 400 ~ 500 DEG C, 1 ~ 2 hour is incubated after last oven dry, room temperature is cooled to furnace temperature, obtained containing ruthenium coating catalyzer.
2. according to a kind of TiO according to claim 1
2nano-tube array load, containing the preparation method of ruthenium coating catalyzer, is characterized in that step (2) ~ (3) of concrete preparation method:
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.10mol/L, and the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.23mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.10 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 10 times and preparing
2on nano-tube array, wherein the 1st time to the 9th time, all first dry under infrared lamp after each coating, then 450 DEG C of thermooxidizings 10 minutes are proceeded in retort furnace, at 450 DEG C, be incubated 1 hour after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
3. according to a kind of TiO according to claim 1
2nano-tube array load, containing the preparation method of ruthenium coating catalyzer, is characterized in that step (2) ~ (3) of concrete preparation method:
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.20mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.22mol/L, the volumetric molar concentration of tin tetrachloride is 0.20mol/L, and the volumetric molar concentration of butter of antimony is 0.04mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.05 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 20 times and preparing
2on nano-tube array, wherein the 1st time to the 19th time, all first dry under infrared lamp after each coating, then 500 DEG C of thermooxidizings 10 minutes are proceeded in retort furnace, at 500 DEG C, be incubated 1 hour after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
4. according to a kind of TiO according to claim 1
2nano-tube array load, containing the preparation method of ruthenium coating catalyzer, is characterized in that step (2) ~ (3) of concrete preparation method:
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.10mol/L, and the volumetric molar concentration of tin tetrachloride is 0.20mol/L, and the volumetric molar concentration of butter of antimony is 0.03mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.2 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 10 times and preparing
2on nano-tube array, wherein the 1st time to the 9th time, all first dry under infrared lamp after each coating, then 400 DEG C of thermooxidizings 15 minutes are proceeded in retort furnace, at 400 DEG C, be incubated 2 hours after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
5. according to a kind of TiO according to claim 1
2nano-tube array load, containing the preparation method of ruthenium coating catalyzer, is characterized in that step (2) ~ (3) of concrete preparation method:
(2), masking liquid preparation
Be the Virahol of 1 ︰ 1 and alcohol mixed solution for masking liquid prepared by solvent with volume ratio, wherein the volumetric molar concentration of ruthenium trichloride is 0.30mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.30mol/L, the volumetric molar concentration of tin tetrachloride is 0.30mol/L, and the volumetric molar concentration of butter of antimony is 0.04mol/L;
(3) containing the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
2nano-tube array 0.05 milliliter measures the masking liquid that step (2) is prepared, and divides the TiO being coated in step (1) for 15 times and preparing
2on nano-tube array, wherein the 1st time to the 14th time, all first dry under infrared lamp after each coating, then 450 DEG C of thermooxidizings 10 minutes are proceeded in retort furnace, at 450 DEG C, be incubated 1.5 hours after last oven dry, be cooled to room temperature with furnace temperature, obtained containing ruthenium coating catalyzer.
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| CN104022289B (en) * | 2014-05-07 | 2017-01-04 | 南通大学 | A kind of DMFC RuNi/TiO2nanotube electrode and preparation method |
| CN104176795B (en) * | 2014-08-28 | 2016-01-20 | 扬州大学 | The preparation method of the titania nanotube of load macropore titanium tetrachloride |
| CN107162116B (en) * | 2017-05-19 | 2020-04-10 | 福州大学 | Ru-doped titanium dioxide electrode material with heterogeneous photoelectrocatalysis performance |
| CN107916446B (en) * | 2017-11-16 | 2019-07-30 | 重庆大学 | The clean manufacturing of chloroacetaldehyde oxime and its RuO used2@TNTs anode |
| CN110129821A (en) * | 2019-05-10 | 2019-08-16 | 上海氯碱化工股份有限公司 | Tin, Sb doped titanium-based ruthenic oxide coated electrode preparation method |
| CN110158087B (en) * | 2019-05-16 | 2020-05-22 | 西安交通大学 | Preparation method of laminated electrolytic oxidation water electrode |
| CN110387558B (en) * | 2019-07-26 | 2020-11-24 | 浙江工业大学 | Ruthenium-tantalum chlorine evolution electrode and preparation method and test method thereof |
| CN113308727B (en) * | 2020-02-26 | 2023-03-28 | 新疆知信科技有限公司 | Titanium dioxide nanotube, composite electrode based on titanium dioxide nanotube, and preparation method and application of composite electrode |
| CN112374585B (en) * | 2020-09-18 | 2023-03-21 | 昆明理工大学 | Method for simultaneously removing antibiotics and resistant bacteria in water environment |
| CN113716658B (en) * | 2021-09-27 | 2022-10-21 | 大连理工大学 | Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure |
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