CN104694991A - Method for preparing platinum-gold double metal doped TiO2 nanotube electrode - Google Patents
Method for preparing platinum-gold double metal doped TiO2 nanotube electrode Download PDFInfo
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- CN104694991A CN104694991A CN201410840507.8A CN201410840507A CN104694991A CN 104694991 A CN104694991 A CN 104694991A CN 201410840507 A CN201410840507 A CN 201410840507A CN 104694991 A CN104694991 A CN 104694991A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002071 nanotube Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title abstract description 6
- 239000002184 metal Substances 0.000 title abstract description 6
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 title abstract 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 229910018885 Pt—Au Inorganic materials 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002659 electrodeposit Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000012876 topography Methods 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 230000010718 Oxidation Activity Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910001651 emery Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000010931 gold Substances 0.000 abstract description 34
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007743 anodising Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 abstract 2
- 229910052939 potassium sulfate Inorganic materials 0.000 abstract 2
- 235000011151 potassium sulphates Nutrition 0.000 abstract 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 238000006056 electrooxidation reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910018949 PtAu Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a method for preparing an electrode and particularly relates to a method for preparing a platinum-gold double metal doped TiO2 nanotube electrode. The method comprises the following steps: (1) preparing a TiO2 nanotube on a titanium substrate in the mixed electrolytic solution of sodium fluoride and phosphoric acid through anodizing and calcining; and (2) applying platinum and gold to the surface of the TiO2 nanotube in two steps in the electrolytic deposition solution of chloroauric acid and potassium sulfate and the electrolytic deposition solution of chloroplatinic acid and potassium sulfate through reducing at a constant potential to obtain the platinum-gold double metal doped TiO2 nanotube electrode. The platinum-gold double metal doped TiO2 nanotube electrode prepared by adopting the method has the advantages that platinum and gold particles are small in size and uniform in distribution. The platinum-gold double metal doped TiO2 nanotube electrode has the activity of eclectically catalyzing and oxidizing methanol, ethanol and glycerol, has a good effect of degrading when being used for photo-eclectically catalyzing and oxidizing organic matters and is improved in photo-eclectically catalyzing properties significantly.
Description
Technical field
The present invention relates to a kind of method preparing electrode, particularly relate to one and prepare platinum bimetal doped Ti O
2the method of nanotube electrode.
Background technology
Titanium dioxide (TiO
2) be a kind of important inorganic semiconductor functional materials, there is the characteristics such as wet sensitive, air-sensitive, dielectric effect, photoelectric conversion and superior photocatalysis performance, there is important application prospect in the field such as the storage of sun power and utilization, opto-electronic conversion, wastewater treatment, dielectric materials, environmental purification, coating, catalyzer, photochromic and photocatalytic degradation environmental pollutant, become one of focus competitively studied both at home and abroad.And following most potential infant industry may be become.
Titania nanotube (TiO
2-NTs) be nano-TiO
2a kind of existence form, wherein TiO
2exist with nanotube form, and with the array format of rule, it has higher specific surface area (because nanotube has larger specific surface area than nanometer film), can improve the dispersiveness of noble metal granule on its surface, and more stably can be combined with metallic particles
[8].TiO
2nanotube redox ability is strong, acid-proof alkaline is good, there is not photoetch, bio-compatibility is good, photocatalysis efficiency is higher, specific surface area is larger, and preparation method is simple, it is a kind of nano-functional material with excellent photoelectric transformation efficiency, optical characteristics, electrology characteristic, Preliminary Applications effect is obtained in Environmental capacity, contamination analysis, new forms of energy are opened etc., be widely used in solar cell and organic degraded aspect, Nano tube array of titanium dioxide is also a study hotspot as the application of sensor in addition.It has good ultraviolet absorption ability, so also for organic matter degradation.Stable, highly sensitive, detectability is low, and the advantage of response fast makes it be mainly used in electrochemical analysis aspect at present.With general nano-TiO
2powder is compared, TiO
2the special construction of nanotube makes it have larger specific surface area and stronger adsorptive power, is expected to the electricity conversion showing better photocatalysis performance and Geng Gao.
But, Detitanium-ore-type TiO
2energy gap be 3.2 eV, absorbing wavelength can only be less than the sunlight of 387.5 nm, and sunlight medium ultraviolet light (the λ < 400 nm) radiant section arriving earth surface only account for about 4% of whole sunlight power spectrum, visible ray content is about 45%, therefore develops the important topic that visible-light-responsive photocatalyst becomes current photocatalysis field.In addition, TiO
2also there is the problem that quantum yield is on the low side and degradation rate is unhappy in photochemical catalysis, its photon efficiency is generally no more than 10%, and the recombination probability how reducing light induced electron and hole is also problem demanding prompt solution.There are some researches show, adopt the methods such as metal ion mixing, nonmetal doping, noble metal loading, semiconductors coupling and surface sensitization to TiO
2carry out suitable doping or surface modification, not only effectively can suppress the compound in light induced electron and hole, and can TiO be expanded
2its photocatalysis performance is improved to the absorption region of visible ray.
TiO
2the preparation method of-NTs mainly contains template, anonizing, induced growth method and hydrothermal method etc.The product that different methods is obtained, the difference of pattern and structure is very large, and the product as template synthesis is subject to the impact of template, and caliber is large, thickness of pipe, specific surface area are little, belongs to Detitanium-ore-type; Product prepared by anonizing belongs to amorphous type, and the features such as thickness of pipe can be controlled by adjusting process parameter.Adopt TiO prepared by anodizing technology
2nanotube is evenly distributed, and is arranged in array format in good order, TiO
2nanotube is directly connected with titanium substrate, in conjunction with very firm, and difficult drop-off.This material structure is orderly, not easily reunites, the experiment proved that it has very high quantum effect, under photoelectric action, show good photoelectric catalytically active.In this research, anonizing is adopted to prepare TiO
2-NTs [Zhang Qinglin, Wang Fuxiang, the sign of summer bright rosy clouds .Ag particle modification Nano tube array of titanium dioxide and photoelectric property thereof. material Leader, 2012,26 (4): 22-24.].
By photoelectric-synergetic effect, the photon energy of visible region and the energy of electronics are worked in coordination with, visible light energy is made full use of, efficiently play a role is promote that TiO2 photocatalysis is the problem paid special attention at present, Wang Yuanhao, Zhao Dan, Xu Baiqing etc. find that the dispersion state (dispersity or utilization ratio) of Pt has the decisive influence [electrochemical oxidation of formic acid on nano-gold loaded platinum (Pt^Au) eelctro-catalyst to the behavior of formic acid electro-oxidation reaction on PtAu eelctro-catalyst, catalysis journal, 2008, 29 (3), 297-302]. the PtAu catalyzer having high Pt dispersity (> 50 %) presents very high catalytic activity in low potential scope to formic acid electro-oxidation reaction, now mainly there is formic acid electrooxidation and directly generate CO
2reaction, but when Pt dispersity reduces, formic acid becomes more important via the electro-oxidation process of toxicity intermediate, containing in the solution of (10.0 ± 1.2) nm Au colloidal solid, introduce different amount K
2ptCl
6with Pt/ Au atomic ratio (m) in adjustment system, and with appropriate polyvinylpyrrolidone (PVP) for protective material, use hydrogen reducing K
2ptCl
6pt is deposited on Au particle and obtains PtAu particle. by the Pt form of Au particle bearing from shell to cluster or the catalyst series that changes of tow-dimensions atom raft, be designated as Pt Au (m is Pt/ Au atomic ratio). with " core-shell " sample Au Pt [Mandal S of the coated Au particle of Pt shell, Mandale A B, Sastry M.
j Mater Chem, 2004,
14(19): 2868, Jin YD, Shen Y, Dong Sh J.
j Phys Chem B, 2004,
108(24): 8142] compare, the sample that Pt exists with cluster or tow-dimensions atom raft on Au surface is described to surperficial plaque-like (Pt-flecks on Au colloids) Pt eelctro-catalyst [Zhao D, Xu B Q.
a ngew Chem, Int Ed, 2006,
45(30): 4955, Zhao D, Xu B Q.
phys Chem Chem Phys, 2006,
8(43): 5106], particularly when m≤0.05, Pt size can be not more than the cluster of 1.0 nm or atom raft form exists at Au particle surface, and its electrochemical surface area (EAS) can reach 236 m
2the dispersity (or utilization ratio) of/g Pt, Pt, close to 100 %, is conventional nano Pt catalyzer [Watanabe M, Saegusa S, Stonehart P.
j Elect roanal Chem, 1989,
271(122): 213, 12 Li L, Wu G, Xu B Q.
carbon, 2006,
44(14): 297313 Pozio A, Francesco M D, Cemmi A, Cardeuini F, GiorgiL.
j Power Sources, 2002,
105(1) more than twice: 13], along with the raising of Pt utilization ratio, the active proportional raising of mass ratio that PtAu catalyzer reacts methanol electro-oxidizing.Zhou Rong, Zhang Hongmei, Du Yu detains, poplar equality find electrodeposition Pt-Au bimetallic catalyst have the good electrooxidation activity to formic acid [chemical journal, 2011,69(13), 1533-1539], the interaction between Study of Support and metal such as Li Na finds Pt/TiO
2the interaction of obvious Metal-Support [Li Na, Chen Qiuyan, Luo Mengfei, Lu Ji, Pt/TiO is there is in catalyst system
2cO oxidation reaction kinetics research on catalyzer, Acta PhySico-Chimica Sinica, 2013,29(5), 1055-1062] and, Alexeev etc. find Pt/TiO
2compare Pt/Al
2o
3catalyzer has higher CO oxidation susceptibility [Alexeev, L. O. S.; Chin, S. Y.; Engelhard, M. H.; Ortiz-Soto, L.; Amiridis, M. D., J. Phys. Chem. B, 2005,109,23430. doi:10.1021/jp054888v], think because TiO2 can be provided in the active oxygen species that Metal-Support interface produces.Niu Fengjuan etc. find that the specific surface area of nanoporous Pd electrode (nano Pd) prepared by hydrothermal method is large, avtive spot is many, active far away higher than crystal Pd electrode to the catalytic oxidation of formic acid, nano Pd electrode deposits Au and obtains Au/nanoPd, find that the existence of a small amount of Au can improve Pd catalyzer active to the catalytic oxidation of formic acid, [Niu Fengjuan, easy fresh breeze, Liu Yunqing, China YouSe Acta Metallurgica Sinica, 2011,21 (8), 1974-1979].
Although now about with precious metals pd, Pt, Ru, Ag or Au to powder TiO
2the research of doping vario-property is existing a lot, but about two noble metal granule Pt and Au of use to high-sequential, self-assembly TiO
2the research report of nanotube doping does not also have.Originally platinum bimetal doped Ti O is researched and proposed
2the method of nanotube electrode, has good catalytic oxidation activity to methyl alcohol, ethanol, glycerol, has good degradation effect for catalyzing oxidation of organic compounds.
Summary of the invention
One is the object of the present invention is to provide to prepare platinum bimetal doped Ti O
2the method of nanotube electrode.The TiO of obtained platinum bimetal doping in this way
2nanotube electrode, platinum bimetal particle is little, is evenly distributed, and has good degradation effect for catalyzing oxidation of organic compounds.
The object of the invention is to be achieved through the following technical solutions:
Prepare the method for platinum bimetal doped Ti O2 nanotube electrode, described method comprises following preparation process:
(1) pre-treatment of Ti substrate: the small pieces pure titanium sheet being cut into 100 mm × 100 mm, the emery paper successively through 1000# is polished to can't see obvious cut, more successively at distilled water, in acetone, ultrasonic immersing cleans 10 minutes, then at 2.0mol/L H
3pO
4after supersound process about 10 minutes, by washed with de-ionized water, drying for standby in vacuum drying oven.
(2) preparation of TiO2 nanotube electrode: adopt range to be the current regulator power supply of 0-30V, high-purity titanium sheet that pre-treatment is good is working electrode (connecing positive pole), amassing equal-sized titanium sheet with working electrode surface is (for obtaining better oxidation effectiveness to electrode (connecing negative pole), positive and negative electrode selects area identical, material is identical, the titanium sheet that preprocessing process is identical).Electrolytic solution is the mixing solutions of 0.25mol/L Sodium Fluoride and 0.50mol/L phosphoric acid.By two interelectrode distance controlling at 1-6cm, anodic oxidation voltage scope is 10-25 V, and the polarization time is 60-360 min, and room temperature is carried out under magnetic stirring.Wash away the electrolytic solution of titanium sheet electrode surface after end with high purity water, naturally dry under room temperature.Titanium sheet electrode anodic oxidation obtained is placed in retort furnace, after calcining 3 hours at 450 DEG C, obtain the stable titanium dioxide nanotube array electrode of surface topography.
(3) preparation of platinum bimetal doped Ti O2 nanotube electrode: obtained TiO2 nanotube is immersed 100mLAu successively
3+(1.0mM)-K
2sO
4(0.2M) or 100mLPt(1.0M)-K
2sO
4(0.2M) in electrodeposit liquid, TiO
2nanometer pipe array electrode is working electrode, and deposition voltage is-0.2V, and the time is 400s, with after pure water cleaning after electroreduction terminates, electrode 200 DEG C of dry 2h in vacuum drying oven is obtained the Au/TiO of Au doping
2-NTs electrode;
Again by the Au/TiO of Au doping
2-NTs electrode immerses 100mLPt
4+(1.0mM)-K
2sO
4(0.2M) in electrodeposit liquid, Au/TiO
2nanometer pipe array electrode working electrode, deposition voltage is-0.2V, and the time is 400s, with after pure water cleaning after electroreduction terminates, by electrode 200 DEG C of dry 2h in vacuum drying oven, obtains the Pt-Au//TiO of Pt-Au/ doping
2-NTs electrode.
Advantage of the present invention and effect are:
The present invention for electrolytic solution, under the voltage of 10 ~ 25 V, adopts anonizing on Ti substrate, to prepare TiO2 nanotube, the TiO2 nanotube after 450 DEG C of thermal treatment with the mixing solutions of 0.25mol/L Sodium Fluoride and 0.50mol/L phosphoric acid.
Obtained TiO2 nanotube is immersed in Au successively
3+(1.0mM)-K
2sO
4(0.2M) and 100mLPt(1.0M)-K
2sO
4(0.2M) in electrodeposit liquid, TiO
2nanometer pipe array electrode is working electrode, constant deposition voltage, constant depositing time, the TiO2 nanotube electrode after obtained doping Pt-Au.The TiO2 nanotube electrode of obtained Pt-Au doping in this way, Pt and Au particle is little, is evenly distributed, and has good catalytic oxidation activity, have good degradation effect for catalyzing oxidation of organic compounds to methyl alcohol, ethanol, glycerol.
Accompanying drawing explanation
The SEM figure of Fig. 1 TiO2 nanotube electrode;
Fig. 2 is the SEM figure of the TiO2 nanotube electrode after doping Au;
Fig. 3 is the SEM figure of the TiO2 nanotube electrode after doping Pt-Au
The EIS figure of the TiO2 nanotube electrode after TiO2, Pt-Au after Fig. 4 Ti, TiO2, doping Au;
Fig. 5 is the electrooxidation figure to methyl alcohol of the TiO2 nanotube electrode after the TiO2 after doping Au, the TiO2 doping Pt-Au after doping Pt.
Note: Fig. 3-Fig. 5 of the present invention is analysis schematic diagram or the photo of product state, word or the unintelligible understanding do not affected technical solution of the present invention of image in figure.
Embodiment
Embodiment 1
Pure titanium sheet is cut into the small pieces of 100 mm × 100 mm, the emery paper successively through 1000# is polished to can't see obvious cut, more successively at distilled water, in acetone, ultrasonic immersing cleans 10 minutes, then at 2.0mol/L H
3pO
4after supersound process about 10 minutes, by washed with de-ionized water, drying for standby in vacuum drying oven.
Range is adopted to be the current regulator power supply of 0-30V, high-purity titanium sheet that pre-treatment is good is working electrode (connecing positive pole), amassing equal-sized titanium sheet with working electrode surface is (for obtaining better oxidation effectiveness to electrode (connecing negative pole), positive and negative electrode selects area identical, material is identical, the titanium sheet that preprocessing process is identical).Electrolytic solution is the mixing solutions of 0.25mol/L Sodium Fluoride and 0.50mol/L phosphoric acid.By two interelectrode distance controlling at 1-6cm, anodic oxidation voltage scope is 10-25 V, and the polarization time is 60-360 min, and room temperature is carried out under magnetic stirring.Wash away the electrolytic solution of titanium sheet electrode surface after end with high purity water, naturally dry under room temperature.Titanium sheet electrode anodic oxidation obtained is placed in retort furnace, after calcining 3 hours at 450 DEG C, obtain the stable titanium dioxide nanotube array electrode of surface topography, and the surface topography of obtained electrode is shown in accompanying drawing 1.
Obtained TiO2 nanotube is immersed 100mLAu successively
3+(1.0mM)-K
2sO
4(0.2M) or 100mLPt(1.0M)-K
2sO
4(0.2M) in electrodeposit liquid, TiO
2nanometer pipe array electrode is working electrode, and deposition voltage is-0.2V, and the time is 400s, with after pure water cleaning after electroreduction terminates, electrode 200 DEG C of dry 2h in vacuum drying oven is obtained the Au/TiO of Au doping
2-NTs electrode, the surface topography of obtained electrode is shown in accompanying drawing 2.
100mLPt
4+(1.0mM)-K
2sO
4(0.2M) in electrodeposit liquid, Au/TiO
2nanometer pipe array electrode working electrode, deposition voltage is-0.2V, and the time is 400s, with after pure water cleaning after electroreduction terminates, electrode 200 DEG C of dry 2h in vacuum drying oven is obtained the Pt-Au//TiO of Pt-Au/ doping
2-NTs electrode, the surface topography of obtained electrode is shown in accompanying drawing 3.
Because the Au first deposited can strengthen the electroconductibility of combined electrode, the deposition making Pt is easier, thus Au nano particle first galvanic deposit at TiO
2on nanotube, and then electrodeposition Pt nano particle.
The method of application alternating-current impedance also can characterize the electrical property change of electrode.At 1mM K
3fe (CN)
6/ 1mM K
4fe (CN)
6in solution, respectively to four kinds of electrodes, be respectively Ti electrode (a), TiO
2-NTs array electrode (b), Au/TiO
2electrode (c), Pt-Au/TiO
2electrode (d), carries out ac impedance measurement.Ti electrode is minimum at the capacitive reactance arc of high frequency region as seen from Figure 4, and capacitive reactance is 412.7ohm, proves that Ti electrode surface is smooth.Along with Ti surface conversion is TiO
2semi-conductor, the capacitive reactance arc of high frequency region increases, and capacitive reactance is 934.5ohm, TiO
2after nano-noble metal is introduced on surface, capacitive reactance progressively reduces, and after gold-supported, capacitive reactance is reduced to 805ohm, then after further Supported Pt Nanoparticles, capacitive reactance is reduced to 450.1ohm;
Adopt three-electrode system cyclic voltammetry Pt-Au doped Ti O2 nanotube electrode (a), Pt/TiO2 nanometer pipe array electrode (b), Au/TiO2 nanometer pipe array electrode (c) to the activity of the sodium hydroxide solution catalytic oxidation at 1.0mol/L of 1.0mol/L methyl alcohol.
Adopt the PhotoelectrocatalytiPerformance Performance of three-electrode system test Pt-Au doped Ti O2 nanotube electrode, with the K of 0.1 mol/L
2sO
4solution is ionogen, and xenon lamp source of parallel light is simulated solar light source, and CHI 660D type electrochemical workstation is power supply, in homemade quartz reactor, with the Pt-Au doped Ti O prepared
2nanotube electrode is working electrode, and platinum guaze is to electrode, and Ag/AgCl electrode is the three-electrode system rhodamine B degradation of reference electrode, and concentration is 20 mg/L, and applying bias is 1000 mV, and degradation time is 3 h.
Test result shows to adopt photoelectrocatalysioxidization oxidization rhodamine B successful, compared to unadulterated TiO
2nanotube electrode, the TiO of Pt-Au doping
2nanotube electrode degrade 60 minutes after degradation rate can reach 85 %, improve nearly 25 %.
Claims (3)
1.
a kind ofprepare the method for platinum bimetal doped Ti O2 nanotube electrode, it is characterized in that, comprise following preparation process:
(1) pre-treatment of Ti substrate: the small pieces pure titanium sheet being cut into 100 mm × 100 mm, the emery paper successively through 1000# is polished to can't see obvious cut, more successively at distilled water, in acetone, ultrasonic immersing cleans 10 minutes, then at 2.0mol/L H
3pO
4after supersound process about 10 minutes, by washed with de-ionized water, drying for standby in vacuum drying oven;
(2) preparation of TiO2 nanotube electrode: adopt range to be the current regulator power supply of 0-30V, high-purity titanium sheet that pre-treatment is good is working electrode (connecing positive pole), amassing equal-sized titanium sheet with working electrode surface is (for obtaining better oxidation effectiveness to electrode (connecing negative pole), positive and negative electrode selects area identical, material is identical, the titanium sheet that preprocessing process is identical);
electrolytic solution is the mixing solutions of 0.25mol/L Sodium Fluoride and 0.50mol/L phosphoric acid;
By two interelectrode distance controlling at 1-6cm, anodic oxidation voltage scope is 10-25 V, and the polarization time is 60-360 min, and room temperature is carried out under magnetic stirring;
wash away the electrolytic solution of titanium sheet electrode surface after end with high purity water, naturally dry under room temperature;
Titanium sheet electrode anodic oxidation obtained is placed in retort furnace, after calcining 3 hours at 450 DEG C, obtain the stable titanium dioxide nanotube array electrode of surface topography;
(3) preparation of platinum bimetal doped Ti O2 nanotube electrode: obtained TiO2 nanotube is immersed 100mLAu successively
3+(1.0mM)-K
2sO
4(0.2M) or 100mLPt(1.0M)-K
2sO
4(0.2M) in electrodeposit liquid, TiO
2nanometer pipe array electrode is working electrode, and deposition voltage is-0.2V, and the time is 400s, with after pure water cleaning after electroreduction terminates, electrode 200 DEG C of dry 2h in vacuum drying oven is obtained the Au/TiO of Au doping
2-NTs electrode; Again by the Au/TiO of Au doping
2-NTs electrode immerses 100mLPt
4+(1.0mM)-K
2sO
4(0.2M) in electrodeposit liquid, Au/TiO
2nanometer pipe array electrode working electrode, deposition voltage is-0.2V, and the time is 400s, with after pure water cleaning after electroreduction terminates, by electrode 200 DEG C of dry 2h in vacuum drying oven, obtains the Pt-Au//TiO of Pt-Au/ doping
2-NTs electrode.
2. according to the method preparing platinum bimetal doped Ti O2 nanotube electrode described in claim 1, it is characterized in that, obtained TiO2 nanotube is immersed in Au successively
3+(1.0mM)-K
2sO
4(0.2M) and 100mLPt(1.0M)-K
2sO
4(0.2M) in electrodeposit liquid, TiO
2nanometer pipe array electrode is working electrode, constant deposition voltage, constant depositing time, the TiO2 nanotube electrode after obtained doping Pt-Au; The TiO2 nanotube electrode of obtained Pt-Au doping in this way, Pt and Au particle is little, is evenly distributed, and has good catalytic oxidation activity, have good degradation effect for catalyzing oxidation of organic compounds to methyl alcohol, ethanol, glycerol.
3. according to the method preparing platinum bimetal doped Ti O2 nanotube electrode described in claim 1, it is characterized in that, have good degradation effect to catalyzing oxidation of organic compounds.
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| CN114431867A (en) * | 2020-11-02 | 2022-05-06 | 北京机械设备研究所 | Electroencephalogram acquisition device, electroencephalogram target identification method and device |
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| CN114512686A (en) * | 2022-03-11 | 2022-05-17 | 南京林业大学 | A kind of photoelectric catalytic material and its preparation method and application |
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