CN108911056A - { 001 } preparation and application for the titanium dioxide photoelectrode that crystal face controllably exposes - Google Patents
{ 001 } preparation and application for the titanium dioxide photoelectrode that crystal face controllably exposes Download PDFInfo
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- CN108911056A CN108911056A CN201810245972.5A CN201810245972A CN108911056A CN 108911056 A CN108911056 A CN 108911056A CN 201810245972 A CN201810245972 A CN 201810245972A CN 108911056 A CN108911056 A CN 108911056A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010936 titanium Substances 0.000 claims abstract description 60
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 230000005693 optoelectronics Effects 0.000 claims abstract description 28
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 230000000593 degrading effect Effects 0.000 claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000005498 polishing Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000005286 illumination Methods 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- -1 phthalic acid diformazan Ester Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 6
- 230000005622 photoelectricity Effects 0.000 description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical group COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention relates to the preparations and application of the titanium dioxide photoelectrode that { 001 } crystal face controllably exposes, using titanium plate as titanium source, using hydrofluoric acid as end-capping reagent, by hydrothermal method in titanium substrate growth in situ TiO2Flower-like microsphere structure, the exposure of { 001 } crystal face is than being 0%~100%, { 001 } TiO being prepared2/ Ti optoelectronic pole can be applied in the degradation of repefral waste water photoelectrocatalysioxidization oxidization.Compared with prior art, { 001 } TiO that { 001 } crystal face prepared by the present invention controllably exposes2/ Ti optoelectronic pole has efficient PhotoelectrocatalytiPerformance Performance, and (density of photocurrent is up to 0.74mA/cm2), 94.3% can reach to the repefral removal rate that concentration is 5mg/L in 8 hours.This electrode material and technology are suitable for the photoelectric catalysis degrading field of phthalate pollutant.
Description
Technical field
The present invention relates to environmental pollution treatment technology and technical field of material chemistry, controllable more particularly, to a kind of { 001 } crystal face
Exposed { 001 } TiO2Application of/Ti the optoelectronic pole in efficiently catalyzing and oxidizing removal phthalic acid ester.
Background technique
Phthalate compound (Phthalates esters, PAEs) be it is a kind of generally use it is artificial synthesized
The Typical Endocrine Disrupting Chemicals for having serious harm to human health, as a kind of modified additive of plastics, to increase modeling
The plasticity and intensity of material, are industrially widely used as the plasticizer of synthetic rubber, paint solvent etc..And PAEs has indissoluble
The features such as Yu Shui, volatility are low, low temperature resistant is used as the production of pesticide, cosmetics, coating, lubricant etc., uses modeling in the mankind
Expect to enter human body by breathing, diet, skin contact, to the reproductive system, cardiovascular system, liver of human body in product process
Important influence is generated with endocrine system.PAEs with Van der Waals force and hydrogen bond in conjunction with plastic molecules, therefore as the mankind make
With plastic product, PAEs is easily transferred into environment, is widely present in atmosphere, soil, water body and organism, is become environment
In immanent pollutant.Especially in China, PAEs usage amount is big, and water environment pollution is serious, and the PAEs in many water bodys is tight
Weight is exceeded, and water safety and life and health, PAEs is threatened to have become current China one of major pollutants of greatest concern.Adjacent benzene
Dicarboxylic acid dimethyl ester (DMP) is a kind of typical phthalic acid ester, in China the Changjiang river, the Yellow River, Huangpu River, Song Hua River, Chaohu
Phthalic acid ester is monitored in equal water bodys and water factory's water outlet, in terms of investigation result, 5 kinds of predominantly DMP etc., and DMP, DBP
Screen priority pollutants blacklist is also classified as by China with DOP.Therefore the DMP in removal water body has important Significance for Environment.
Based on TiO2The photo-electrocatalytic technology of equal semiconductor catalysts has been found to effectively remove adjacent benzene two in water body
Formate ester pollutant.Photoelectricity oxidation reaction is, by applying electric field, light induced electron to be promoted to be transferred in optical electro-chemistry system
Cathode restrains the simple composite of electronics, hole, to improve the quantization efficiency of photochemical catalytic oxidation with this method.Due to
Photoelectrocatalysis reaction is an interfacial reaction in itself, and pollutant while being adsorbed in catalyst surface, occurs immediately by diffusion
Catalytic oxidation.Therefore catalyst surface characteristic, the cumulant in hole, catalyst surface adsorbed state all greatly
It is influenced by catalyst surface property, to greatly influence the path entirely reacted and rate.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of { 001 } crystal face is controllable
Exposed { 001 } TiO2Application of/Ti the optoelectronic pole in terms of efficient photoelectricity treater catalyzing oxidizing degrading organic pollutant.
The purpose of the present invention can be achieved through the following technical solutions：
{ 001 } preparation method for the titanium dioxide photoelectrode that crystal face controllably exposes is envelope with hydrofluoric acid using titanium plate as titanium source
Hold agent, by hydrothermal method in titanium substrate growth in situ TiO2Flower-like microsphere structure, TiO2Size is about at 500nm to 1 μm, shape
Shape is flower-like microsphere structure, and the exposure of { 001 } crystal face specifically uses following steps than being 0%~100%：
(1) by titanium plate chemical polishing in the polishing fluid that nitric acid, hydrofluoric acid and water are mixed to get, surface grease, miscellaneous is removed
Matter and metal oxide；
(2) by the bright and clean titanium plate after chemical polishing be put into the reaction solution that hydrofluoric acid and water are mixed to get carry out hydro-thermal it is anti-
It answers；
(3) it after sample takes out cleaning-drying, is calcined in air atmosphere.
The volume ratio of nitric acid, hydrofluoric acid and water described in step (1) is 2:1:6~4:1:6, as preferred embodiment party
Formula, the volume ratio of nitric acid, hydrofluoric acid and water preferably 3:1:6.
The volume ratio of hydrofluoric acid described in step (2) and water is 0.007:25~0.027:30, as preferred embodiment party
The volume ratio of formula, hydrofluoric acid and water preferably 0.027:30, hydrothermal temperature is 140 DEG C~180 DEG C, and the time is 0h~4h, is made
For preferred embodiment, hydrothermal temperature is 180 DEG C, time 4h.
The heating rate of calcining is 1~5 DEG C/min, and calcination temperature is 400 DEG C~550 DEG C, and calcination time is 2~5h.
{ 001 } application for the titanium dioxide photoelectrode that crystal face controllably exposes, with { 001 } TiO2/ Ti electrode is as anode, platinum
For piece as cathode, saturated calomel electrode is reference electrode, using three-electrode system, applies+0.2~+0.8V bias, in ultraviolet light
Illumination condition under, carry out photoelectrocatalysioxidization oxidization degradation concentration be 5~10mg/L repefral waste water, illumination item
Light intensity under part is 50~200W/cm2.Degradation time is 3~8h.
Compared with prior art, the present invention has the following advantages that：
(1) { 001 } TiO that { 001 } crystal face prepared by the present invention controllably exposes2/ Ti optoelectronic pole, the hydrogen in precursor solution
Fluoric acid is not only used as end-capping reagent, but also as etching agent.In 0h between 4h, hydrofluoric acid is the end-capping reagent of { 001 } crystal face, is inhibited
{ 001 } crystal face is grown.As the hydro-thermal time increases, { 001 } crystal face exposure ratio is gradually increased, in hydro-thermal time 4h, { 001 }
Crystal face exposure ratio reaches 100%, obtains most efficient PhotoelectrocatalytiPerformance Performance.It is further increased when the hydro-thermal time, hydrofluoric acid is then
Initially as etching agent, corrode { 001 } crystal face, the exposure ratio of { 001 } crystal face is gradually reduced, when the hydro-thermal time is 6h, cruelly
Dew ratio is 0.
(2) in titanium substrate growth in situ { 001 } TiO2It solves the powder photocatalyst in catalytic process to be not easy back
It receives, it is difficult to the problem of reusing, in addition, growth in situ improves TiO2The shortcomings that poorly conductive；
(3){001}TiO2Photoelectrocatalysioxidization oxidization system promotes catalyst light by being biased in three-electrode system
Efficient photoelectricity treater concerted catalysis oxidation is realized in the separation of raw electron-hole.
Detailed description of the invention
Fig. 1 is 4h- { 001 } TiO prepared in embodiment 12The scanning electron microscope (SEM) photograph of/Ti optoelectronic pole；
Fig. 2 is 2h- { 001 } TiO prepared in embodiment 22The scanning electron microscope (SEM) photograph of/Ti optoelectronic pole；
Fig. 3 is { 001 } TiO prepared by embodiment 1,22/ Ti optoelectronic pole is degraded during DMP, DMP concentration and initial concentration
Ratio and time plot；
Fig. 4 is { 001 } TiO prepared by embodiment 1,22/ Ti optoelectronic pole is degraded during DMP, and corresponding first order reaction is dynamic
Mechanical analysis figure.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of { 001 } TiO that { 001 } crystal face controllably exposes2The preparation method of/Ti optoelectronic pole, specifically includes following steps：
(1) titanium plate is subjected to chemical polishing in the polishing fluid that nitric acid, hydrofluoric acid and water mix, the proportion of polishing fluid is nitre
Acid：Hydrofluoric acid：Water volume ratio 3：1：6.
(2) hydrofluoric acid of 27uL (>=38wt%) is mixed with the deionized water of 30mL, stirs evenly, moves into 100mL's
In autoclave, it is put into step (1) by the titanium plate of chemical polishing processing, sealing, the hydro-thermal reaction in 180 DEG C of baking ovens
4h。
(3) after the reaction was completed to step (2), make reaction kettle cooling at room temperature, rinsed after taking-up with deionized water, it is natural
It dries.Under air atmosphere, heating rate is 3 DEG C/min, and calcination temperature is 450 DEG C, calcination time 3h.Obtain 4h-
{001}TiO2/ Ti optoelectronic pole.
The pattern of electrode is characterized using field emission scanning electron microscope technology (HitachiS-4800), sees figure
1, Fig. 1 shows TiO2Pattern is the class mirror-like microballoon of nano-scale, and TiO2It is evenly distributed in titanium substrate.It is prepared
4h- { 001 } TiO2{ 001 } the crystal face exposure ratio of/Ti optoelectronic pole can reach close to 100%.
Embodiment 2
A kind of { 001 } TiO that { 001 } crystal face controllably exposes2The preparation method of/Ti optoelectronic pole, specifically includes following steps：
(1) titanium plate is subjected to chemical polishing in the polishing fluid that nitric acid, hydrofluoric acid and water mix, the proportion of polishing fluid is nitre
Acid：Hydrofluoric acid：Water volume ratio 3：1：6.
(2) hydrofluoric acid of 27uL (>=38wt%) is mixed with the deionized water of 30mL, stirs evenly, moves into 100mL's
In autoclave, it is put into step (1) by the titanium plate of chemical polishing processing, sealing, the hydro-thermal reaction in 180 DEG C of baking ovens
2h。
(3) after the reaction was completed to step (2), make reaction kettle cooling at room temperature, rinsed after taking-up with deionized water, it is natural
It dries.Under air atmosphere, heating rate is 3 DEG C/min, and calcination temperature is 450 DEG C, calcination time 3h.Obtain 2h-
{001}TiO2/ Ti optoelectronic pole.
The pattern of electrode is characterized using field emission scanning electron microscope technology (HitachiS-4800), sees figure
2, Fig. 2 show TiO2Pattern is the flower-like microsphere of nano-scale, and TiO2It is evenly distributed in titanium substrate.The 2h- being prepared
{001}TiO2{ 001 } the crystal face exposure of/Ti optoelectronic pole is than being 30%.
Embodiment 3
Using 2h- { 001 } TiO prepared in case study on implementation 22/ Ti optoelectronic pole ({ 001 } crystal face exposure ratio 30%) efficiency light
Electrically-degradable DMP simulated wastewater, specific steps include as follows：
Photoelectrochemical degradation DMP experiment carries out in electrochemical reaction cell, and additional a set of cups with circulating water keeps reaction system
Constant temperature is at 25 DEG C.Using three electrode degrading systems, with { 001 } TiO2/ Ti electrode is working electrode, and platinized platinum is to electrode, work
Electrode with to the distance between electrode be 1cm, effective optoelectronic pole area be 3 × 5cm2.Use 0.1molL-1Sodium sulphate go from
Repefral is configured to the simulated wastewater that concentration is 5mg/L by sub- aqueous solution, and processing volume is 100mL.Ultraviolet xenon
Lamp (dominant wavelength 365nm) is light source, intensity of illumination 120mW/cm2,+0.4V is biased (relative to saturation calomel electricity
Pole), it is sampled every 1h, degrade 8h, carries out high performance liquid chromatography measurement to sample.High-efficient liquid phase analysis uses Agilent1260
High performance liquid chromatograph.Specific degradation results are as shown in Figures 3 and 4.In Fig. 3, b indicates 2h- { 001 } TiO2/ Ti optoelectronic pole
({ 001 } crystal face exposure ratio 30%) photoelectric catalysis degrading curve.
Test result shows 2h- { 001 } TiO2It is useless that/Ti optoelectronic pole is successfully realized dimethyl terephthalate simulation
The efficient photoelectricity treater catalyzing oxidizing degrading of water.DMP waste water is in { 001 } TiO2It is anti-that removal process on/Ti optoelectronic pole meets pseudo-first-order
Answer dynamics (see the b in Fig. 4).After 8h, 2h- { 001 } TiO2/ Ti optoelectronic pole photoelectric catalysis degrading removal rate reaches 68.7%.
Embodiment 4
Using 4h- { 001 } TiO prepared in case study on implementation 12/ Ti optoelectronic pole ({ 001 } crystal face exposes ratio close to 100%)
Efficient photoelectricity treater degradation DMP simulated wastewater, specific steps include as follows：
Photoelectrochemical degradation DMP experiment carries out in electrochemical reaction cell, and additional a set of cups with circulating water keeps reaction system
Constant temperature is at 25 DEG C.Using three electrode degrading systems, with { 001 } TiO2/ Ti electrode is working electrode, and platinized platinum is to electrode, work
Electrode with to the distance between electrode be 1cm, effective optoelectronic pole area be 3 × 5cm2.Use 0.1molL-1Sodium sulphate go from
Repefral is configured to the simulated wastewater that concentration is 5mg/L by sub- aqueous solution, and processing volume is 100mL.Ultraviolet xenon
Lamp (dominant wavelength 365nm) is light source, intensity of illumination 120mW/cm2,+0.6V is biased (relative to saturation calomel electricity
Pole), it is sampled every 1h, degrade 8h, carries out high performance liquid chromatography measurement to sample.High-efficient liquid phase analysis uses Agilent1260
High performance liquid chromatograph.Specific degradation results are as shown in Figures 3 and 4.In Fig. 3, a indicates 4h- { 001 } TiO2/ Ti optoelectronic pole
({ 001 } crystal face exposes ratio close to 100%) photoelectric catalysis degrading curve.
Test result shows 4h- { 001 } TiO2/ Ti optoelectronic pole is successfully realized repefral simulated wastewater
Efficient photoelectricity treater catalyzing oxidizing degrading.DMP waste water is in { 001 } TiO2Removal process on/Ti optoelectronic pole meets pseudo first order reaction
Dynamics (see a in Fig. 4).After 8h, 4h- { 001 } TiO2/ Ti optoelectronic pole photoelectric catalysis degrading removal rate reaches 94.3%.
Embodiment 5
{ 001 } preparation method for the titanium dioxide photoelectrode that crystal face controllably exposes is envelope with hydrofluoric acid using titanium plate as titanium source
Hold agent, by hydrothermal method in titanium substrate growth in situ TiO2Flower-like microsphere structure, TiO2Size is at 500nm to 1 μm, shape
For flower-like microsphere structure, following steps are specifically used：
(1) by titanium plate chemical polishing in the polishing fluid that nitric acid, hydrofluoric acid and water are mixed to get, nitric acid, hydrofluoric acid and water
Volume ratio be 2:1:6, removal surface grease, impurity and metal oxide；
(2) sample takes out be cleaned and dried after, calcined in air atmosphere, the heating rate of calcining is 1 DEG C/
Min, calcination temperature are 400 DEG C, calcination time 5h.
The titanium dioxide photoelectrode being prepared can be used for photoelectrocatalysioxidization oxidization degradable organic pollutant, with { 001 }
TiO2/ Ti electrode is as anode, and for platinized platinum as cathode, saturated calomel electrode is reference electrode, using three-electrode system, apply+
0.2~+0.8V bias carries out photoelectrocatalysioxidization oxidization degradation of dimethyl phthalate waste water under the illumination condition of ultraviolet light,
Light intensity under illumination condition is 50W/cm2, degradation time 8h.
Embodiment 6
{ 001 } preparation method for the titanium dioxide photoelectrode that crystal face controllably exposes is envelope with hydrofluoric acid using titanium plate as titanium source
Hold agent, by hydrothermal method in titanium substrate growth in situ TiO2Flower-like microsphere structure, TiO2Size is about at 500nm to 1 μm, shape
Shape is flower-like microsphere structure, and the exposure of { 001 } crystal face specifically uses following steps than being 20%：
(1) by titanium plate chemical polishing in the polishing fluid that nitric acid, hydrofluoric acid and water are mixed to get, nitric acid, hydrofluoric acid and water
Volume ratio be 4:1:6, removal surface grease, impurity and metal oxide；
(2) by the bright and clean titanium plate after chemical polishing be put into the reaction solution that hydrofluoric acid and water are mixed to get carry out hydro-thermal it is anti-
It answers, the volume ratio of hydrofluoric acid and water is 0.007:25, hydrothermal temperature control is at 140 DEG C, time 3h；
(3) sample takes out be cleaned and dried after, calcined in air atmosphere, the heating rate of calcining is 5 DEG C/
Min, calcination temperature are 550 DEG C, calcination time 2h.
The titanium dioxide photoelectrode being prepared can be used for photoelectrocatalysioxidization oxidization degradable organic pollutant, with { 001 }
TiO2/ Ti electrode is as anode, and for platinized platinum as cathode, saturated calomel electrode is reference electrode, using three-electrode system, apply+
0.2~+0.8V bias carries out photoelectrocatalysioxidization oxidization degradation of dimethyl phthalate waste water under the illumination condition of ultraviolet light,
Light intensity under illumination condition is 200W/cm2, degradation time 3h.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. { 001 } preparation method for the titanium dioxide photoelectrode that crystal face controllably exposes, which is characterized in that this method is using titanium plate as titanium
Source, using hydrofluoric acid as end-capping reagent, by hydrothermal method in titanium substrate growth in situ TiO2Flower-like microsphere structure, { 001 } are brilliant
Face exposure ratio can be controlled in 0%~100%.
2. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 1 controllably exposes, feature exist
In this method specifically uses following steps：
(1) by titanium plate chemical polishing in the polishing fluid that nitric acid, hydrofluoric acid and water are mixed to get；
(2) the clean titanium plate after chemical polishing is put into the reaction solution that hydrofluoric acid and water are mixed to get and carries out hydro-thermal reaction；
(3) it after sample takes out cleaning-drying, is calcined in air atmosphere.
3. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 2 controllably exposes, feature exist
In the volume ratio of nitric acid, hydrofluoric acid and water described in step (1) is 2:1:6~4:1:6.
4. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 2 controllably exposes, feature exist
In the volume ratio preferably 3 of nitric acid, hydrofluoric acid and water described in step (1):1:6.
5. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 2 controllably exposes, feature exist
In the volume ratio of hydrofluoric acid described in step (2) and water is 0.007:25~0.027:30.
6. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 2 controllably exposes, feature exist
In the volume ratio preferably 0.027 of hydrofluoric acid described in step (2) and water:30.
7. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 2 controllably exposes, feature exist
In hydrothermal temperature is 140 DEG C~180 DEG C, preferably 180 DEG C in step (2)；The hydro-thermal time is 0h~4h, preferably 4h.
8. the preparation method for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 2 controllably exposes, feature exist
The heating rate calcined in, step (3) is 1~5 DEG C/min, and calcination temperature is 400 DEG C~550 DEG C, calcination time is 2~
5h。
9. { 001 } application for the titanium dioxide photoelectrode that crystal face controllably exposes, which is characterized in that with { 001 } TiO2/ Ti optoelectronic pole
As working electrode, platinized platinum is used as to electrode, and saturated calomel electrode is reference electrode, in three-electrode system, using sodium sulphate
Deionized water solution is electrolyte, using ultraviolet light and is biased lower photoelectrocatalysioxidization oxidization degradation phthalic acid diformazan
Ester waste water.
10. the application for the titanium dioxide photoelectrode that { 001 } crystal face according to claim 9 controllably exposes, which is characterized in that
Ultraviolet light light intensity is 50~200mW/cm2, it is biased as+0.2~+0.8V, the illumination degrading time is 3~8h.
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