CN109569684A - Plasma modification metal oxide and the co-modified titanium dioxide nano-rod composite photo-catalyst of g- carbonitride and its preparation and application - Google Patents
Plasma modification metal oxide and the co-modified titanium dioxide nano-rod composite photo-catalyst of g- carbonitride and its preparation and application Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002073 nanorod Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract 5
- 230000004048 modification Effects 0.000 title description 13
- 238000012986 modification Methods 0.000 title description 13
- 230000004888 barrier function Effects 0.000 claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 54
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004408 titanium dioxide Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 8
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- 239000007788 liquid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
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- 238000001179 sorption measurement Methods 0.000 claims description 2
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- 239000003054 catalyst Substances 0.000 abstract description 18
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- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
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- 239000000243 solution Substances 0.000 description 45
- 208000028659 discharge Diseases 0.000 description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
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- 239000011651 chromium Substances 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical class [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229910052805 deuterium Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- -1 Ethyl alcohol Chemical compound 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
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- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F1/46—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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of metal oxide and the co-modified titanium dioxide nano-rod composite photo-catalyst of g- carbonitride and its preparations and application, and (1) is using dielectric barrier discharge plasma method respectively to metal oxide and g-C3N4It is modified；Or to metal oxide-g-C3N4Compound is modified；(2) to modified metal-oxide and modified g-C3N4Carry out distribution electro-deposition or to modified metal-oxide-g-C3N4One step electro-deposition of compound；(3) it dries and then is calcined after electro-deposition under nitrogen atmosphere to obtain the final product.Preparation method of the present invention is simply easily made, the catalyst practical application effect stability and high efficiency being prepared, being capable of Synergistic degradation phenol and heavy metal Cr VI mixed pollutants.
Description
Technical field
The present invention relates to one kind with dielectric barrier discharge plasma auxiliary law synthesis of metal oxide and g-C3N4It is co-modified
The preparation method of titanium dioxide nano-rod composite photoelectric catalyst, belongs to photoelectrocatalysimaterial material technical field.
Background technique
In recent years, photocatalysis technology has always been considered as being to solve energy problem and the most potential means of environmental pollution.It receives
Rice TiO2Photochemical catalyst is the one kind to attract most attention in catalysis material family, has efficient, chemical property stabilization, nontoxic nothing
The advantages that harmful, cheap has been always photochemical catalyst of greatest concern since 1972 are found.
For example, the Chinese invention of Publication No. CN105597723A discloses a kind of supported titanium2The preparation of photochemical catalyst
Method uses TiO2Adhere to inorganic active charcoal in colloidal sol, preparation is calcined by Muffle furnace and generates inorganic active carbon loaded type TiO2Light
Catalyst.The Chinese invention of Publication No. CN1105032479A discloses a kind of TiO2The preparation method of photochemical catalyst, being related to
Work technical field, preparation method of the invention are molten using acid catalysis using butyl titanate as predecessor using natural zeolite as carrier
Glue-gel method prepares natural zeolite supported titanium2Photochemical catalyst.
But nano-TiO2It still is apparent not enough in the use aspects of photocatalysis efficiency and visible light, TiO2Forbidden bandwidth be
3.2eV, the ultraviolet light that can only be less than 5% to accounting in sunlight is absorbed and is utilized, and cannot make full use of the sun
Visible light part in energy, in order to solve TiO2The disadvantage, researchers use semiconductors coupling, ion doping, noble metal
The multiple means such as deposition are modified.
g-C3N4, because it is with very high thermal stability and chemical stability and characteristic electron, become current photocatalysis
The new lover of area research.There are scholar's chemical vapour deposition technique and electrodeposition process by TiO2And g-C3N4It is combined with each other, obtains
Efficient photoelectrocatalysis property, but all there are many and diverse preparation method, severe reaction conditions or urge in these existing catalyst
The problem of agent performance is further improved.
Summary of the invention
The present invention provide a kind of metal oxide and the co-modified titanium dioxide nano-rod composite photo-catalyst of g- carbonitride and
Preparation method and application, preparation method are simply easily made, and the catalyst practical application effect stability and high efficiency being prepared can assist
With degradation of phenol and heavy metal Cr VI mixed pollutants.
A kind of metal oxide and g-C3N4The preparation method of co-modified titanium dioxide nano-rod composite photo-catalyst, it is special
Sign is, includes the following steps:
(1) using dielectric barrier discharge plasma method respectively to metal oxide and g-C3N4It is modified；Or using Jie
Matter barrier discharge plasma method is to metal oxide-g-C3N4Compound is modified；
(2) first conductive using the solution containing modified metal oxide as the FTO of electrodeposit liquid, carried titanium dioxide nanometer rods
It is that reference electrode progress electro-deposition obtains target that glass, which is working electrode, titanium sheet is to electrode, Ag/AgCl electrode, then again
To contain g-C3N4Solution be electrodeposit liquid, gained target is working electrode, titanium sheet be to electrode, Ag/AgCl electrode is ginseng
Electro-deposition is carried out than electrode；
Or to contain modified metal oxide-g-C3N4The solution of compound is electric depositing solution, carried titanium dioxide nanometer
It is that reference electrode carries out electro-deposition that the FTO electro-conductive glass of stick, which is working electrode, titanium sheet is to electrode, Ag/AgCl electrode；
(3) it dries and then is calcined after electro-deposition under nitrogen atmosphere to obtain the final product.
Dielectric barrier discharge, as representative cold plasma generator, " gas discharge " refer in atmospheric pressure and
Strong nonequilibrium plasma is generated at a temperature of medium gas, generates dielectric barrier between the electrode that two separate.It is situated between
Matter barrier discharge is suitable for pollutant removal, and the every field such as nano material synthesis and analysis application, this is attributable to its uniqueness
The advantages of, including mildly discharge, small in size, structure is simple, low in energy consumption.During discharge, it compared with traditional technology, provides
Higher energy density.So far, most of researchs are only limitted to the in-situ reducing precious metal ion on various host materials, with
Use H2Compound is generated in dielectric barrier discharge plasma as working gas.In the prior art, using in air
Electric discharge manufacture metal oxide composite is still rare and limited.
The modified graphitic nitralloy carbon of dielectric barrier discharge plasma can greatly improve g-C3N4Specific surface area, and lead to
The doping vario-property of O and N are crossed, g-C is improved3N4Photoelectric properties；The modified Ag of dielectric barrier discharge plasma2O nano material table
Reveal crystallinity, the angle of diffraction is slightly displaced from, and this material even if can also show excellent redox property at high temperature.
g-C3N4And Ag2The combination of O has good matching, can easily manufacture p-n heterojunction,
Compared with conventional composite materials, this will bring the more effective interfacial migration of light induced electron and hole.In addition, Ag2O
Nano particle is dispersed in g-C3N4Surface on, this can greatly reduce the use of Ag to improve photocatalytic activity.
The modified g-C of dielectric barrier discharge plasma3N4-Mn3O4Compound, which has, to be significantly affected, gained catalyst
Size becomes smaller, and specific surface area is bigger, the more active sites of exposure.Mn3O4Particle is in g-C3N4It is upper that there is preferably dispersibility, promote
Into contaminant degradation.The auxiliary synthesis of this dielectric barrier discharge plasma be it is solvent-free, can Rapid Implementation at room temperature,
Without additional oxidant/reducing agent.
The g-C3N4It is commercially available to prepare by the following method:
It weighs a certain amount of melamine to be put in crucible, be heat-treated in Muffle furnace, grind 1 hour obtain product g- later
C3N4.Wherein, heat treatment condition are as follows: in Muffle furnace, rise to 520 DEG C with the heating rate of 5 DEG C/min, keep the temperature 4h.
The FTO electro-conductive glass of carried titanium dioxide nanometer rods, which is that working electrode is commercially available, to be prepared by the following method:
(1) FTO electro-conductive glass successively use acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15min, after dry；
(2) it prepares hydrochloric acid solution and is placed in 50mL beaker, seal stirring 10min coated with preservative film, add butyl titanate
Stir 5min；
(3) the FTO electro-conductive glass of wash clean is tiltedly placed in autoclave autoclave body, glass is conductive up, and above-mentioned match is added
Solution processed tightens autoclave and is placed in baking oven, heats 4h at 170 DEG C, and titanium dioxide nano-rod is made.
Preferably, the metal oxide is Ag2O or Mn2+Oxide.
Ag2O is commercially available to be prepared by the following method:
It takes NaOH in distilled water and stirs 30 minutes.0.1M AgNO is added dropwise under stiring3, under dark condition,
Mixture is continuously stirred 30 minutes, product is collected by centrifugation and is washed with distilled water for several times, finally, by solid product at 60 DEG C
It is dried overnight, obtains Ag2O。
Mn2+Oxide is commercially available to be prepared by the following method:
By MnCl2·4H2O is add to deionized water.Ultrasonic treatment 30 minutes, is then protected at 80 DEG C in vacuum drying oven
It holds 2 hours, obtains Mn2+Oxide.
Preferably, the modified condition of dielectric barrier discharge plasma method in step (1) are as follows: 30~45V of voltage, time 10
~40min.Modification time is more preferably 10~30min, most preferably 20min.
In the present invention, using plasma processing is to change g-C3N4G-C can be improved in surface nature3N4Specific surface area,
Promote powder evenly dispersed, while improving its photocatalysis performance, significantly increases the performance of photocatalytic pollutant degradation.By medium
G-C after barrier discharge plasma reactor for treatment3N4Powder has very big mention to the photoelectric properties of titanium dioxide nano-rod
It rises, excessively prolonged plasma modification is easily destroyed g-C3N4The active point on surface and the surface topography of material, thus shadow
Its catalytic performance is rung, and the doping of dispersed catalyst and O, N active material is then not achieved in the modification of too low time, is also not achieved
The purpose of catalyst modification, therefore the modification time of catalyst controlled by optimum condition to be conducive to catalyst modification best.
Preferably, ethylene glycol solution of the solution containing modified metal oxide for metal oxide, the second in step (2)
The concentration of metal oxide is 0.2~0.8mg/mL in glycol solution；Containing g-C3N4Solution be g-C3N4Ethanol solution, should
G-C in ethanol solution3N4Concentration be 0.8~1.2mg/mL；Containing modified metal oxide-g-C3N4The solution of compound is
The ethylene glycol solution of compound, metal oxide-g-C in the ethylene glycol solution3N4The concentration of compound is 2~3mg/mL.
It is further preferred that the solution containing modified metal oxide is that the ethylene glycol of metal oxide is molten in step (2)
Liquid, the concentration of metal oxide is 0.4~0.6mg/mL in the ethylene glycol solution；Containing g-C3N4Solution be g-C3N4Ethyl alcohol
Solution, g-C in the ethanol solution3N4Concentration be 0.9~1.1mg/mL；Containing modified metal oxide-g-C3N4Compound
Solution is the ethylene glycol solution of compound, metal oxide-g-C in the ethylene glycol solution3N4The concentration of compound be 2.4~
2.6mg/mL。
Most preferably, the solution containing modified metal oxide is the ethylene glycol solution of metal oxide in step (2), should
The concentration of metal oxide is 0.5mg/mL in ethylene glycol solution；Containing g-C3N4Solution be g-C3N4Ethanol solution, the ethyl alcohol
G-C in solution3N4Concentration be 1mg/mL；Containing modified metal oxide-g-C3N4The solution of compound is the second two of compound
Alcoholic solution, metal oxide-g-C in the ethylene glycol solution3N4The concentration of compound is 2.5mg/mL.Ethyl alcohol is 50% ethyl alcohol.
Under above-mentioned optimum condition: in the plasma, by the collision and energy transfer production between oxygen molecule and high energy electron
Raw oxygen carrier, including O, O2 -, O3Deng high activity, to molecular oxygen with higher oxidability, by the Ag with absorption+/Mn2+Reaction, is formed in g-C3N4Modified Ag on surface2O/Mn3O4.It is only needed with the help of dielectric barrier discharge plasma
A few minutes, so that it may obtain composite material.The auxiliary synthesis of this dielectric barrier discharge plasma be it is solvent-free, can be in room
The lower Rapid Implementation of temperature, without additional oxidant/reducing agent.
Preferably, the metal oxide-g-C3N4Compound is prepared by the following method:
By g-C3N4Powder and metal oxide precursor are added in deionized water, after ultrasonic treatment to adsorption equilibrium, then
It is obtained by drying in vacuum drying oven.It is subsequently placed in plasma discharge reactor and carries out discharge treatment.Product spend from
Sub- water is rinsed well to remove unreacted oxide, is finally dried in an oven.
It can independent plasma modification Ag in step (1)2O、Mn3O4、g-C3N4, can also be to Ag2O/g-C3N4、Mn3O4/
g-C3N4Mixture carries out total modification；Independent Ag is obtained through step (1) is modified2O、Mn3O4、g-C3N4Or Ag2O/g-C3N4、
Mn3O4/g-C3N4Mixture.
Preferably, electrodeposition process condition all in step (2) are as follows: electro-deposition 10 under the conditions of -0.4~-0.8V~
20min。
Overtension will affect electrode material stability, be easy to cause electrode damage or electrode surface to fall off, brownout
It then can not effective depositing metal oxide and g-C3N4, for metal oxide and g-C3N4For effective deposition voltage.Meanwhile it is heavy
Product overlong time metal oxide easy to form and g-C3N4Deposition is excessive, and electrode surface deposition is uneven, be easy to cause fall off with
And became uneven, influence the service life of electrode, and sedimentation time is too short then can not form the gold of even compact in electrode surface
Belong to oxide and g-C3N4Film, the same preparation for influencing electrode.In above-mentioned preferred scope, the electrode quality being prepared is more
It is good.
Further preferably are as follows: electro-deposition 15min under the conditions of -0.4~-0.8V；Most preferably: electro-deposition under the conditions of -0.6V
15min。
Preferably, in step (3) calcination condition be 350~450 DEG C calcining at constant temperature 1~1.5 hour.
The present invention also provides a kind of metal oxides and g-C being prepared such as the preparation method3N4Co-modified titanium dioxide
Titanium nanometer rods composite photo-catalyst.
The present invention also provides a kind of electrochemical process for treating of organic polluting water, include the following steps:
With the metal oxide and g-C3N4Co-modified titanium dioxide nano-rod composite photo-catalyst is anode, titanium sheet is
Cathode is biased 2~4V, electrolysis processing 1.5~2.5h of organic polluting water.
Preferably, electrolyte solution is 0.1M Na2SO4, selected pollutant is phenol and chromium (VI).
Compared with prior art, the present invention uses dielectric barrier discharge plasma auxiliary law synthesis of metal oxide and g-
C3N4The method of co-modified titanium dioxide nano-rod composite photoelectric catalyst, bring have the technical effect that
(1) the raw materials used in the present invention is cheap, and preparation method is simple, at low cost, high-efficient, without any pollution in preparation process
Object generates, and is conducive to further realize large-scale production；
(2) nanocomposite reactivity site made from method of the invention is more, since light-catalyzed reaction is main
Occur on the surface of photochemical catalyst, therefore relatively bigger specific surface area has more reactivity site for photochemical catalyst
Catalytic performance have apparent facilitation, to promote the degradation rate of pollutant.
Detailed description of the invention
Fig. 1 is prepared in embodiment 1 with dielectric barrier discharge plasma auxiliary law synthesis g-C3N4With titanium dioxide
The photoelectricity flow graph of titanium nanometer rods composite photocatalyst electrode；
Fig. 2 is prepared in embodiment 1 with dielectric barrier discharge plasma auxiliary law synthesis g-C3N4With titanium dioxide
The scanning electron microscope (SEM) photograph of titanium nanometer rods composite photocatalyst electrode；
Fig. 3 is to synthesize g-C in embodiment 2 with dielectric barrier discharge plasma auxiliary law3N4It is multiple with titanium dioxide nano-rod
The degradation efficiency figure of light combination catalysis electrode degradation of phenol and Cr VI in plasma reactor；
Fig. 4 is to synthesize g-C in embodiment 3 with dielectric barrier discharge plasma auxiliary law3N4It is multiple with titanium dioxide nano-rod
Light combination catalysis electrode degradation of phenol and Cr VI are using deuterium lamp as the degradation efficiency figure of light source；
Fig. 5 is to synthesize Ag in embodiment 4 with dielectric barrier discharge plasma auxiliary law2O and g-C3N4Co-modified titanium dioxide
The photoelectricity flow graph of titanium nanometer rods composite photocatalyst electrode；
Fig. 6 is to synthesize Ag in embodiment 4 with dielectric barrier discharge plasma auxiliary law2O and g-C3N4Co-modified titanium dioxide
Titanium nanometer rods composite photocatalyst electrode degrading phenol and Cr VI are using deuterium lamp as the degradation efficiency figure of light source.
Fig. 7 is prepared in embodiment 6 with dielectric barrier discharge plasma auxiliary law synthesis Mn3O4And g-C3N4
The photoelectricity flow graph of co-modified titanium dioxide nano-rod composite photocatalyst electrode.
Specific embodiment
Embodiment 1
(1) by dielectric barrier discharge plasma method to g-C3N4Powder is modified
Take appropriate g-C3N4Powder uses air as working gas in dielectric barrier discharge plasma reactor,
Start plasma reaction under 30V voltage, the reaction time is 0~40min, more preferably 10~30min, most preferably 20min.
(2)g-C3N4The preparation of modified titanic oxide nanorod electrodes
It is added what 0.1g was modified by dielectric barrier discharge plasma reactor in the ethanol solution of 100mL 50%
g-C3N4Powder, ultrasound 12 hours, is centrifugated, takes supernatant, later as electrodeposit liquid after being stirred continuously.With electrochemistry work
Make station and electro-deposition is carried out using three-electrode system, using the titanium dioxide nano-rod of hydro-thermal method preparation as working electrode, titanium sheet is pair
Electrode, Ag/AgCl electrode is reference electrode, electro-deposition 15 minutes under the conditions of electro-deposition voltage is -0.6V.Room temperature dry after
Under nitrogen atmosphere, g-C is made after calcining 1 hour with 400 DEG C of thermostatic3N4Modified titanic oxide nanorod electrodes.
LSV characterization is carried out to electrode using CHI660E electrochemical workstation, can be seen that from LSV photoelectricity flow graph (such as Fig. 1)
G-C after dielectric barrier discharge plasma reactor for treatment3N4Powder has the photoelectric properties of titanium dioxide nano-rod
Very big promotion, and in g-C3N4After powder modification 20min, density of photocurrent improves nearly three times.
Surface topography table is carried out to combination electrode prepared by embodiment 1 using field emission scanning electron microscope (such as Fig. 2)
It levies, it can be seen that g-C in figure3N4Succeed and is evenly distributed on titanium dioxide nano-rod.
Embodiment 2
80 μm of ol/L (100mL) hexavalent chromium solutions, 10mg/L are handled using combination electrode prepared by embodiment (1)
(100mL) phenol solution, with 0.1M Na2SO4For electrolyte solution, dropped in dielectric barrier discharge plasma reactor
Solution, voltage 30V, 10min take a sample, react one hour.Experimental result is as shown in Figure 3, it is seen that after 10min, Cr VI is complete
Full removal.
Embodiment 3
80 μm of ol/L (100mL) hexavalent chromium solutions, 10mg/L are handled using combination electrode prepared by embodiment (1)
(100mL) phenol solution, with 0.1M Na2SO4For electrolyte solution, applying bias 3V is secretly adsorbed before opening light power
30min reaches adsorption/desorption balance.
Half an hour takes a sample, reacts two hours.Experimental result is as shown in Figure 4, it is seen that after 2h, hexavalent chromium removal rate is about
It is 70%.
Embodiment 4
(1)Ag2O-5/TiO2The preparation of-NRs
0.05g is taken to pass through the Ag of plasma modification 5min2O powder is dissolved in 100mL ethylene glycol, ultrasonic disperse 30min.With
The solution is electric depositing solution, and using the titanium dioxide nano-rod of hydro-thermal method preparation as working electrode, titanium sheet is to electrode, Ag/
AgCl electrode is reference electrode, electro-deposition 30min under the conditions of electro-deposition voltage is -0.6V.Deposition process is spent after completing
Ionized water rinses, and dries, and obtains Ag2O/TiO2-NRs；
(2)Ag2O-5/g-C3N4-5/TiO2The preparation of-NRs
Electro-deposition is carried out using three-electrode system with electrochemical workstation, it is molten as electro-deposition using acquired solution in embodiment 1
Liquid, with Ag2O-5/TiO2- NRs is working electrode, and titanium sheet is to electrode, and Ag/AgCl electrode is reference electrode, in electro-deposition voltage
For electro-deposition 15 minutes under the conditions of -0.6V.Room temperature dry after under nitrogen atmosphere, calcined 1 hour with 400 DEG C of thermostatic,
Obtain Ag2O-5/g-C3N4-5/TiO2-NRs。
LSV characterization is carried out to electrode using CHI660E electrochemical workstation, can be seen that from LSV photoelectricity flow graph (such as Fig. 5)
Ag after dielectric barrier discharge plasma reactor for treatment 5min2O-5/g-C3N4- 5 powder References are not modified g-C3N4Powder
The photoelectric properties of foot couple titanium dioxide nano-rod have very big promotion.
Embodiment 5
160 μm of ol/L (100mL) hexavalent chromium solutions, 10mg/L are handled using combination electrode prepared by embodiment (4)
(100mL) phenol solution, with 0.1M Na2SO4For electrolyte solution, applying bias 3V is secretly adsorbed before opening light power
30min reaches adsorption/desorption balance.Half an hour takes a sample, reacts two hours.Experimental result is as shown in fig. 6, after 2h, benzene
Phenol removal rate is about 70%.
Embodiment 6
Mn3O4/g-C3N4The preparation of composite material: taking 2mL deionized water, be separately added into 0.2g, 0.4g, 0.6g, 1.0g,
The g-C of 1.5g3N4Powder.Then by Mn2+It is added to dissolved with original g-C3N4In the 2mL deionized water of powder.In vacuum after ultrasound
It is kept for 2 hours at 80 DEG C in baking oven.It is subsequently placed in plasma discharge reactor, 45V, 10min.Product (is expressed as
Mn3O4/g-C3N4- X, X indicate g-C3N4Additional amount) it is rinsed well with deionized water to remove unreacted Mn2+, finally at 80 DEG C
Baking oven in dry.
2.5mg/mL Mn is taken respectively3O4/g-C3N4- X ethylene glycol solution, ultrasonic disperse 30min.To prepare with
TiO2The FTO electrode of nanometer rods is immersed in 30min in the good solution of ultrasound, conductive face-up.Finally in N2In atmosphere pipe type furnace
400 DEG C, constant temperature 1 hour are risen to the heating rate of 5 DEG C/min.
Fig. 7 is difference Mn after dielectric barrier discharge plasma reactor for treatment3O4/g-C3N4- X powder dosage is to two
The photoelectric properties LSV photoelectricity flow graph of TiOx nano stick.It can be seen that initial g-C3N4Additional amount to prepared electrode
Photoelectric properties have a significant effect, Mn3O4/g-C3N4- 0.4 density of photocurrent is Mn3O4/g-C3N4Nearly five times of -1.5.
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (10)
1. a kind of metal oxide and g-C3N4The preparation method of co-modified titanium dioxide nano-rod composite photo-catalyst, feature
It is, includes the following steps:
(1) using dielectric barrier discharge plasma method respectively to metal oxide and g-C3N4It is modified；Or it is hindered using medium
Discharge plasma method is kept off to metal oxide-g-C3N4Compound is modified；
(2) first using the solution containing modified metal oxide as electrodeposit liquid, the FTO electro-conductive glass of carried titanium dioxide nanometer rods
For working electrode, titanium sheet, to be to electrode, Ag/AgCl electrode be that reference electrode carries out electro-deposition obtains target, then again to contain
g-C3N4Solution be electrodeposit liquid, gained target is working electrode, titanium sheet is to electrode, Ag/AgCl electrode be reference electricity
Pole carries out electro-deposition；
Or to contain modified metal oxide-g-C3N4The solution of compound is electric depositing solution, carried titanium dioxide nanometer rods
It is that reference electrode carries out electro-deposition that FTO electro-conductive glass, which is working electrode, titanium sheet is to electrode, Ag/AgCl electrode；
(3) it dries and then is calcined after electro-deposition under nitrogen atmosphere to obtain the final product.
2. preparation method according to claim 1, which is characterized in that the metal oxide is Ag2O or Mn2+Oxide.
3. preparation method according to claim 1, which is characterized in that dielectric barrier discharge plasma method changes in step (1)
The condition of property are as follows: 30~45V of voltage, 10~40min of time.
4. preparation method according to claim 1, which is characterized in that the solution containing modified metal oxide in step (2)
For the ethylene glycol solution of metal oxide, the concentration of metal oxide is 0.2~0.8mg/mL in the ethylene glycol solution；Containing g-
C3N4Solution be g-C3N4Ethanol solution, g-C in the ethanol solution3N4Concentration be 0.8~1.2mg/mL；Containing modified gold
Belong to oxide-g-C3N4The solution of compound is the ethylene glycol solution of compound, metal oxide-g- in the ethylene glycol solution
C3N4The concentration of compound is 2~3mg/mL.
5. preparation method according to claim 1, which is characterized in that the metal oxide-g-C3N4Compound is by such as lower section
Method preparation:
By g-C3N4Powder and metal oxide precursor are added in deionized water, after ultrasonic treatment to adsorption equilibrium, then true
It is obtained by drying in empty baking oven.
6. preparation method according to claim 1, which is characterized in that all electrodeposition process conditions in step (2) are as follows:-
10~20min of electro-deposition under the conditions of 0.4~-0.8V.
7. preparation method according to claim 1, which is characterized in that calcination condition in step (3): for 350~450 DEG C of constant temperature
Calcining 1~1.5 hour.
8. a kind of metal oxide and g-C that the preparation method as described in any one of claim 1~7 claim is prepared3N4
Co-modified titanium dioxide nano-rod composite photo-catalyst.
9. a kind of electrochemical process for treating of organic polluting water, which comprises the steps of:
With metal oxide described in claim 8 and g-C3N4Co-modified titanium dioxide nano-rod composite photo-catalyst is anode, titanium
Piece is cathode, is biased 2~4V, electrolysis processing 1.5~2.5h of organic polluting water.
10. electrochemical process for treating according to claim 9, which is characterized in that pollutant is in the organic polluting water
Phenol and Cr VI.
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