CN103285845A - Preparation method of graphene oxide wrapped titania microsphere photocatalyst - Google Patents
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Abstract
The invention discloses a preparation method of a graphene oxide wrapped titania microsphere photocatalyst. By utilizing organic groups enriched on the surfaces of a titania microsphere and graphene, the prepared monodisperse titania microsphere interacts with a graphene oxide solution according to the esterification condensation reaction bonding principle under a definite condition, so that the graphene wrapped titania microsphere photocatalyst is prepared. According to the method, the graphene oxide and the titania are stably combined together. The method has the advantages of short experimental period, convenience for operation, rapid synthesizing speed, high efficiency and low in energy consumption. Therefore, the method can be applied to the industrial production.
Description
Technical field
The invention belongs to the Composite Preparation technical field, relate to a kind of graphene oxide parcel titanium dioxide microballoon sphere preparation methods, be specifically related to a kind of preparation method of graphene oxide parcel titanic oxide microsphere photocatalyst.
Background technology
Nanoscale TiO
2Cause many concerns in recent years, be widely used in fields such as catalysis material, solar cell, gas sensor and optoelectronics device.With regard to photocatalysis research, TiO
2Photo-catalysis capability depend on its crystal formation, grain size and crystallization degree, comparatively speaking, the nano-TiO of the anatase phase that degree of crystallinity is higher, crystal grain is less
2Show better photocatalysis performance.And electronics-hole-recombination, photon scattering etc. all can have influence on TiO
2Final photon utilization ratio.
Graphene has good thermal conductivity [3000W/ (mK)], very high intensity (110GPa) and the specific area (2630mz/g) of super large.These excellent performances make Graphene have a extensive future in nano electron device, gas sensor, energy storage and prepare composite.
New carbon and TiO
2Be compounded to form composite, brought into play both synergies, strengthened the photocatalysis performance of material to organic matter, pollutant, its reason have following some: the bigger specific area of (1) composite has improved material to the organic pollutant adsorption ability; (2) material with carbon element-TiO
2The formation of interface hetero-junctions has improved compound between light induced electron and hole; (3) than pure TiO
2, the fermi level of composite may be to the direction skew of corrigendum, and then has improved the utilization rate of long wavelength photons more; (4) after carbon material surface absorbs photon, electronics is injected into TiO
2Conduction band forms reaction exciton (the superoxide radical O in order to degradable organic pollutant
2-With hydroxyl radical free radical HO).Existing microballoon catalysis material has many shortcomings, for example Chang Gui TiO
2Has wideer Bands crack (Detitanium-ore-type TiO
2Energy gap be 3.2eV), the light induced electron hole is compound to being easy to, and less specific area and lower dyestuff adsorption capacity is only arranged, these have seriously limited greatly developing of microballoon photocatalysis industry.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of graphene oxide parcel titanic oxide microsphere photocatalyst has solved that existing microballoon catalysis material Bands crack is wideer to cause using limited problem.
The technical solution adopted in the present invention is, a kind of preparation method of graphene oxide parcel titanic oxide microsphere photocatalyst specifically implements according to following steps:
Step 1: the adding mass concentration is 98% the concentrated sulfuric acid in the beaker of drying, is cooled to 0 ℃, adds natural flake graphite, sodium nitrate, potassium permanganate in the stirring successively; The control reaction temperature is 10～30 ℃, stir 3h, the beaker that will fill mixed solution then places 35 ℃ of waters bath with thermostatic control, the question response temperature rises to 35 ℃ and continues to stir 30min, control reaction temperature at last at 0-100 ℃, drip deionized water, continue to stir 30min, add the mixed solution that 30% hydrogen peroxide and deionized water are formed at last, centrifugal washing obtains yellowish-brown mud shape thing;
Step 2: the mud shape thing drying with step 1 obtains, be dispersed in the deionized water, ultrasonic 1～3h obtains the bronzing supernatant centrifugal twice;
Step 3: be that the KCl solution of 0.5mmol/L joins in the absolute ethyl alcohol with concentration, magnetic agitation 30min slowly splashes into tetrabutyl titanate, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains white powder;
Step 4: the white powder that the supernatant that step 2 is obtained and step 3 obtain mixes, at room temperature condition, and magnetic agitation 24h, centrifugal and wash 4 times, obtain the canescence powder;
Step 5: the canescence powder that step 4 is obtained places Muffle furnace, and under the condition of vacuum, the control heating rate is 1 ℃/min, and insulation 2h obtains graphene oxide parcel titanic oxide microsphere photocatalyst.
Characteristics of the present invention also are,
Quality-the volumetric concentration of natural flake graphite, sodium nitrate, potassium permanganate is respectively in the step 1 wherein: 43.48g/L, 43.48g/L, 130.43g/L.
The volume ratio of hydrogen peroxide and deionized water is 1:1～10 in the step 1 wherein.
The rate of addition of deionized water is 0.3～0.5mL/ second in the step 1 wherein.
The volume ratio of mud shape thing and deionized water is 1:1000～125 in the step 2 wherein.
The volume ratio of KCl solution and absolute ethyl alcohol is 1:300～200 in the step 3 wherein, and the volume ratio of KCl solution and tetrabutyl titanate is 1:5～2.
The ratio of supernatant and white powder is 200:1～1000:1mL/g in the step 4 wherein.
The invention has the beneficial effects as follows: the present invention adopts simple and practical method, with graphene oxide and stable the combining of titanium dioxide.Experimental period is short, is convenient to operation, has that aggregate velocity is fast, efficient is high and advantage of low energy consumption, has industrial production foreground.
Utilize the huge specific area of Graphene can improve the dyestuff adsorption capacity of composite photo-catalyst greatly, the conductivity of two-dimensional structure excellence can greatly improve transmission, the transfer in light induced electron and hole, improve separative efficiency, and the energy gap that the impurity energy level effect that produces of Graphene can be cut down composite is greatly laid a solid foundation for excellent photocatalysis performance in composite photo-catalyst.In addition, the mechanical property of the excellence that Graphene has can be kept the special structure of composite, and this provides material base for the realization of composite catalyzing to a certain extent.
Description of drawings
Fig. 1 is a series of stereoscan photographs of the graphene oxide parcel titanic oxide microsphere photocatalyst that makes of the embodiment of the invention 1, wherein, a is that graphite oxide amplifies 18000 times stereoscan photograph, and b is that titanium dioxide microballoon sphere amplifies 120000 stereoscan photograph; C is the transmission electron microscope photo of graphene oxide parcel titanium dioxide microballoon sphere, and corresponding scale is 100nm; D is the transmission electron microscope photo of graphene oxide parcel titanium dioxide microballoon sphere, and corresponding scale is 5nm;
Fig. 2 is the infrared spectrum that the embodiment of the invention 2 is finished a series of products in the graphene oxide parcel titanium dioxide process, wherein curve a is the infrared spectrum curve of graphene oxide, curve b is the infrared spectrum curve of pure titinium dioxide, and curve c is the infrared spectrum curve of graphene oxide parcel titanium dioxide microballoon sphere;
Fig. 3 is the photocatalysis figure that the embodiment of the invention 3 makes graphene oxide parcel titanium dioxide microballoon sphere material, and wherein, a is gained under the UV-irradiation condition; B is gained under the radiation of visible light condition.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Graphene oxide parcel titanic oxide microsphere photocatalyst of the present invention, the pattern homogeneous, the parcel thickness of graphene oxide can conveniently be controlled, can not come off, single good dispersion, diameter of micro ball is about 500nm, and the size of graphene oxide lamella can be controlled by ultrasonic time, and the parcel number of plies can be by time and concentration adjustment.
The present invention prepares the method for graphene oxide parcel titanic oxide microsphere photocatalyst, specifically carries out according to following steps:
Step 1: the adding mass concentration is 98% the concentrated sulfuric acid in the beaker of drying, is cooled to about 0 ℃, adds natural flake graphite, sodium nitrate, potassium permanganate in the stirring successively.Wherein quality-the volumetric concentration of natural flake graphite, sodium nitrate, potassium permanganate is respectively: 43.48g/L, 43.48g/L and 130.43g/L.
The control reaction temperature is 10～30 ℃, stirs 3h, then above-mentioned solution beaker is placed the water bath with thermostatic control about 35 ℃, and the question response temperature rises to and continues to stir 30min about 35 ℃.Control reaction temperature at last in 100 ℃, drip deionized water, continue to stir 30min, rate of addition is 0.3～0.5mL/ second.Add the mixed solution that an amount of 30% hydrogen peroxide and deionized water are formed at last.The hydrogen peroxide that adds, the ratio of deionized water are 1:1～1:10.Centrifugal washing while hot obtains yellowish-brown mud shape thing.
Step 2: with above-mentioned mud shape thing drying, take by weighing 0.2g and be dispersed in the deionized water, lasting ultrasonic then, last centrifugal twice taking-up bronzing supernatant.Ultrasonic time is 1～3h.The volume ratio of mud shape thing and deionized water is 1:1000～1:125.
Step 3: be that 0.5mmol/L KCl solution joins in the 300mL absolute ethyl alcohol with 1.5mL concentration, magnetic agitation 30min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains a kind of lily powder.The volume ratio of KCl solution and absolute ethyl alcohol is 1:300～200, and the volume ratio of KCl solution and tetrabutyl titanate is 1:5～2.
Step 4: the white powder in the supernatant of gained in the step 2 and the step 3 is mixed, under the condition of room temperature, continue magnetic agitation 24h, last centrifugal and wash 4 times, obtain the canescence powder.The ratio of supernatant and white powder is 200:1～1000:1mL/g.
Step 5: gained canescence powder in the step 4 is placed Muffle furnace, under the condition of vacuum, rationally control 1 ℃/min of heating rate and obtain light grey powder with insulation 2h, be i.e. graphene oxide parcel titanic oxide microsphere photocatalyst.
The consumption of the concentrated sulfuric acid and potassium permanganate among the present invention, and the temperature control of gentle pyroreaction in the low temperature, and the addition of water all can influence the quality of graphite oxide, and the interlamellar spacing of graphite oxide.Final size and the number of plies that influences graphene oxide.
Calcination time among the present invention and heating rate can influence the integrality of graphene oxide parcel titanium dioxide microballoon sphere, and long calcination time and too fast heating rate can cause the microscopic appearance of graphene oxide parcel titanium dioxide microballoon sphere to be damaged.
Embodiment 1
The concentrated sulfuric acid 115mL of adding 98% is cooled to about 0 ℃ in the beaker of drying, adds natural flake graphite 5g in the stirring successively, sodium nitrate 5g, potassium permanganate 15g.The control reaction temperature is 10～30 ℃, stirs 3h, then above-mentioned solution beaker is placed the water bath with thermostatic control about 35 ℃, and the question response temperature rises to and continues to stir 30min about 35 ℃.Control reaction temperature at last in 100 ℃, drip deionized water, continue to stir 30min, rate of addition is 0.3～0.5mL/ second.Add the mixed solution that an amount of 30% hydrogen peroxide and 50mL deionized water are formed at last.The hydrogen peroxide that adds, the ratio of deionized water are 1:5.Centrifugal washing while hot obtains yellowish-brown mud shape thing.With above-mentioned mud shape thing drying, take by weighing 0.2g and be dispersed in the deionized water, continue ultrasonic 3h then, last centrifugal twice taking-up bronzing supernatant.Ultrasonic time is 1～3h.The ratio of mud shape thing and deionized water is 1:125.Be that 0.5mmol/L KCl solution joins in the 300mL absolute ethyl alcohol with 1.5mL concentration, magnetic agitation 30min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains a kind of lily powder.The ratio of KCl solution, absolute ethyl alcohol, tetrabutyl titanate is 1:300:5.White powder in the supernatant of above-mentioned gained and the step 3 is mixed, under the condition of room temperature, continue magnetic agitation 24h, last centrifugal and wash 4 times, obtain the canescence powder.How many 1000:1mL/g are the ratio of supernatant and white powder be.Above-mentioned gained canescence powder is placed Muffle furnace, under the condition of vacuum, rationally control 1 ℃/min of heating rate and obtain light grey powder with insulation 2h.As can be seen from Figure 1, prepared graphene oxide parcel titanium dioxide microballoon sphere, the pattern homogeneous, the good dispersion diameter of micro ball is about 500nm.The graphene oxide parcel does not come off.
Embodiment 2
The concentrated sulfuric acid 115mL of adding 98% is cooled to about 0 ℃ in the beaker of drying, adds natural flake graphite 5g in the stirring successively, sodium nitrate 5g, potassium permanganate 15g.The control reaction temperature is 10～30 ℃, stirs 3h, then above-mentioned solution beaker is placed the water bath with thermostatic control about 35 ℃, and the question response temperature rises to and continues to stir 30min about 35 ℃.Control reaction temperature at last in 100 ℃, drip deionized water, continue to stir 30min, rate of addition is 0.3～0.5mL/ second.Add the mixed solution that an amount of 30% hydrogen peroxide and 50mL deionized water are formed at last.The hydrogen peroxide that adds, the ratio of deionized water are 1:1.Centrifugal washing while hot obtains yellowish-brown mud shape thing.With above-mentioned mud shape thing drying, take by weighing 0.2g and be dispersed in the deionized water, continue ultrasonic 3h then, last centrifugal twice taking-up bronzing supernatant.Ultrasonic time is 1～3h.The ratio of mud shape thing and deionized water is 1:500.Be that 0.5mmol/L KCl solution joins in the 300mL absolute ethyl alcohol with 1.5mL concentration, magnetic agitation 30min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains a kind of lily powder.The ratio of KCl solution, absolute ethyl alcohol, tetrabutyl titanate is 1:600:10.White powder in the supernatant of above-mentioned gained and the step 3 is mixed, under the condition of room temperature, continue magnetic agitation 24h, last centrifugal and wash 4 times, obtain the canescence powder.How many 500:1mL/g are the ratio of supernatant and white powder be.Above-mentioned gained canescence powder is placed Muffle furnace, under the condition of vacuum, rationally control 1 ℃/min of heating rate and obtain light grey powder with insulation 2h.As can be seen from Figure 2, prepared graphene oxide parcel titanium dioxide microballoon sphere, series of intermediate products all reaches requirement fully in the process, and corresponding infrared spectrum shows its preparation process generation esterification bonding, and titanium dioxide and graphene oxide are combined closely.
Embodiment 3
The concentrated sulfuric acid 115mL of adding 98% is cooled to about 0 ℃ in the beaker of drying, adds natural flake graphite 5g in the stirring successively, sodium nitrate 5g, potassium permanganate 15g.The control reaction temperature is 10～30 ℃, stirs 3h, then above-mentioned solution beaker is placed the water bath with thermostatic control about 35 ℃, and the question response temperature rises to and continues to stir 30min about 35 ℃.Control reaction temperature at last in 100 ℃, drip deionized water, continue to stir 30min, rate of addition is 0.3～0.5mL/ second.Add the mixed solution that an amount of 30% hydrogen peroxide and 50mL deionized water are formed at last.The hydrogen peroxide that adds, the ratio of deionized water are 1:10.Centrifugal washing while hot obtains yellowish-brown mud shape thing.With above-mentioned mud shape thing drying, take by weighing 0.2g and be dispersed in the deionized water, continue ultrasonic 3h then, last centrifugal twice taking-up bronzing supernatant.Ultrasonic time is 1～3h.The ratio of mud shape thing and deionized water is 1:1000.Be that 0.5mmol/L KCl solution joins in the 300mL absolute ethyl alcohol with 1.5mL concentration, magnetic agitation 30min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains a kind of lily powder.The ratio of KCl solution, absolute ethyl alcohol, tetrabutyl titanate is 2:1000:10.White powder in the supernatant of above-mentioned gained and the step 3 is mixed, under the condition of room temperature, continue magnetic agitation 24h, last centrifugal and wash 4 times, obtain the canescence powder.How many 600:1mL/g are the ratio of supernatant and white powder be.Above-mentioned gained canescence powder is placed Muffle furnace, under the condition of vacuum, rationally control 1 ℃/min of heating rate and obtain light grey powder with insulation 2h.As can be seen from Figure 3, prepared graphene oxide parcel titanium dioxide microballoon sphere, its photo-catalysis capability is very strong, and under the visible light condition, the short time can degradation of organic substances.
Embodiment 4
The concentrated sulfuric acid 115mL of adding 98% is cooled to about 0 ℃ in the beaker of drying, adds natural flake graphite 5g in the stirring successively, sodium nitrate 5g, potassium permanganate 15g.The control reaction temperature is 10～30 ℃, stirs 3h, then above-mentioned solution beaker is placed the water bath with thermostatic control about 35 ℃, and the question response temperature rises to and continues to stir 30min about 35 ℃.Control reaction temperature at last in 100 ℃, drip deionized water, continue to stir 30min, rate of addition is 0.3～0.5mL/ second.Add the mixed solution that an amount of 30% hydrogen peroxide and 50mL deionized water are formed at last.The hydrogen peroxide that adds, the ratio of deionized water are 1:4.Centrifugal washing while hot obtains yellowish-brown mud shape thing.With above-mentioned mud shape thing drying, take by weighing 0.2g and be dispersed in the deionized water, continue ultrasonic 3h then, last centrifugal twice taking-up bronzing supernatant.Ultrasonic time is 1～3h.The ratio of mud shape thing and deionized water is 1:900.Be that 0.5mmol/L KCl solution joins in the 300mL absolute ethyl alcohol with 1.5mL concentration, magnetic agitation 30min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains a kind of lily powder.The ratio of KCl solution, absolute ethyl alcohol, tetrabutyl titanate is 1:200:2.White powder in the supernatant of above-mentioned gained and the step 3 is mixed, under the condition of room temperature, continue magnetic agitation 24h, last centrifugal and wash 4 times, obtain the canescence powder.How many 200:1mL/g are the ratio of supernatant and white powder be.Above-mentioned gained canescence powder is placed Muffle furnace, under the condition of vacuum, rationally control 1 ℃/min of heating rate and obtain light grey powder with insulation 2h.
The concentrated sulfuric acid 115mL of adding 98% is cooled to about 0 ℃ in the beaker of drying, adds natural flake graphite 5g in the stirring successively, sodium nitrate 5g, potassium permanganate 15g.The control reaction temperature is 10～30 ℃, stirs 3h, then above-mentioned solution beaker is placed the water bath with thermostatic control about 35 ℃, and the question response temperature rises to and continues to stir 30min about 35 ℃.Control reaction temperature at last in 100 ℃, drip deionized water, continue to stir 30min, rate of addition is 0.3～0.5mL/ second.Add the mixed solution that an amount of 30% hydrogen peroxide and 50mL deionized water are formed at last.The hydrogen peroxide that adds, the ratio of deionized water are 1:2.Centrifugal washing while hot obtains yellowish-brown mud shape thing.With above-mentioned mud shape thing drying, take by weighing 0.2g and be dispersed in the deionized water, continue ultrasonic 3h then, last centrifugal twice taking-up bronzing supernatant.Ultrasonic time is 1～3h.The ratio of mud shape thing and deionized water is 1:700.Be that 0.5mmol/L KCl solution joins in the 300mL absolute ethyl alcohol with 1.5mL concentration, magnetic agitation 30min, slowly splash into the tetrabutyl titanate of 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains a kind of lily powder.The ratio of KCl solution, absolute ethyl alcohol, tetrabutyl titanate is 4:500:5.White powder in the supernatant of above-mentioned gained and the step 3 is mixed, under the condition of room temperature, continue magnetic agitation 24h, last centrifugal and wash 4 times, obtain the canescence powder.How many 400:1mL/g are the ratio of supernatant and white powder be.Above-mentioned gained canescence powder is placed Muffle furnace, under the condition of vacuum, rationally control 1 ℃/min of heating rate and obtain light grey powder with insulation 2h.
Claims (7)
1. the preparation method of a graphene oxide parcel titanic oxide microsphere photocatalyst is characterized in that, specifically implements according to following steps:
Step 1: the adding mass concentration is 98% the concentrated sulfuric acid in the beaker of drying, is cooled to 0 ℃, adds natural flake graphite, sodium nitrate, potassium permanganate in the stirring successively; The control reaction temperature is 10～30 ℃, stir 3h, the beaker that will fill mixed solution then places 35 ℃ of waters bath with thermostatic control, the question response temperature rises to 35 ℃ and continues to stir 30min, control reaction temperature at last at 0-100 ℃, drip deionized water, continue to stir 30min, add the mixed solution that 30% hydrogen peroxide and deionized water are formed at last, centrifugal washing obtains yellowish-brown mud shape thing;
Step 2: the mud shape thing drying with step 1 obtains, be dispersed in the deionized water, ultrasonic 1～3h obtains the bronzing supernatant centrifugal twice;
Step 3: be that the KCl solution of 0.5mmol/L joins in the absolute ethyl alcohol with concentration, magnetic agitation 30min slowly splashes into tetrabutyl titanate, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively with absolute ethyl alcohol and deionized water, and drying obtains white powder;
Step 4: the white powder that the supernatant that step 2 is obtained and step 3 obtain mixes, at room temperature condition, and magnetic agitation 24h, centrifugal and wash 4 times, obtain the canescence powder;
Step 5: the canescence powder that step 4 is obtained places Muffle furnace, and under the condition of vacuum, the control heating rate is 1 ℃/min, and insulation 2h obtains graphene oxide parcel titanic oxide microsphere photocatalyst.
2. graphene oxide according to claim 1 wraps up the preparation method of titanic oxide microsphere photocatalyst, it is characterized in that the quality-volumetric concentration of natural flake graphite, sodium nitrate, potassium permanganate is respectively in the described step 1: 43.48g/L, 43.48g/L, 130.43g/L.
3. the preparation method of graphene oxide parcel titanic oxide microsphere photocatalyst according to claim 1 is characterized in that the volume ratio of hydrogen peroxide and deionized water is 1:1～10 in the described step 1.
4. the preparation method of graphene oxide parcel titanic oxide microsphere photocatalyst according to claim 1 is characterized in that the rate of addition of deionized water is 0.3～0.5mL/ second in the described step 1.
5. the preparation method of graphene oxide parcel titanic oxide microsphere photocatalyst according to claim 1 is characterized in that the volume ratio of mud shape thing and deionized water is 1:1000～125 in the described step 2.
6. graphene oxide according to claim 1 wraps up the preparation method of titanic oxide microsphere photocatalyst, it is characterized in that, the volume ratio of KCl solution and absolute ethyl alcohol is 1:300～200 in the described step 3, and the volume ratio of KCl solution and tetrabutyl titanate is 1:5～2.
7. the preparation method of graphene oxide parcel titanic oxide microsphere photocatalyst according to claim 1 is characterized in that the ratio of supernatant and white powder is 200:1～1000:1mL/g in the described step 4.
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| CN109777245A (en) * | 2019-02-19 | 2019-05-21 | 安徽企服工程技术有限公司 | A kind of photocuring film forming coating for wall surface |
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