CN103285845B - Preparation method of graphene oxide wrapped titania microsphere photocatalyst - Google Patents
Preparation method of graphene oxide wrapped titania microsphere photocatalyst Download PDFInfo
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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 technical field of composite preparation, relate to the preparation method of a kind of graphene oxide parcel titanium dioxide microballoon sphere material, be specifically related to the preparation method of a kind of graphene oxide parcel titanic oxide microsphere photocatalyst.
Background technology
Nanoscale TiO
2cause many concerns in recent years, be widely used in the 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, the nano-TiO of the Anatase that comparatively speaking, degree of crystallinity is higher, crystal grain is less
2show better photocatalysis performance.And electron-hole compound, photon equilibrium state etc. all can have influence on TiO
2final photon utilization ratio.
Graphene has the specific area (2630mz/g) of good thermal conductivity [3000W/ (mK)], very high intensity (110GPa) and super large.The performance of these excellences makes Graphene have a extensive future in fields such as nano electron device, gas sensor, stored energy and composites.
New carbon and TiO
2be compounded to form composite, played both synergies, enhance the photocatalysis performance of material to organic matter, pollutant, its reason have following some: the specific area that (1) composite is larger improves the adsorption capacity of material to organic pollution; (2) material with carbon element-TiO
2the formation of interface hetero-junctions improves the compound between light induced electron and hole; (3) compared to pure TiO
2, the fermi level of composite to the direction skew of corrigendum, and then may improve the utilization rate to longer wavelength photon; (4), after carbon material surface absorb photons, TiO will be electronically injected to
2conduction band, forms reaction exciton (the superoxide radical O in order to degradable organic pollutant
2-and Hydroxyl radical HO).Existing microballoon catalysis material has many shortcomings, such as conventional TiO
2there is wider with gap (Detitanium-ore-type TiO
2energy gap be 3.2eV), photo-generate electron-hole to being easy to compound, and less specific area and only have lower Dye Adsorption capacity, these seriously limit greatly developing of microballoon photocatalysis industry.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of graphene oxide parcel titanic oxide microsphere photocatalyst, solve the wider problem causing application limited of existing microballoon catalysis material with gap.
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: add the concentrated sulfuric acid that mass concentration is 98% in the beaker of drying, be cooled to 0 DEG C, add natural flake graphite, sodium nitrate, potassium permanganate successively in stirring; Controlling reaction temperature is 10 ~ 30 DEG C, stir 3h, then the beaker filling mixed solution is placed in 35 DEG C of waters bath with thermostatic control, question response temperature rises to 35 DEG C and continues to stir 30min, finally control reaction temperature at 0-100 DEG C, drip deionized water, continue to stir 30min, finally add the hydrogen peroxide of 30% and the mixed solution of deionized water composition, centrifugal washing obtains yellowish-brown purees;
Step 2: the purees that step 1 obtained is dry, in deionized water, ultrasonic 1 ~ 3h, centrifugally obtains bronzing supernatant for twice in dispersion;
Step 3: be that the KCl solution of 0.5mmol/L joins in absolute ethyl alcohol by concentration, magnetic agitation 30min, slowly instills tetrabutyl titanate, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by absolute ethyl alcohol and deionized water, and drying obtains white powder;
Step 4: white powder that supernatant step 2 obtained and step 3 obtain mixing, at room temperature condition, magnetic agitation 24h, centrifugal and wash 4 times, obtain canescence powder;
Step 5: canescence powder step 4 obtained is placed in Muffle furnace, under the condition of vacuum, controlling heating rate is 1 DEG C/min, and insulation 2h obtains graphene oxide parcel titanic oxide microsphere photocatalyst.
Feature of the present invention is also,
In step 1 wherein, the quality-volumetric concentration of natural flake graphite, sodium nitrate, potassium permanganate is respectively: 43.48g/L, 43.48g/L, 130.43g/L.
In step 1 wherein, the volume ratio of hydrogen peroxide and deionized water is 1:1 ~ 10.
In step 1 wherein, the rate of addition of deionized water is 0.3 ~ 0.5mL/ second.
In step 2 wherein, the volume ratio of purees and deionized water is 1:1000 ~ 125.
In step 3 wherein, 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.
In step 4 wherein, the ratio of supernatant and white powder is 200:1 ~ 1000:1mL/g.
The invention has the beneficial effects as follows: the present invention adopts simple and practical method, by graphene oxide and stable the combining of titanium dioxide.Experimental period is short, convenient operation, has the advantage that aggregate velocity is fast, efficiency is high and energy consumption is low, has the prospect of suitability for industrialized production.
Utilize the huge specific area of Graphene greatly can improve the Dye Adsorption capacity of composite photo-catalyst, the conductivity of two-dimensional structure excellence greatly can improve transmission, the transfer in light induced electron and hole, improve separative efficiency, and the energy gap that the impurity energy level effect that Graphene produces in composite photo-catalyst can cut down composite is greatly that excellent photocatalysis performance is laid a solid foundation.In addition, the mechanical property of the excellence that Graphene has can maintain the special structure of composite, and this is to a certain extent for the realization of composite catalyzing provides material base.
Accompanying drawing explanation
Fig. 1 is a series of stereoscan photographs of the graphene oxide parcel titanic oxide microsphere photocatalyst that the embodiment of the present invention 1 obtains, wherein, a is the stereoscan photograph that graphite oxide amplifies 18000 times, and b is the stereoscan photograph that titanium dioxide microballoon sphere amplifies 120000; 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 present invention 2 completes a series of product in 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 present invention 3 obtains graphene oxide parcel titanium dioxide microballoon sphere material, and wherein, a is gained under UV-irradiation condition; B is gained under radiation of visible light condition.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Graphene oxide parcel titanic oxide microsphere photocatalyst of the present invention, pattern is homogeneous, the Jacket thickness of graphene oxide can conveniently control, can not come off, single dispersing is good, the diameter of microballoon is about 500nm, and the size of graphene oxide lamella can be controlled by ultrasonic time, and the parcel number of plies can 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: add the concentrated sulfuric acid that mass concentration is 98% in the beaker of drying, is cooled to about 0 DEG C, adds natural flake graphite successively, sodium nitrate, potassium permanganate in stirring.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.
Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then above-mentioned solution beaker is placed in the water bath with thermostatic control of about 35 DEG C, and question response temperature rises to about 35 DEG C and continues to stir 30min.Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second.Finally add the mixed solution of appropriate 30% hydrogen peroxide and deionized water composition.The hydrogen peroxide added, the ratio of deionized water are 1:1 ~ 1:10.Centrifugal washing while hot obtains yellowish-brown purees.
Step 2: above-mentioned purees is dry, takes 0.2g dispersion in deionized water, then continual ultrasonic, finally takes out bronzing supernatant centrifugal twice.Ultrasonic time is 1 ~ 3h.The volume ratio of purees and deionized water is 1:1000 ~ 1:125.
Step 3: be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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: by the white powder mixing in the supernatant of gained in step 2 and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder.The ratio of supernatant and white powder is 200:1 ~ 1000:1mL/g.
Step 5: gained canescence powder in step 4 is placed in Muffle furnace, under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder, i.e. graphene oxide parcel titanic oxide microsphere photocatalyst.
The consumption of the concentrated sulfuric acid and potassium permanganate in the present invention, and in low temperature, the temperature of gentle pyroreaction controls, and the addition of water all can affect the quality of graphite oxide, and the interlamellar spacing of graphite oxide.Final size and the number of plies affecting graphene oxide.
Calcination time in the present invention and heating rate can affect the integrality of graphene oxide parcel titanium dioxide microballoon sphere, and the microscopic appearance that long calcination time and too fast heating rate can cause graphene oxide to wrap up titanium dioxide microballoon sphere is damaged.
Embodiment 1
In the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to about 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g.Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then above-mentioned solution beaker is placed in the water bath with thermostatic control of about 35 DEG C, and question response temperature rises to about 35 DEG C and continues to stir 30min.Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second.Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition.The hydrogen peroxide added, the ratio of deionized water are 1:5.Centrifugal washing while hot obtains yellowish-brown purees.Above-mentioned purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice.Ultrasonic time is 1 ~ 3h.The ratio of purees and deionized water is 1:125.Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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.By the white powder mixing in the supernatant of above-mentioned gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder.The ratio of supernatant and white powder is how many 1000:1mL/g.Above-mentioned gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder.As can be seen from Figure 1, prepared graphene oxide parcel titanium dioxide microballoon sphere, pattern is homogeneous, and the diameter of good dispersion microballoon is about 500nm.Graphene oxide parcel does not have to come off.
Embodiment 2
In the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to about 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g.Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then above-mentioned solution beaker is placed in the water bath with thermostatic control of about 35 DEG C, and question response temperature rises to about 35 DEG C and continues to stir 30min.Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second.Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition.The hydrogen peroxide added, the ratio of deionized water are 1:1.Centrifugal washing while hot obtains yellowish-brown purees.Above-mentioned purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice.Ultrasonic time is 1 ~ 3h.The ratio of purees and deionized water is 1:500.Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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.By the white powder mixing in the supernatant of above-mentioned gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder.The ratio of supernatant and white powder is how many 500:1mL/g.Above-mentioned gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder.As can be seen from Figure 2, prepared graphene oxide parcel titanium dioxide microballoon sphere, in process, series of intermediate products reaches requirement all completely, and corresponding infrared spectrum shows its preparation process generation esterification bonding, and titanium dioxide and graphene oxide are combined closely.
Embodiment 3
In the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to about 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g.Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then above-mentioned solution beaker is placed in the water bath with thermostatic control of about 35 DEG C, and question response temperature rises to about 35 DEG C and continues to stir 30min.Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second.Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition.The hydrogen peroxide added, the ratio of deionized water are 1:10.Centrifugal washing while hot obtains yellowish-brown purees.Above-mentioned purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice.Ultrasonic time is 1 ~ 3h.The ratio of purees and deionized water is 1:1000.Be that 0.5mmol/LKCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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.By the white powder mixing in the supernatant of above-mentioned gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder.The ratio of supernatant and white powder is how many 600:1mL/g.Above-mentioned gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder.As can be seen from Figure 3, prepared graphene oxide parcel titanium dioxide microballoon sphere, its photo-catalysis capability is very strong, and under visible light conditions, the short time can degradation of organic substances.
Embodiment 4
In the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to about 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g.Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then above-mentioned solution beaker is placed in the water bath with thermostatic control of about 35 DEG C, and question response temperature rises to about 35 DEG C and continues to stir 30min.Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second.Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition.The hydrogen peroxide added, the ratio of deionized water are 1:4.Centrifugal washing while hot obtains yellowish-brown purees.Above-mentioned purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice.Ultrasonic time is 1 ~ 3h.The ratio of purees and deionized water is 1:900.Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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.By the white powder mixing in the supernatant of above-mentioned gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder.The ratio of supernatant and white powder is how many 200:1mL/g.Above-mentioned gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder.
Embodiment 5
In the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to about 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g.Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then above-mentioned solution beaker is placed in the water bath with thermostatic control of about 35 DEG C, and question response temperature rises to about 35 DEG C and continues to stir 30min.Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second.Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition.The hydrogen peroxide added, the ratio of deionized water are 1:2.Centrifugal washing while hot obtains yellowish-brown purees.Above-mentioned purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice.Ultrasonic time is 1 ~ 3h.The ratio of purees and deionized water is 1:700.Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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.By the white powder mixing in the supernatant of above-mentioned gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder.The ratio of supernatant and white powder is how many 400:1mL/g.Above-mentioned gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder.
Claims (1)
1. a preparation method for graphene oxide parcel titanic oxide microsphere photocatalyst, is characterized in that, specifically implement according to following steps:
In the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g; Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then beaker is placed in the water bath with thermostatic control of 35 DEG C, and question response temperature rises to 35 DEG C and continues to stir 30min; Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second; Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition; The hydrogen peroxide added, the ratio of deionized water are 1:5; Centrifugal washing while hot obtains yellowish-brown purees; Purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice; Ultrasonic time is 1 ~ 3h; The ratio of purees and deionized water is 1:125; Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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; By the white powder mixing in the supernatant of gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder; The ratio of supernatant and white powder is 1000:1mL/g; Gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder;
Or, in the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g; Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then beaker is placed in the water bath with thermostatic control of 35 DEG C, and question response temperature rises to 35 DEG C and continues to stir 30min; Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second; Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition; The hydrogen peroxide added, the ratio of deionized water are 1:1; Centrifugal washing while hot obtains yellowish-brown purees; Purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice; Ultrasonic time is 1 ~ 3h; The ratio of purees and deionized water is 1:500; Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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; By the white powder mixing in the supernatant of gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder; The ratio of supernatant and white powder is 500:1mL/g; Gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder;
Or, in the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g; Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then beaker is placed in the water bath with thermostatic control of 35 DEG C, and question response temperature rises to 35 DEG C and continues to stir 30min; Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second; Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition; The hydrogen peroxide added, the ratio of deionized water are 1:10; Centrifugal washing while hot obtains yellowish-brown purees; Purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice; Ultrasonic time is 1 ~ 3h; The ratio of purees and deionized water is 1:1000; Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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; By the white powder mixing in the supernatant of gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder; The ratio of supernatant and white powder is 600:1mL/g; Gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder;
Or, in the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g; Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then beaker is placed in the water bath with thermostatic control of 35 DEG C, and question response temperature rises to 35 DEG C and continues to stir 30min; Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second; Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition; The hydrogen peroxide added, the ratio of deionized water are 1:4; Centrifugal washing while hot obtains yellowish-brown purees; Purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice; Ultrasonic time is 1 ~ 3h; The ratio of purees and deionized water is 1:900; Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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; By the white powder mixing in the supernatant of gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder; The ratio of supernatant and white powder is 200:1mL/g; Gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder;
Or, in the beaker of drying, add the concentrated sulfuric acid 115mL of 98%, be cooled to 0 DEG C, in stirring, add natural flake graphite 5g successively, sodium nitrate 5g, potassium permanganate 15g; Controlling reaction temperature is 10 ~ 30 DEG C, stirs 3h, then beaker is placed in the water bath with thermostatic control of 35 DEG C, and question response temperature rises to 35 DEG C and continues to stir 30min; Finally control reaction temperature within 100 DEG C, drip deionized water, continue to stir 30min, rate of addition is 0.3 ~ 0.5mL/ second; Finally add the mixed solution of appropriate 30% hydrogen peroxide and 50mL deionized water composition; The hydrogen peroxide added, the ratio of deionized water are 1:2; Centrifugal washing while hot obtains yellowish-brown purees; Purees is dry, take 0.2g dispersion in deionized water, then continual ultrasonic 3h, finally take out bronzing supernatant centrifugal twice; Ultrasonic time is 1 ~ 3h; The ratio of purees and deionized water is 1:700; Be that 0.5mmol/L KCl solution joins in 300mL absolute ethyl alcohol by 1.5mL concentration, magnetic agitation 30min, the tetrabutyl titanate of slow instillation 5.4mL, vigorous stirring reaction 30min, ageing 4h, centrifugation is also cleaned successively by 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; By the white powder mixing in the supernatant of gained and step 3, under the condition of room temperature, continuing magnetic force stirs 24h, finally centrifugal and wash 4 times, obtains canescence powder; The ratio of supernatant and white powder is 400:1mL/g; Gained canescence powder is placed in Muffle furnace, and under the condition of vacuum, conservative control heating rate 1 DEG C/min and insulation 2h obtains light grey powder.
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