CN103861575A - Method for preparing doped-modified TiO2/graphene composite material - Google Patents
Method for preparing doped-modified TiO2/graphene composite material Download PDFInfo
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Abstract
The invention relates to a method for preparing a doped-modified TiO2/graphene composite material, belongs to the technical field of photocatalytic oxidation printing and dyeing wastewater treatment, and particularly relates to methods for preparing TiO2 composite photocatalysts which are loaded onto graphene and are doped with rare earth elements and transition metal ions. According to the method, the rare earth elements and the transition metal ions are doped into TiO2 firstly by a sol-gel method, and then, doped and modified TiO2 is loaded into a graphene oxide material through hydrothermal reaction, thus the doped-modified TiO2/reduced graphene composite material is obtained. The composite photocatalyst prepared by the method can play a role in catalytically degrading organic pollutants in the presence of ultraviolet light and can play a role in catalysis under the conditions of visible light and even infrared light, and the utilization ratio of sunlight is increased greatly.
Description
Technical field
The invention belongs to photochemical catalytic oxidation techniques of Dyeing Wastewater Treatment field, particularly a kind of being carried on Graphene, doped with the TiO of rare earth element, transition metal ions
2the preparation method of composite photocatalyst.
Background technology
Water is human lives and the requisite important natural resources of production, and along with developing rapidly of dyestuff, textile industry, kind and the quantity of dyestuff increase day by day, and destruction and the environmental pollution of dyeing waste water to natural, ecological is more and more serious.Statistics demonstration, the industrial wastewater of the annual discharge of dyeing just reaches 2,300,000,000 tons, accounts for 10.6% of national industrial wastewater discharge total amount, occupies the 3rd of national each industrial department total emission volumn.Dyeing waste water has the features such as colourity is dark, COD is high, and Acidity of Aikalinity is strong, is the difficult problem in wastewater treatment always.A small amount of dyeing waste water enters water body and will reduce water transparency, affects aquatile and growth of microorganism, is unfavorable for the self-purification of water, easily causes visual pollution.Therefore, dyeing waste water must, through processing, meet national emission request before entering water body.
Utilize TiO from Carey etc.
2suspension, since under UV-irradiation, degradation of polychlorinated biphenyl and cyanide succeed, photocatalytic degradation environmental contaminants become the method for treating water of broad research over nearly 30 years, and its research and development work is ascendant trend year by year, have every year the research report about photocatalysis research aspect in a large number.
TiO
2it is one of conductor photocatalysis material using at present, in actual use, have two outstanding problems: (1) needs ultraviolet light to activate, and the ultraviolet light part that is radiated ground only accounts for 5% left and right of sunshine, so the utilization ratio of sunshine is very low.(2) recombination probability in light induced electron and hole is high.Therefore, how to suppress right compound in light induced electron-hole, expand the wave-length coverage of exciting light, improve the study hotspot that its utilization rate to sunshine is current photocatalysis field.
Improve TiO
2the method of photocatalytic activity mainly contains: noble metal loading, surface sensitizing etc., noble metal loading is to TiO by noble metal loadings such as micro-Ag, Au, Pt, Pd, Ni
2its catalytic activity is improved on surface.Due to the price of noble metal costliness, limit the actual use of the method.Surface sensitizing is that some Photoactive compounds (as dyestuff, conjugated polymer) are adsorbed on to TiO with physics or chemical state
2surface, these optical active substances can have larger motivating factor under visible ray, can expand photocatalyst activity wave-length coverage.The method is mainly used in solar cell, also improper aspect photocatalysis to degrade organic matter pollutant, because these Photoactive compounds self also can be by photocatalytic degradation in photocatalytic process.
Summary of the invention
Technical problem to be solved by this invention is: the object of the invention is to improve TiO
2photocatalytic activity, based on this object, the invention provides a kind of TiO
2the preparation method of composite photocatalyst specifically, is using Graphene as catalyst carrier, at doped Ti O
2basis on, simultaneously to doped with rare-earth elements and transition metal ions in composite photocatalyst.
Preparation method is, first by sol-gel process, by rare earth element and doped transition metal ions to TiO
2in, then by hydro-thermal reaction, by doping vario-property TiO
2, load in graphene oxide material, obtain doping vario-property TiO
2/ reduced graphene composite.
Be specially:
(1) tetrabutyl titanate is added in absolute ethyl alcohol and constantly and stir, obtain the yellow solution of homogeneous transparent, then be added dropwise to a small amount of red fuming nitric acid (RFNA), regulating pH value is 2-3, drips rear continuation and stirs 0.5-2 hour, obtains the yellow solution of homogeneous transparent, is A liquid,
Butyl titanate: the volume ratio of absolute ethyl alcohol is 1: 4;
(2) by cerous nitrate, europium nitrate, being mixed with mixed solution, is B liquid,
Solvent is water or ethanol, and in solution, the total concentration of rare earth element ion (cerium ion and europium ion) is 0.1-0.5mol/L, and the mol ratio of cerium ion and europium ion is 1:1---3:1;
(3) the A liquid obtaining in above-mentioned 2 steps, B liquid are mixed, in mixed liquor, add transition metal salt, after stirring, obtain the colloidal sol of homogeneous transparent, ageing to colloidal sol loses flowability and obtains gel,
Transition metal salt is a kind of in Cr, Mn, Fe, Co, Ni, Cu slaine or wherein several mixing,
In this step, the mol ratio of controlling between titanium ion, rare earth element ion, transition metal ions is 100:2-5:2-3;
(4) gel obtaining in step (3) is dried, xerogel is pulverized last, be placed in Muffle furnace and heat, intensification, sintering, cooling with stove, obtain doping vario-property TiO
2,
Bake out temperature is 50-80 DEG C,
Heating rate was 5-10 DEG C/min, in 400-600 DEG C of sintering 1-2 hours;
(5) by the doping vario-property TiO obtaining in step (4)
2, be placed in the aqueous solution of graphene oxide, and add NaBH
4, stirring, ultrasonic being uniformly dispersed, hydro-thermal reaction is complete, naturally cools to room temperature, and reactant is filtered, cleans, is dried, and obtains doping vario-property TiO
2/ graphene composite material,
The concentration of graphene oxide dispersion liquid is 0.1g/L-10g/L,
Doping vario-property TiO
2, with the mass ratio of graphene oxide be 1-2.5:10,
NaBH
4with the mass ratio of graphene oxide be 0.5-1:4,
Hydrothermal temperature is 80-150 DEG C, and the reaction time is 2h-6h.
Beneficial effect of the present invention is: preparation method's technique of the present invention is simple, easy and simple to handle, produces without other impurity; The composite photocatalyst of preparing can well suppress right compound in light induced electron-hole, improves the speed of electrical conductivity to photocatalyst surface, significantly improves the photocatalytic activity of composite; Composite photocatalyst prepared by the present invention not only can play the effect of catalyze and degrade organic pollutants under action of ultraviolet light, and at visible ray, under even infrared condition, also can play catalytic action, and the utilization rate of sunshine is improved greatly.Technical scheme of the present invention, to solving the water resource of worsening shortages, realizes the strategy of sustainable development significant.
Brief description of the drawings
Fig. 1 is the doping vario-property TiO of preparation in embodiment 1
2the SEM of/graphene composite material schemes, and can find out clearly the TiO of doping vario-property from figure
2the evengranular Graphene surface that covers.
Detailed description of the invention
Embodiment 1
(1) tetrabutyl titanate is added in absolute ethyl alcohol and constantly and stir, obtain the yellow solution of homogeneous transparent, then be added dropwise to a small amount of red fuming nitric acid (RFNA), regulating pH value is 3, drips rear continuation and stirs 1 hour, obtains the yellow solution of homogeneous transparent, is A liquid,
Butyl titanate: the volume ratio of absolute ethyl alcohol is 1: 4;
(2) by cerous nitrate, europium nitrate, being mixed with mixed solution, is B liquid,
Solvent is water, and in solution, the total concentration of cerium ion and europium ion is 0.2mol/L, and the mol ratio of cerium ion and europium ion is 1:1;
(3) the A liquid obtaining in above-mentioned 2 steps, B liquid are mixed, in mixed liquor, add transition metal salt Cu (NO
3)
2, after stirring, obtaining the colloidal sol of homogeneous transparent, ageing to colloidal sol loses flowability and obtains gel,
In this step, the mol ratio of controlling between titanium elements, rare earth element (cerium and europium), copper is 100:3:3;
(4) gel obtaining in step (3) is dried, xerogel is pulverized last, be placed in Muffle furnace and heat, intensification, sintering, cooling with stove, obtain doping vario-property TiO
2,
Bake out temperature is 50 DEG C,
Heating rate was 8 DEG C/min, in 500 DEG C of sintering 1.5 hours;
(5) by the doping vario-property TiO obtaining in step (4)
2, be placed in the aqueous solution of graphene oxide, and add NaBH
4, stirring, ultrasonic being uniformly dispersed, hydro-thermal reaction is complete, naturally cools to room temperature, and reactant is filtered, cleans, is dried, and obtains doping vario-property TiO
2/ graphene composite material,
The concentration of graphene oxide dispersion liquid is 2g/L,
Doping vario-property TiO
2, with the mass ratio of graphene oxide be 2:10,
NaBH
4with the mass ratio of graphene oxide be 1:4,
Hydrothermal temperature is 100 DEG C, and the reaction time is 4h.
Photocatalysis performance is evaluated:
Get the doping vario-property TiO of preparation in 50mg embodiment 1
2/ graphene composite photocatalyst, join in the methylene blue solution that 80mL concentration is 50mg/L, solution is placed in to dark place and stirs 2h, after balance upon adsorption, UV light (power 15W, wavelength 365nm) irradiate, light source distance liquid level distance is 10cm, and illumination, after 2 hours, is got 5mL reaction suspension, after (10000r/min) centrifugation, get supernatant liquor at a high speed, under λ max, measure the absorbance of solution with 722s visible spectrophotometer.Be calculated as follows degradation rate:
In formula: η is degradation rate, C
0before light degradation, the concentration of methylene blue solution, C
tafter the illumination t moment, the concentration of methylene blue solution,
After light-catalyzed reaction 2 hours, this doping vario-property TiO
2/ graphene composite photocatalyst material is 90.5% to the degradation rate of methylene blue.
By " UV light " light source in above-mentioned " photocatalysis performance " test experience, change visible light source (power 15W, wavelength 580nm) into, all the other testing conditions are constant:
After light-catalyzed reaction 2 hours, this doping vario-property TiO
2/ graphene composite photocatalyst material is 88.2% to the degradation rate of methylene blue.
By " UV light " light source in above-mentioned " photocatalysis performance " test experience, change infrared light supply (power 15W, wavelength 1000nm) into again, all the other testing conditions are constant:
After light-catalyzed reaction 2 hours, this doping vario-property TiO
2/ graphene composite photocatalyst material is 86.9% to the degradation rate of methylene blue.
Comparative run: the doping vario-property TiO that gets preparation in 50mg embodiment 1
2/ graphene composite photocatalyst, join in the methylene blue solution that 80mL concentration is 50mg/L, solution is placed in to dark place and stirs 2h, after balance upon adsorption, in the dark place after 2 hours (unglazed photograph), get 5mL reaction suspension, after (10000r/min) centrifugation, get supernatant liquor at a high speed, under λ max, measure the absorbance of solution with 722s visible spectrophotometer
In the dark place after 2 hours this doping vario-property TiO
2/ graphene composite photocatalyst material is 9.5% to the degradation rate of methylene blue.
Embodiment 2
(1) tetrabutyl titanate is added in absolute ethyl alcohol and constantly and stir, obtain the yellow solution of homogeneous transparent, then be added dropwise to a small amount of red fuming nitric acid (RFNA), regulating pH value is 2, drips rear continuation and stirs 2 hours, obtains the yellow solution of homogeneous transparent, is A liquid,
Butyl titanate: the volume ratio of absolute ethyl alcohol is 1: 4;
(2) by cerous nitrate, europium nitrate, being mixed with mixed solution, is B liquid,
Solvent is ethanol, and in solution, the total concentration of rare earth element ion (cerium ion and europium ion) is 0.4mol/L, and the mol ratio of cerium ion and europium ion is 3:1;
(3) the A liquid obtaining in above-mentioned 2 steps, B liquid are mixed, in mixed liquor, add transition metal salt Mn (NO
3)
24H
2o, after stirring, obtains the colloidal sol of homogeneous transparent, and ageing to colloidal sol loses flowability and obtains gel,
In this step, the mol ratio of controlling between titanium ion, rare earth element ion, manganese ion is 100:2:2;
(4) gel obtaining in step (3) is dried, xerogel is pulverized last, be placed in Muffle furnace and heat, intensification, sintering, cooling with stove, obtain doping vario-property TiO
2,
Bake out temperature is 60 DEG C,
Heating rate was 5 DEG C/min, in 400 DEG C of sintering 2 hours;
(5) by the doping vario-property TiO obtaining in step (4)
2, be placed in the aqueous solution of graphene oxide, and add NaBH
4, stirring, ultrasonic being uniformly dispersed, hydro-thermal reaction is complete, naturally cools to room temperature, and reactant is filtered, cleans, is dried, and obtains doping vario-property TiO
2/ graphene composite material,
The concentration of graphene oxide dispersion liquid is 1g/L,
Doping vario-property TiO
2, with the mass ratio of graphene oxide be 2.5:10,
NaBH
4with the mass ratio of graphene oxide be 0.5:4,
Hydrothermal temperature is 120 DEG C, and the reaction time is 2.5h.
Photocatalysis performance is evaluated:
Get the doping vario-property TiO of preparation in 50mg embodiment 2
2/ graphene composite photocatalyst, joining 80mL concentration is in the rhodamine B solution of 50mg/L, solution is placed in to dark place and stirs 2h, after balance upon adsorption, UV light (power 15W, wavelength 365nm) irradiate, light source distance liquid level distance is 10cm, and illumination, after 2 hours, is got 5mL reaction suspension, after (10000r/min) centrifugation, get supernatant liquor at a high speed, under λ max, measure the absorbance of solution with 722s visible spectrophotometer.Be calculated as follows degradation rate:
In formula: η is degradation rate, C
0before light degradation, the concentration of rhodamine B solution, C
tafter the illumination t moment, the concentration of rhodamine B solution,
After light-catalyzed reaction 2 hours, this doping vario-property TiO
2/ graphene composite photocatalyst material is 91.7% to the degradation rate of rhodamine B.
By " UV light " light source in above-mentioned " photocatalysis performance " test experience, change visible light source (power 15W, wavelength 480nm) into, all the other testing conditions are constant:
After light-catalyzed reaction 2 hours, this doping vario-property TiO
2/ graphene composite photocatalyst material is 90.2% to the degradation rate of rhodamine B.
By " UV light " light source in above-mentioned " photocatalysis performance " test experience, change infrared light supply (power 15W, wavelength 900nm) into again, all the other testing conditions are constant:
After light-catalyzed reaction 2 hours, this doping vario-property TiO
2/ graphene composite photocatalyst material is 87.5% to the degradation rate of rhodamine B.
Comparative run: the doping vario-property TiO that gets preparation in 50mg embodiment 2
2/ graphene composite photocatalyst, joining 80mL concentration is in the rhodamine B solution of 50mg/L, solution is placed in to dark place and stirs 2h, after balance upon adsorption, in the dark place after 2 hours (unglazed photograph), get 5mL reaction suspension, after (10000r/min) centrifugation, get supernatant liquor at a high speed, under λ max, measure the absorbance of solution with 722s visible spectrophotometer
In the dark place after 2 hours this doping vario-property TiO
2/ graphene composite photocatalyst material is 7.1% to the degradation rate of rhodamine B.
Embodiment 3
(1) tetrabutyl titanate is added in absolute ethyl alcohol and constantly and stir, obtain the yellow solution of homogeneous transparent, then be added dropwise to a small amount of red fuming nitric acid (RFNA), regulating pH value is 3, drips rear continuation and stirs 1.5 hours, obtains the yellow solution of homogeneous transparent, is A liquid,
Butyl titanate: the volume ratio of absolute ethyl alcohol is 1: 4;
(2) by cerous nitrate, europium nitrate, being mixed with mixed solution, is B liquid,
Solvent is water, and in solution, the total concentration of rare earth element ion (cerium ion and europium ion) is 0.3mol/L, and the mol ratio of cerium ion and europium ion is 2:1;
(3) the A liquid obtaining in above-mentioned 2 steps, B liquid are mixed, in mixed liquor, add transition metal salt Co (NO
3)
26H
2o, after stirring, obtains the colloidal sol of homogeneous transparent, and ageing to colloidal sol loses flowability and obtains gel,
In this step, the mol ratio of controlling between titanium ion, rare earth element ion, cobalt ions is 100:5:3;
(4) gel obtaining in step (3) is dried, xerogel is pulverized last, be placed in Muffle furnace and heat, intensification, sintering, cooling with stove, obtain doping vario-property TiO
2,
Bake out temperature is 80 DEG C,
Heating rate was 10 DEG C/min, in 600 DEG C of sintering 1 hour;
(5) by the doping vario-property TiO obtaining in step (4)
2, be placed in the aqueous solution of graphene oxide, and add NaBH
4, stirring, ultrasonic being uniformly dispersed, hydro-thermal reaction is complete, naturally cools to room temperature, and reactant is filtered, cleans, is dried, and obtains doping vario-property TiO
2/ graphene composite material,
The concentration of graphene oxide dispersion liquid is 10g/L,
Doping vario-property TiO
2, with the mass ratio of graphene oxide be 1:10,
NaBH
4with the mass ratio of graphene oxide be 1:4,
Hydrothermal temperature is 80 DEG C, and the reaction time is 2h.
Photocatalysis performance is evaluated:
Get the doping vario-property TiO of preparation in embodiment 3
2/ graphene composite photocatalyst, join in dyeing waste water, dosage is " 100mg photochemical catalyst/L dyeing waste water ", stirs, after balance upon adsorption, UV light (power 15W, wavelength 365nm) irradiates, and light source distance liquid level distance is 10cm, after illumination 2 hours, measure the COD in waste water, the clearance of BOD and colourity reaches 98%, meets discharge standard;
By " UV light " light source in above-mentioned " photocatalysis performance " test experience, change visible light source (power 15W, wavelength 600nm) into, all the other testing conditions are constant:
After light-catalyzed reaction 2 hours, measure the COD in waste water, the clearance of BOD and colourity reaches 99%, meets discharge standard;
By " UV light " light source in above-mentioned " photocatalysis performance " test experience, change infrared light supply (power 15W, wavelength 850nm) into again, all the other testing conditions are constant:
After light-catalyzed reaction 2 hours, measure the COD in waste water, the clearance of BOD and colourity reaches 98.5%, meets discharge standard.
Comparative example: in above-mentioned " photocatalysis performance " test experience, all the other testing conditions are constant, is not used light source to irradiate (comprising visible ray, ultraviolet, infrared), after stirring, in the dark place after 2 hours, measure the COD in waste water, the clearance of BOD and colourity reaches 14.5%.
Claims (10)
1. a doping vario-property TiO
2the preparation method of/graphene composite material, is characterized in that: described preparation method is, first by sol-gel process, by rare earth element and doped transition metal ions to TiO
2in, obtain doping vario-property TiO
2; Again by hydro-thermal reaction, by doping vario-property TiO
2, load in graphene oxide material, obtain doping vario-property TiO
2/ reduced graphene composite.
2. doping vario-property TiO as claimed in claim 1
2the preparation method of/graphene composite material, is characterized in that: the concrete steps of described method are,
(1) tetrabutyl titanate is added in absolute ethyl alcohol and constantly and stir, obtain the yellow solution of homogeneous transparent, then be added dropwise to a small amount of red fuming nitric acid (RFNA), regulating pH value is 2-3, drips rear continuation and stirs 0.5-2 hour, obtains the yellow solution of homogeneous transparent, is A liquid;
(2) by cerous nitrate, europium nitrate, being mixed with mixed solution, is B liquid;
(3) the A liquid obtaining in above-mentioned 2 steps, B liquid are mixed, in mixed liquor, add transition metal salt, after stirring, obtain the colloidal sol of homogeneous transparent, ageing to colloidal sol loses flowability and obtains gel;
(4) gel obtaining in step (3) is dried, xerogel is pulverized last, be placed in Muffle furnace and heat, intensification, sintering, cooling with stove, obtain doping vario-property TiO
2;
(5) by the doping vario-property TiO obtaining in step (4)
2, be placed in the aqueous solution of graphene oxide, and add NaBH
4, stirring, ultrasonic being uniformly dispersed, hydro-thermal reaction is complete, naturally cools to room temperature, and reactant is filtered, cleans, is dried, and obtains doping vario-property TiO
2/ graphene composite material.
3. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in described step (1), the volume ratio of butyl titanate and absolute ethyl alcohol is 1: 4.
4. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (2), the mol ratio of cerium ion and europium ion is 1:1---3:1.
5. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (3), described transition metal salt is a kind of in Cr, Mn, Fe, Co, Ni, Cu slaine or several mixture wherein.
6. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (3), the mol ratio between titanium elements, rare earth element, transition metal is 100:2-5:2-3.
7. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (4), heating rate is 5-10 DEG C/min, in 400-600 DEG C of sintering 1-2 hours.
8. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (5), and doping vario-property TiO
2, with the mass ratio of graphene oxide be 1-2.5:10.
9. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (5), hydrothermal temperature is 80-150 DEG C, and the reaction time is 2h-6h.
10. doping vario-property TiO as claimed in claim 2
2the preparation method of/graphene composite material, is characterized in that: in step (5), and NaBH
4with the mass ratio of graphene oxide be 0.5-1:4.
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