CN103014752A - Preparation method of TiO2-nanotube-array-supported ruthenium-containing coating catalyst - Google Patents
Preparation method of TiO2-nanotube-array-supported ruthenium-containing coating catalyst Download PDFInfo
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- CN103014752A CN103014752A CN2013100124832A CN201310012483A CN103014752A CN 103014752 A CN103014752 A CN 103014752A CN 2013100124832 A CN2013100124832 A CN 2013100124832A CN 201310012483 A CN201310012483 A CN 201310012483A CN 103014752 A CN103014752 A CN 103014752A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 81
- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 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
- 239000003054 catalyst Substances 0.000 title abstract description 4
- 239000002071 nanotube Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims description 30
- 230000000873 masking effect Effects 0.000 claims description 30
- 238000006555 catalytic reaction Methods 0.000 claims description 29
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 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
- 238000009413 insulation Methods 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
- 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
- 239000010936 titanium Substances 0.000 abstract description 27
- 239000000460 chlorine Substances 0.000 abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 2
- JPRQEIKKWFCTMS-UHFFFAOYSA-N [Ti].[Ru].[Sn] Chemical compound [Ti].[Ru].[Sn] JPRQEIKKWFCTMS-UHFFFAOYSA-N 0.000 abstract 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 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
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 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
- QXNDHEDXHAAPMR-UHFFFAOYSA-N [Sn]=O.[Sb].[Ti] Chemical compound [Sn]=O.[Sb].[Ti] QXNDHEDXHAAPMR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture 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
- YTJIRARJCQGWQI-UHFFFAOYSA-N [Sb].[Sn].[Ti].[Ru] Chemical compound [Sb].[Sn].[Ti].[Ru] YTJIRARJCQGWQI-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect 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
- 150000003608 titanium Chemical class 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The invention provides a preparation method of a TiO2-nanotube-array-supported ruthenium-containing coating catalyst, belonging to the technical field of chlor-alkali industry. An anodic oxidation process is utilized to form an ordered TiO2 nanotube array on a Ti substrate, thereby increasing the specific area of the supporter, reducing the transmission path of charges in the electrode material, enhancing the catalytic property of the anode coating and lowering the chlorine-oxygen potential difference; and a sintering process is utilized to dope titanium tin stibium oxide with similar ionic radius to RuO2 into a RuO2 coating, and the strong interaction between the ruthenium titanium tin stibium solid solution oxide and the substrate is utilized to enhance the stability of the electrode. The method provided by the invention is simple and easy to implement, and has the advantages of high operational safety and low production cost; and the prepared anode coating catalyst has higher electrocatalytic activity for inhibiting oxygen evolution and accelerating chlorine evolution reaction, and can be widely used in the fields of chlor-alkali industry.
Description
Technical field
The invention belongs to the chlorine industry technical field, particularly a kind of TiO
2The nano-tube array load contains 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
2All be important Chemical Manufacture raw material, can further be processed into multiple Chemicals.Industrial widely used DSA dimensional stable anode is to apply RuO at the titanium plate at present
2Content〉the ruthenium titanium oxide of 30at.%, exist analyse the chlorine oxygen evolution potential poor less, the high current density stability inferior is poor, the electrode price is more expensive and produce the shortcomings such as chlorine efficient is low.In addition, after electrode uses certain hour, because RuO
2The coatingsurface active sites is occupied by the impurity in indissoluble species or the electrolytic solution, and the gas that produces in the electrolytic process constantly descends the true area of electrode to the souring of coating, analyse the chlorine overpotential and increase, chlorine oxygen potential difference further reduces, and then causes the selectivity of electrode to descend.And be accompanied by the carrying out of oxygen evolution reaction, between Ti matrix and coating interface, form TiO
2Passive film causes coating resistance to raise, and further makes RuO
2The coating activity decreased.Therefore, how increasing chlorine oxygen potential difference, reduce and analyse chlorine reaction overpotential, improve the oxygen evolution reaction overpotential, improve the stability of electrode, is the key that realizes efficient, energy-conservation chlorine industry.
Form binary or ternary mixed oxide mainly for mix in the ruthenium titanium oxide coating other elements and oxide compound in the present research, content by changing dopant species, preparation condition etc. change composition and the pattern of coating, perhaps add the middle layer, change electrode structure, improve thus its catalytic performance.Chinese invention patent CN 102505127 A disclose " preparation method of noble metal modified titanium anode materials ", although should invent the titanium anode electrochemical excellent property of preparation, long service life, yet adopting the precious metal organic coordination compound is presoma, organic solvent is dimethyl sulfoxide (DMSO), cost is higher, and solvent is poisonous, causes easily environmental pollution.Chinese invention patent CN 102268688 A disclose " the ruthenium palladium cobalt coated titanium electrode of tin-antimony interlayer ", and the coated titanium electrode of this invention preparation is with respect to traditional RuO
2/ Ti has longer work-ing life, but chlorine oxygen potential difference is less, and the selectivity of electrode is relatively poor.
Summary of the invention
The shortcomings such as the chlorine oxygen potential difference that the present invention is directed to existing DSA dimensional stable anode existence is little, poor stability provide a kind of TiO
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer.At first form orderly TiO by anonizing in the Ti substrate
2Nano-tube array, the specific surface area of increase 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 with ionic radius and RuO
2Close titanium tin-antimony oxide is doped to RuO
2In the coating, utilize the strong interaction between ruthenium titanium tin antimony solid solution, oxide and substrate, improve the stability of electrode.
A kind of TiO provided by the invention
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer, and its concrete grammar step comprises:
(1), TiO
2The preparation of nano-tube array
First Ti sheet mechanical grinding is removed oxide on surface, then distinguish ultrasonic 15 minutes successively in acetone and ethanol, processed 30 seconds with chemical brightening solution, wherein polishing fluid is the mixed aqueous solution of concentrated nitric acid and hydrofluoric acid, and volume ratio is HF ︰ HNO
3︰ H
2O=1 ︰, 4 ︰ 5 rinses well stand-by at last with ultrapure water; Adopt two electrode systems, take the Ni sheet as to electrode, the Ti sheet is working electrode, massfraction is that the hydrofluoric acid aqueous solution of 0.5 % is electrolyte solution, under the room temperature condition, at working electrode and the voltage that applies 20 V between to electrode processed 40 minutes, rinse well with ultrapure water, oven dry makes TiO
2Nano-tube array;
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, wherein the volumetric molar concentration of ruthenium trichloride is 0.10～0.30 mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0～0.30 mol/L, the volumetric molar concentration of tin tetrachloride is 0～0.30 mol/L, and the volumetric molar concentration of butter of antimony is 0～0.04 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.05～0.2 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 10～20 times
2On the nano-tube array, wherein the 1st time to the 9th～19 time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 400～500 ℃ of thermooxidizings 10～15 minutes over to, under 400～500 ℃, be incubated 1～2 hour after the last oven dry, be cooled to room temperature with furnace temperature, make and contain the ruthenium coating catalyzer.
After the present invention adopts technique scheme, mainly contain following advantage:
(1) the TNTs electrode materials is owing to have ordered structure, specific surface area is larger, is conducive to improve the dispersiveness of active specy, and perpendicular to electrode surface, thereby reduce to greatest extent the transmission route of electric charge in electrode materials, improve the catalytic performance of anode coating.
(2) by carrier and coating while anneal, with ionic radius and RuO
2Close titanium tin-antimony oxide is doped to RuO
2In the coating, be conducive to make the obvious refinement of crystal grain of catalyzer, and form sosoloid, thereby strengthened the reactive force between coating and substrate, prolong the life-span of electrode.
The inventive method is simple, operational safety, the TiO that adopts the present invention to prepare
2The nano-tube array load contains the ruthenium coating catalyzer and has the catalytic activity that better inhibition is analysed oxygen, promoted to analyse the chlorine reaction, and what can be used as chlorine industry analyses the chlorine anode.
Description of drawings
Fig. 1, Fig. 2, Fig. 3 are embodiment 1 and 2 and the scanning electron microscope picture of the electrode of contrast experiment preparation.
Among the figure: Fig. 1 is the TiO of embodiment 1 preparation
2The nano-tube array load contains the scanning electron microscope picture of ruthenium coating catalysis electrode;
Fig. 2 is the TiO of embodiment 2 preparations
2The nano-tube array load contains the scanning electron microscope picture of ruthenium coating catalysis electrode;
Fig. 3 contains the scanning electron microscope picture of ruthenium coating catalysis electrode for the Ti load of contrast experiment's preparation.
Fig. 4 is the linear time base sweep curve of the electrode of embodiment 1, embodiment 2, embodiment 3, embodiment 4 and contrast experiment's preparation.
Among the figure: curve A and a are the TiO that executes example 1 preparation
2It is working electrode that the nano-tube array load contains the ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and the Pt/Ti sheet is supporting electrode, the NaNO of the NaCl of 5 mol/L and 5 mol/L
3The aqueous solution is electrolyte solution, and probe temperature is 40 ℃, and scanning speed is the linear time base sweep curve under the 5 mV/s conditions.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 that executes example 2 preparations
2It is working electrode that the nano-tube array load contains the ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and the Pt/Ti sheet is supporting electrode, the NaNO of the NaCl of 5 mol/L and 5 mol/L
3The aqueous solution is electrolyte solution, and probe temperature is 40 ℃, and scanning speed is the linear time base sweep curve under the 5 mV/s conditions.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 that executes example 3 preparations
2It is working electrode that the nano-tube array load contains the ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and the Pt/Ti sheet is supporting electrode, the NaNO of the NaCl of 5 mol/L and 5 mol/L
3The aqueous solution is electrolyte solution, and probe temperature is 40 ℃, and scanning speed is the linear time base sweep curve under the 5 mV/s conditions.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 that executes example 1 preparation
2It is working electrode that the nano-tube array load contains the ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and the Pt/Ti sheet is supporting electrode, the NaNO of the NaCl of 5 mol/L and 5 mol/L
3The aqueous solution is electrolyte solution, and probe temperature is 40 ℃, and scanning speed is the linear time base sweep curve under the 5 mV/s conditions.Its center line D analyses chlorine linear time base sweep curve, and line d analyses oxygen linear time base sweep curve.
It is working electrode that the Ti load that curve E and e prepare for the contrast experiment contains the ruthenium coating catalysis electrode, and saturated calomel electrode is reference electrode, and the Pt/Ti sheet is supporting electrode, the NaNO of the NaCl of 5 mol/L and 5 mol/L
3The aqueous solution is electrolyte solution, and probe temperature is 40 ℃, and scanning speed is the linear time base sweep curve under the 5 mV/s conditions.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 specify the present invention.
Embodiment 1
(1), TiO
2The preparation of nano-tube array
First Ti sheet mechanical grinding is removed oxide on surface, then distinguish ultrasonic 15 minutes successively in acetone and ethanol, processed 30 seconds with chemical brightening solution, wherein polishing fluid is the mixed aqueous solution of concentrated nitric acid and hydrofluoric acid, and volume ratio is HF ︰ HNO
3︰ H
2O=1 ︰, 4 ︰ 5 rinses well stand-by at last with ultrapure water; Adopt two electrode systems, take the Ni sheet as to electrode, the Ti sheet is working electrode, massfraction is that the hydrofluoric acid aqueous solution of 0.5 % is electrolyte solution, under the room temperature condition, at working electrode and the voltage that applies 20 V between to electrode processed 40 minutes, rinse well with ultrapure water, oven dry makes TiO
2Nano-tube array;
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, and wherein the volumetric molar concentration of ruthenium trichloride is 0.10 mol/L, and the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.23 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.10 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 10 times
2On the nano-tube array, wherein the 1st time to the 9th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 450 ℃ of thermooxidizings 10 minutes over to, last oven dry is rear to be cooled to room temperature 450 ℃ of lower insulations 1 hour with furnace temperature, makes to contain the ruthenium coating catalyzer.
(4), contain sign and the performance test of ruthenium coating catalysis electrode
The ruthenium coating catalysis electrode that contains for preparing obtains scanning electron microscope (SEM) photo among Fig. 1 with sem test.
Adopt three-electrode system, with the NaCl of 5 mol/L and the NaNO of 5 mol/L
3The aqueous solution is as electrolyte solution, the ruthenium coating catalysis electrode that contains of preparation is working electrode in the step (3), saturated calomel electrode is reference electrode, the Pt/Ti sheet is supporting electrode, (CHI660D, Shanghai occasion China instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve on electrochemical workstation, and probe temperature is 40 ℃, scanning speed is 5 mV/s, curve A, a in the test result corresponding diagram 4.
Step (1) is with step (1) among the embodiment 1
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, and wherein the volumetric molar concentration of ruthenium trichloride is 0.20 mol/L; The volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.22 mol/L; The volumetric molar concentration of tin tetrachloride is 0.20 mol/L; The volumetric molar concentration of butter of antimony is 0.04 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.05 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 20 times
2On the nano-tube array, wherein the 1st time to the 19th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 500 ℃ of thermooxidizings 10 minutes over to, last oven dry is rear to be cooled to room temperature 500 ℃ of lower insulations 1 hour with furnace temperature, makes to contain the ruthenium coating catalyzer.
(4), contain sign and the performance test of ruthenium coating catalysis electrode
The ruthenium coating catalysis electrode that contains for preparing obtains scanning electron microscope (SEM) photo among Fig. 2 with sem test.
Adopt three-electrode system, with the NaCl of 5 mol/L and the NaNO of 5 mol/L
3The aqueous solution is as electrolyte solution, the ruthenium coating catalysis electrode that contains of preparation is working electrode in the step (3), saturated calomel electrode is reference electrode, the Pt/Ti sheet is supporting electrode, (CHI660D, Shanghai occasion China instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve on electrochemical workstation, and probe temperature is 40 ℃, scanning speed is 5 mV/s, curve B, b in the test result corresponding diagram 4.
Step (1) is with step (1) among the embodiment 1
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, and wherein the volumetric molar concentration of ruthenium trichloride is 0.10 mol/L, and the volumetric molar concentration of tin tetrachloride is 0.20 mol/L, and the volumetric molar concentration of butter of antimony is 0.03 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.2 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 10 times
2On the nano-tube array, wherein the 1st time to the 9th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 400 ℃ of thermooxidizings 15 minutes over to, last oven dry is rear to be cooled to room temperature 400 ℃ of lower insulations 2 hours with furnace temperature, makes to contain the ruthenium coating catalyzer.
(4), contain the performance test of ruthenium coating catalysis electrode
Adopt three-electrode system, with the NaCl of 5 mol/L and the NaNO of 5 mol/L
3The aqueous solution is as electrolyte solution, the ruthenium coating catalysis electrode that contains of preparation is working electrode in the step (3), saturated calomel electrode is reference electrode, the Pt/Ti sheet is supporting electrode, (CHI660D, Shanghai occasion China instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve on electrochemical workstation, and probe temperature is 40 ℃, scanning speed is 5 mV/s, curve C, c in the test result corresponding diagram 4.
Embodiment 4
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, and wherein the volumetric molar concentration of ruthenium trichloride is 0.30 mol/L; The volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.30 mol/L; The volumetric molar concentration of tin tetrachloride is 0.30 mol/L; The volumetric molar concentration of butter of antimony is 0.04 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.05 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 15 times
2On the nano-tube array, wherein the 1st time to the 14th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 450 ℃ of thermooxidizings 10 minutes over to, last oven dry is rear to be cooled to room temperature 450 ℃ of lower insulations 1.5 hours with furnace temperature, makes to contain the ruthenium coating catalyzer.
(4), contain the performance test of ruthenium coating catalysis electrode
Adopt three-electrode system, with the NaCl of 5 mol/L and the NaNO of 5 mol/L
3The aqueous solution is as electrolyte solution, the ruthenium coating catalysis electrode that contains of preparation is working electrode in the step (3), saturated calomel electrode is reference electrode, the Pt/Ti sheet is supporting electrode, (CHI660D, Shanghai occasion China instrument company) tests it and analyses chlorine and analyse oxygen linear sweep voltammetry curve on electrochemical workstation, and probe temperature is 40 ℃, scanning speed is 5 mV/s, curve D, d in the test result corresponding diagram 4.
The contrast experiment
The Ti sheet is removed the oxide compound on surface through mechanical grinding, and then successively in acetone and ethanol ultrasonic 15 minutes respectively, then 90 ℃ of etchings of oxalic acid solution 1.5 hours of putting into massfraction again and be 10 wt % rinsed well stand-by with ultrapure water.Contain the preparation of ruthenium coating catalyzer with step (3) among the embodiment 1, make the Ti load and contain the ruthenium coating catalysis electrode, scanning electron microscope (SEM) picture such as Fig. 3; Its catalytic performance test is with step (4) among the embodiment 1, curve E, e in the test result corresponding diagram 4.
Test-results of the present invention:
Can find out from Fig. 1 and Fig. 2, take TNTs as the carrier loaded almost leakless of ruthenium coating catalyst surface that contains, crystal grain is tiny, be uniformly dispersed, and segmentation crack in various degree appears in the coated electrode surface of the conventional Ti sheet that Fig. 3 shows preparation, be " dried mud shape " pattern, this shows that TNT can improve the dispersiveness of active specy.
As can be seen from Figure 4, compare with the coated electrode of conventional Ti sheet preparation, take TNTs as carrier loaded contain that ruthenium coating has better catalytic activity and a Geng Gao analyse the chlorine selectivity, its chlorine oxygen potential difference obviously improves, this shows that the TNTs with bigger serface is conducive to improve the dispersiveness of active specy, by sintering method with ionic radius and RuO
2Close titanium tin-antimony oxide is doped to RuO
2In the coating, be conducive to form sosoloid, and make the obvious refinement of catalyzer crystal grain, thus the catalytic performance of raising anode coating.
Claims (5)
1. TiO
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer, and its concrete grammar step comprises
(1), TiO
2The preparation of nano-tube array
First Ti sheet mechanical grinding is removed oxide on surface, then distinguish ultrasonic 15 minutes successively in acetone and ethanol, processed 30 seconds with chemical brightening solution, wherein polishing fluid is the mixed aqueous solution of concentrated nitric acid and hydrofluoric acid, and volume ratio is HF ︰ HNO
3︰ H
2O=1 ︰, 4 ︰ 5 rinses well stand-by at last with ultrapure water; Adopt two electrode systems, take the Ni sheet as to electrode, the Ti sheet is working electrode, massfraction is that the hydrofluoric acid aqueous solution of 0.5 % is electrolyte solution, under the room temperature condition, at working electrode and the voltage that applies 20 V between to electrode processed 40 minutes, rinse well with ultrapure water, oven dry makes TiO
2Nano-tube array;
It is characterized in that:
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, wherein the volumetric molar concentration of ruthenium trichloride is 0.10～0.30 mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0～0.30 mol/L, the volumetric molar concentration of tin tetrachloride is 0～0.30 mol/L, and the volumetric molar concentration of butter of antimony is 0～0.04 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.05～0.2 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 10～20 times
2On the nano-tube array, wherein the 1st time to the 9th～19 time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 400～500 ℃ of thermooxidizings 10～15 minutes over to, under 400～500 ℃, be incubated 1～2 hour after the last oven dry, be cooled to room temperature with furnace temperature, make and contain the ruthenium coating catalyzer.
2. according to a kind of TiO claimed in claim 1
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer, it is characterized in that concrete preparation method's step (2)～(3):
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, and wherein the volumetric molar concentration of ruthenium trichloride is 0.10 mol/L, and the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.23 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.10 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 10 times
2On the nano-tube array, wherein the 1st time to the 9th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 450 ℃ of thermooxidizings 10 minutes over to, last oven dry is rear to be cooled to room temperature 450 ℃ of lower insulations 1 hour with furnace temperature, makes to contain the ruthenium coating catalyzer.
3. according to a kind of TiO claimed in claim 1
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer, it is characterized in that concrete preparation method's step (2)～(3):
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, wherein the volumetric molar concentration of ruthenium trichloride is 0.20 mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.22 mol/L, the volumetric molar concentration of tin tetrachloride is 0.20 mol/L, and the volumetric molar concentration of butter of antimony is 0.04 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.05 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 20 times
2On the nano-tube array, wherein the 1st time to the 19th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 500 ℃ of thermooxidizings 10 minutes over to, last oven dry is rear to be cooled to room temperature 500 ℃ of lower insulations 1 hour with furnace temperature, makes to contain the ruthenium coating catalyzer.
4. according to a kind of TiO claimed in claim 1
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer, it is characterized in that concrete preparation method's step (2)～(3):
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, and wherein the volumetric molar concentration of ruthenium trichloride is 0.10 mol/L, and the volumetric molar concentration of tin tetrachloride is 0.20 mol/L, and the volumetric molar concentration of butter of antimony is 0.03 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.2 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 10 times
2On the nano-tube array, wherein the 1st time to the 9th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 400 ℃ of thermooxidizings 15 minutes over to, last oven dry is rear to be cooled to room temperature 400 ℃ of lower insulations 2 hours with furnace temperature, makes to contain the ruthenium coating catalyzer.
5. according to a kind of TiO claimed in claim 1
2The nano-tube array load contains the preparation method of ruthenium coating catalyzer, it is characterized in that concrete preparation method's step (2)～(3):
(2), masking liquid preparation
Virahol take volume ratio as 1 ︰ 1 and alcohol mixed solution are solvent preparation masking liquid, wherein the volumetric molar concentration of ruthenium trichloride is 0.30 mol/L, the volumetric molar concentration of positive four butyl esters of metatitanic acid is 0.30 mol/L, the volumetric molar concentration of tin tetrachloride is 0.30 mol/L, and the volumetric molar concentration of butter of antimony is 0.04 mol/L;
(3) contain the preparation of ruthenium coating catalysis electrode
By every square centimeter of TiO
20.05 milliliter of masking liquid of measuring step (2) preparation of nano-tube array divides the TiO that is coated in step (1) preparation for 15 times
2On the nano-tube array, wherein the 1st time to the 14th time, after each the coating, all under infrared lamp, dry first, then change in the retort furnace 450 ℃ of thermooxidizings 10 minutes over to, last oven dry is rear to be cooled to room temperature 450 ℃ of lower insulations 1.5 hours with furnace temperature, makes to contain the ruthenium coating catalyzer.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924262A (en) * | 2014-04-03 | 2014-07-16 | 重庆大学 | Method for preparing ruthenium-containing coating catalyst by adopting hydrothermal method |
| CN104022289A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | Direct methanol fuel cell RuNi/TiO2 nanotube electrode and preparation method thereof |
| CN104176795A (en) * | 2014-08-28 | 2014-12-03 | 扬州大学 | Preparation method for titanium dioxide nanotube loaded with macroporous antimony tin oxide |
| CN107162116A (en) * | 2017-05-19 | 2017-09-15 | 福州大学 | The titania-doped electrode materials of Ru with heterogeneous PhotoelectrocatalytiPerformance Performance |
| CN107916446A (en) * | 2017-11-16 | 2018-04-17 | 重庆大学 | The clean manufacturing of chloroacetaldehyde oxime and its RuO used2@TNTs anodes |
| 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 |
| CN110158087A (en) * | 2019-05-16 | 2019-08-23 | 西安交通大学 | A kind of preparation method of lamination shape electrolytic oxidation water electrode |
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| CN113716658A (en) * | 2021-09-27 | 2021-11-30 | 大连理工大学 | Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050117194A1 (en) * | 2003-10-14 | 2005-06-02 | Sang-Ho Kim | Method for preparing electrode system, electrode system prepared therefrom, and electric device comprising the same |
| US7239076B2 (en) * | 2003-09-25 | 2007-07-03 | General Electric Company | Self-aligned gated rod field emission device and associated method of fabrication |
| CN101113525A (en) * | 2007-02-09 | 2008-01-30 | 南京航空航天大学 | Pt-TiO2/Ti combination electrode and method for making same |
| CN102658130A (en) * | 2012-04-20 | 2012-09-12 | 大连理工大学 | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof |
-
2013
- 2013-01-14 CN CN201310012483.2A patent/CN103014752B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7239076B2 (en) * | 2003-09-25 | 2007-07-03 | General Electric Company | Self-aligned gated rod field emission device and associated method of fabrication |
| US20050117194A1 (en) * | 2003-10-14 | 2005-06-02 | Sang-Ho Kim | Method for preparing electrode system, electrode system prepared therefrom, and electric device comprising the same |
| CN101113525A (en) * | 2007-02-09 | 2008-01-30 | 南京航空航天大学 | Pt-TiO2/Ti combination electrode and method for making same |
| CN102658130A (en) * | 2012-04-20 | 2012-09-12 | 大连理工大学 | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| WANG YONG-GANG: "Preparation and electrochemical capacitance of RuO2/TiO2 nanotubes composites", 《ELECTROCHIMICA ACTA》 * |
| XUEMING CHEN ET.AL: "stable Ti/RuO2-Sb2O5-SnO2 electrodes for O2 evolution", 《ELECTROCHIMICA ACTA》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924262B (en) * | 2014-04-03 | 2017-01-04 | 重庆大学 | The hydro-thermal method preparation method containing ruthenium coating catalyst |
| CN103924262A (en) * | 2014-04-03 | 2014-07-16 | 重庆大学 | Method for preparing ruthenium-containing coating catalyst by adopting hydrothermal method |
| CN104022289A (en) * | 2014-05-07 | 2014-09-03 | 南通大学 | Direct methanol fuel cell RuNi/TiO2 nanotube electrode and preparation method thereof |
| CN104176795A (en) * | 2014-08-28 | 2014-12-03 | 扬州大学 | Preparation method for titanium dioxide nanotube loaded with macroporous antimony tin oxide |
| CN104176795B (en) * | 2014-08-28 | 2016-01-20 | 扬州大学 | The preparation method of the titania nanotube of load macropore titanium tetrachloride |
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| 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 |
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