CN109833862A - A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material - Google Patents
A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material Download PDFInfo
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Abstract
The invention discloses a kind of redox graphene/titanium dioxide double shells hollow sphere (RGO/TiO2 HS) composite photocatalyst material preparation methods, belong to optic catalytic composite material and water-treatment technology field.Specifically, it is to prepare silica (SiO2) powder template and graphene oxide (GO) first, then using 3- aminopropyl trimethoxy siloxane (APTES) to SiO2 powder amination, and the SiO2 ball for being coated the compound obtained GO of GO and SiO2 powder by ultrasonic method, then butyl titanate (TBOT) hydrolysis is controlled by hydrolysis inhibitor of sulfuric acid, the SiO2 ball of GO cladding is coated again, and forms RGO/TiO2 HS double shells hollow sphere nanocomposite by high-temperature calcination, the etching of sodium hydroxide.Composite photocatalyst material prepared by the method for the present invention is significant to the degradation of methyl orange coloration, coloration is able to satisfy " textile dyeing and finishing industrial water pollution object discharge standard " (GB4287-2012) after processing, provides a kind of new way for processing color degree of dyeing waste water.
Description
Technical field
The content of present invention belongs to optic catalytic composite material and water-treatment technology field, particularly, is related to a kind of reduction-oxidation
Graphene/titanium dioxide double shells hollow sphere composite photocatalyst material preparation method.
Background technique
As industrial process is accelerated, water environment pollution problem is increasingly serious.Persistent organic pollutants have chemical property
The features such as stabilization, bio-toxicity is big, significant damage will be brought to the ecosystem and human health by being discharged into water body.Wherein printing and dyeing are useless
Contain azo hardly degraded organic substance in water, has the characteristics that big coloration, difficult for biological degradation, complicated component, discharge amount are big, therefore
It handles up to standard relatively difficult.Photochemical catalytic oxidation is proved to be a kind of oxidation activity height, and selectivity is small, water efficiently without secondary pollution
Processing method, wherein TiO2Catalyst is stablized with chemical property, and inexpensively, the characteristics such as nontoxic are widely used in pollutant and control
Reason etc..Currently, many research workers utilize TiO2Photocatalysis technology is to some Recalcitrant chemicals matter, such as oil refining
Sewage, dyeing waste water, coking wastewater etc. carry out photocatalysis treatment, obtain significant effect.
The pattern of nano material has great influence to its performance.The hollow structure appearance structure special as one kind,
Catalyst, medicament slow release, micro-capsule reactor, biosensor, electrochemical device etc. are widely applied.TiO2It is hollow
Ball density is low, and Surface Permeability is good, and surface area is high, has higher smooth capture effect and chemical mobility of the surface, significantly increases light
Catalytic performance.And pure TiO2The compound recombination rates of photo-generate electron-hole pairs that catalysis material generates after light excitation are higher, lead
Photocatalytic activity is caused to reduce.Therefore it is badly in need of taking effective method, to TiO2It is modified.There is graphene electronics to receive and transport
Defeated performance, with TiO2The compound separation that can effectively realize electron-hole pair；There is graphene the theory of superelevation to compare table simultaneously
Area can effectively improve graphene oxide/titanium dioxide (GO/TiO2) composite material specific surface area, increase to pollutant
Absorption, is conducive to the enrichment to pollutant, to improve its photocatalysis performance.
GO/TiO2The preparation of composite photocatalyst material is always research hotspot, but the GO/TiO synthesized at present2Composite material,
Its graphene oxide (GO) lamella is coated on TiO2On, excessive GO will affect the transmitance of light, improves to photocatalytic activity and imitates
Fruit is undesirable.In addition, in the prior art, the coloured organic pollutant techniques of Dyeing Wastewater Treatment containing methyl orange is generally existing to be processed into
This height, complex process and there are the technical problems such as secondary pollution.
Summary of the invention
Graphene oxide/titanium dioxide (GO/TiO of the present invention primarily directed to prior art preparation2) composite material light
Catalytic activity effect is undesirable, and is processed into the coloured organic pollutant techniques of Dyeing Wastewater Treatment containing methyl orange is generally existing
This height, complex process and there are the technical problems such as secondary pollution provide a kind of high performance redox graphene/titanium dioxide
Titanium (RGO/TiO2HS) the preparation method of double shells Hollow Sphere Composites.
The present invention is achieved through the following technical solutions.
A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material, it is special
Sign is, in turn includes the following steps: 1) preparing amination SiO2Powder template；2) graphene oxide and configuration oxidation stone are prepared
Black alkene stock solution；3) by amination SiO2Powder template and graphene oxide stock solution prepare the SiO of clad structure2/ graphite oxide
Alkene ball；4) by the SiO of clad structure2/ graphene oxide ball and butyl titanate and strong sulfuric acid response, prepare secondary clad structure
SiO2/ graphene oxide/TiO2Ball；5) by the SiO of secondary clad structure2/ graphene oxide/TiO2Ball calcining thermal reduction, goes
Except SiO2Template prepares target product redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material.
A kind of preparation of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material as described above
Method, which is characterized in that the operating method of step 1) is, by dehydrated alcohol, distilled water, the ammonia that mass fraction is 20~30 %
Water is uniformly mixed for 37:7:1 according to volume ratio, is then slowly added into the ethyl orthosilicate of appropriate 99.9 % of mass fraction >
(TEOS), 4 ~ 8 h of magnetic agitation under the stirring rate of 800 ~ 1200 r/min, dehydrated alcohol wash, and do at 60 ~ 100 DEG C
It is dry, obtain SiO2Powder template；Then again by SiO2The nothing of powder template and the trimethoxy siloxane of aminopropyl containing 3- (APTES)
Hydrous ethanol solution is uniformly mixed according to volume ratio for 10:1 ~ 2:1,4 ~ 8 h of reflux operation, dehydrated alcohol under the conditions of 60 ~ 80 DEG C
It washs, it is dry at 60 ~ 100 DEG C, obtain amination SiO2Powder template.
A kind of preparation of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material as described above
Method, which is characterized in that the operating method of step 2 is that the nitre of 2.5 parts of mass parts is added in the concentrated sulfuric acid of 115 parts of parts by volume
Sour sodium adds 5 parts of graphite after mixing, and 1 ~ 3 h is stirred under the rate conditions of 800 ~ 1200 r/min, is then being reacted
Temperature be lower than 5 DEG C under the conditions of be slowly added to 15 parts of potassium permanganate, start reaction after reaction vessel is placed in water bath with thermostatic control,
After heating the reaction was continued a period of time, appropriate amount of deionized water is added after heating up again, react be added after 10~20 min again it is suitable
The reaction was continued for the hydrogenperoxide steam generator that amount deionized water and mass fraction are 20 ~ 40 % to reaction terminating, then uses mass fraction
Centrifuge washing is carried out to reaction product for the dilute hydrochloric acid of 1 ~ 10 %, then is washed with distilled water to neutrality, it is dry, obtain graphite oxide
Alkene (GO), then disperses distilled water for the GO of preparation again, and through ultrasonic Separation, centrifugal mixer, and being diluted with water configuration concentration is 5
The GO stock solution of ~ 15 mg/mL.A preferred technical solution is, in aforementioned preparation process, 15 parts of potassium permanganate is added and carry out
Before reaction, reaction vessel is placed in ice water bath environment；In the preparation process of GO, after reaction vessel is placed in water bath with thermostatic control,
30 ~ 40 DEG C are warming up to for the first time, the reaction time is 1 ~ 3 h after heating, is warming up to 90 ~ 100 DEG C again；The preparation of GO stock solution
Cheng Zhong, ultrasonic Separation time are 2 ~ 4 h, and centrifugal mixer rate is 5000 ~ 7000 r/min, and the centrifugal mixer time is 4 ~ 10
min。
A kind of preparation of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material as described above
Method, which is characterized in that the operating method of step 3) is the amination SiO for obtaining step 1)2Powder template is obtained with step 2
To GO stock solution difference ultrasonic disperse in appropriate amount of deionized water, obtain amination SiO2Mixed liquor and concentration is 0.02 ~
The GO mixed liquor of 0.08 mg/mL, is then added dropwise amination SiO dropwise in GO mixed liquor2Mixed liquor continues ultrasound 30 ~ 60
Min, magnetic agitation, ageing are washed with distilled water, dry, obtain the SiO of clad structure2/ GO ball.Further, aforementioned operation
In method, amination SiO2The quality of powder template and the mass ratio of GO are 100:1 ~ 100:4；It is added dropwise dropwise in GO mixed liquor
Amination SiO2After mixed liquor, magnetic agitation speed is 800 ~ 1000 r/min, 1 ~ 2 h of mixing time, digestion time 12 ~ 36
h。
A kind of preparation of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material as described above
Method, which is characterized in that the operating method of step 4) is the SiO for the clad structure for obtaining step 3)2/ GO ball ultrasonic disperse
In suitable dehydrated alcohol, butyl titanate (TBOT) and the concentrated sulfuric acid is added, stirs evenly, gained mixed liquor is in 60 ~ 80 DEG C
Suitable quantity of water is slowly added under the conditions of temperature, flow back 8 ~ 12 h, dehydrated alcohol washing, and it is dry, obtain the SiO of secondary cladding2/GO/
TiO2Ball.Further, in aforementioned operation method, dehydrated alcohol: water: the volume ratio of TBOT is (7 ~ 10): 1:(0.03 ~
0.04)；(SiO2/ GO ball): the mass ratio of TBOT is 1:(0.8 ~ 1.2)；The additive amount of the concentrated sulfuric acid be overall solution volume 0.1 ~
0.3 %(V/V).
A kind of preparation of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material as described above
Method, which is characterized in that the operating method of step 5) is, by step 4) resulting materials in N2Under atmosphere, at 500 ~ 700 DEG C
Then calcining thermal reduction etches removal SiO with NaOH solution under the conditions of 80 ~ 100 DEG C2Template, distillation water washing, 60 ~ 100
DEG C drying, obtains target product redox graphene/titanium dioxide (RGO/TiO2HS) double shells hollow sphere composite photocatalyst
Material.A preferred technical solution is, in aforementioned preparation process, uses tube furnace during calcining thermal reduction；Etching removal
SiO2During template, the concentration of NaOH solution is 1 ~ 3 mol/L, 3 ~ 4 h of reaction time.
Redox graphene of the present invention/titanium dioxide double shells hollow sphere composite photocatalyst material preparation method
Advantage and technological progress are as follows:
(1) firstly, the present invention uses SiO2Template prepares RGO/TiO2HS double shells Hollow Sphere Composites, material appearance
Uniform controllable, mechanical stability is strong.Pass through ultrasound, amination SiO2The amino of powder template and the surface GO oxygen-containing official abundant
It can roll into a ball and be bonded, so that the SiO of GO cladding2Ball has stronger stability.RGO is wrapped in TiO2Layer inside, avoids
RGO/TiO2The loss of RGO, improves RGO/TiO during HS double shells hollow sphere is recycled2HS composite photocatalyst material
Recycle efficiency, have good environmental benefit.
(2) secondly, regulating and controlling unformed TiO by the volume ratio of adjusting dehydrated alcohol and water, the concentration of TBOT2Life
It is long, calcination temperature and time are adjusted to control TiO2Crystal phase and grain size, so that crystal grain is regular, is uniformly dispersed.System of the present invention
Standby RGO/TiO2HS composite photocatalyst material has unique double shells hollow ball structure, effectively increases specific surface area, has
Conducive to its enrichment and absorption to pollutant, RGO and TiO2Synergistic effect inhibit the compound of photo-generate electron-hole pair, add
Fast substance circulating causes its photocatalysis performance to significantly increase, thus the value that the method for the present invention promotes and applies is high, has preferable
Economic benefit.
(3) again, the RGO/TiO that the method for the present invention is prepared2HS composite photocatalyst material is applied to print containing methyl orange
The processing for contaminating waste water can effectively improve material to the transmitance of light, inhibit the compound of photo-generate electron-hole pair, best real
Under the conditions of applying example, ultraviolet light 30min, methyl orange chroma removal rate can reach 99% or more, and treated, and chroma in waste water is lower than
" the textile dyeing and finishing industrial water pollution object discharge standard " requirement of (GB4287-2012) to coloration, to guarantee surface water and underground water
Water quality safety and benign cycle, have apparent social benefit.
Detailed description of the invention
Fig. 1 is that RGO/TiO is prepared in the embodiment of the present invention 12HS double shells Hollow Sphere Composites SEM figure.
Specific embodiment
Preparation method and applications effect disclosed in this patent, but this hair are further described below by specific embodiment
It is bright to be not limited only to these embodiments.
Embodiment 1
1) preparation of GO, specific steps are as follows: the concentrated sulfuric acid (98 wt %) and the sodium nitrate of 2.5 g of 115 mL stirs evenly, and is added
5 g graphite continue to stir 1.5 h；Under condition of ice bath, be slowly added to 15 g potassium permanganate, 5 DEG C of reacting liquid temperature of control hereinafter,
It reacts 2.5 h to be placed in water bath with thermostatic control, is warming up to 35 DEG C the reaction was continued 2 h；98 DEG C of 230 mL of addition are then raised temperature to go
About 700 mL deionized waters are added after 15 min, while the hydrogen peroxide of 25 mL 30% is added for ionized water, and solution is from dark brown
Become vivid yellowish-brown, reaction terminating.5 centrifuge washings are carried out to it with the dilute hydrochloric acid of 5 %(wt), later with distillation washing
It washs to neutrality, 60 DEG C of drying for standby.
2) preparation of SiO 2 powder template, specific steps are as follows: by 92 mL ethyl alcohol, 17.2 mL water, 2.48 mL ammonium hydroxide
(28%) 30 min are mixed；3.44 mL of TEOS, with 0.1 mL min-1Rate is slowly injected into the above mixed liquor, and magnetic force stirs
6 h are mixed, centrifugation is washed 2 times with dehydrated alcohol, and 60 DEG C of dryings obtain SiO2Ball powder.1 g SiO2Ball is scattered in containing 0.2 mL
In the 150 mL ethanol solutions of APTES, 30min is stirred；60 DEG C of 8 h of reflux, centrifugation, with dehydrated alcohol and water washing two
Secondary (C2H5OH:H2O volume ratio is 1:1), 60 DEG C of dryings obtain amidized SiO2Powder template.
3) GO for obtaining step 1) is scattered in distilled water, and 3 h of ultrasound are centrifuged 5 points through 5000 rpm to be completely exfoliated
The GO of the difficult dispersion of clock removal, and it is diluted with water the graphene stock solution for being configured to 10 mg/mL.100 mg step 2 are obtained
Amination SiO2With 0.2 mL concentration be 10 mg/mL GO stock solution distinguish ultrasonic disperse in 50 mL water, GO mixed liquor by
It is added dropwise to amination SiO2In mixed liquor, continue 30 min of ultrasound.1 h of magnetic agitation is aged 24 h.It is multiple to change water, 60 DEG C dry
It is dry, obtain the SiO of GO cladding2Ball.
4) SiO for obtaining 100 mg step 3)2/ GO is scattered in 100 mL dehydrated alcohols, 30 min of ultrasound.It is added
0.36 mL of TBOT, 0.11 mL of the concentrated sulfuric acid, 1 h of magnetic agitation are stood overnight；Gained mixed liquor is slowly added to water at 80 DEG C
10 mL(rate, 0.5 mL min-1) be vigorously stirred simultaneously, 80 DEG C of 12 h of reflux.Respectively with dehydrated alcohol, water washing 3 times into
Property, 60 DEG C of dryings.SiO2/GO/TiO2Material is in tube furnace N210 DEG C of min of the lower 650 DEG C of 3 h(heating rates of calcining of atmosphere-1), it is down to 80 DEG C of taking-ups；
5) by step 4) products therefrom and NaOH(2 mol/L) solution reacts 4 h in 90 DEG C, distillation water washing to neutrality, and 60
DEG C drying, obtain target product RGO/TiO2HS double shells Hollow Sphere Composites.
RGO/TiO2The application of HS double shells hollow sphere composite photocatalyst material processing methyl orange dyeing waste water.Ultraviolet light
Source is 250 W mercury lamps, and dyeing waste water is 100 mL of methyl orange solution of 10 mg/L, and control water temperature is 30 DEG C, adjusts pH value of solution
Value is 6.5, and the RGO/TiO that 0.01 g embodiment 1 is prepared then is added2HS, 30 min of dark reaction reach adsorption equilibrium,
After 30 min of light reaction, methyl orange solution absorbance is measured under 464nm using ultraviolet-uisible spectrophotometer.In lower quality
The coloration of solution and methyl orange absorbance are directly proportional in fraction range, thus chroma removal rate can quantificational expression be formula: coloration is gone
Except rate (%)=(A0- A)/A0× 100%(A0For the initial absorbance of methyl orange；A is the absorbance of different time methyl orange).Knot
Fruit is shown in Table 1.
Embodiment 2
Present embodiment and the difference of specific embodiment 1 are: the amination SiO for obtaining 100 mg step 2 in step 3)2
Ultrasonic disperse is distinguished in 50 mL water for the GO stock solution of 10 mg/mL with 0.4 mL concentration, and amino is added dropwise in GO mixed liquor
Change SiO2In mixed liquor, continue 30 min of ultrasound.1 h of magnetic agitation is aged 24 h.It is multiple to change water, 60 DEG C of dryings obtain GO
The SiO of cladding2Ball is other identical as example 1.
RGO/TiO2The application of HS double shells hollow sphere composite photocatalyst material processing methyl orange dyeing waste water.Ultraviolet light
Source is 250 W mercury lamps, and dyeing waste water is 100 mL of methyl orange solution of 10 mg/L, and control water temperature is 25 DEG C, adjusts pH value of solution
Value is 7.0, and the RGO/TiO that 0.01 g embodiment 2 is prepared then is added2HS, 30 min of dark reaction reach adsorption equilibrium,
After 30 min of light reaction, measures remaining methyl orange absorbance in solution and calculate to obtain chroma removal rate.It the results are shown in Table 1.
Embodiment 3
Present embodiment and the difference of specific embodiment 1 are: in step 4), 0.30 mL of TBOT, the concentrated sulfuric acid 0.11 is added
ML stirs 1 h, stands overnight；Gained mixed liquor is slowly added to 10 mL(rate of water, 0.5 mL min at 80 DEG C-1) acute simultaneously
Strong stirring, 80 DEG C of 12 h of reflux.Respectively with dehydrated alcohol, water washing 3 times extremely neutral, 60 DEG C of dryings.It is other with 1 phase of embodiment
Together.
RGO / TiO2The application of HS double shells hollow sphere composite photocatalyst material processing methyl orange dyeing waste water.It is ultraviolet
Light source is 250 W mercury lamps, and dyeing waste water is 100 mL of methyl orange solution of 10 mg/L, and control water temperature is 30 DEG C, adjusts solution
PH value is 6.0, and the RGO/TiO that 0.01 g embodiment 4 is prepared then is added2It is flat that HS, 30 min of dark reaction reach absorption
It weighs, after light reaction 30min, measures remaining methyl orange absorbance in solution and calculate to obtain chroma removal rate.It the results are shown in Table 1.
Embodiment 4
Present embodiment and the difference of specific embodiment 1 are: in step 4), SiO2/GO/TiO2Material is in tube furnace N2Atmosphere
10 DEG C of min of lower 600 DEG C of 4 h(heating rates of calcining-1), it is down to 80 DEG C of taking-ups.Gains in NaOH(3 mol/L) solution
90 DEG C of 3 h of reaction, distillation water washing to neutrality, 60 DEG C dry to get target product RGO/TiO is arrived2HS double shells hollow sphere
Composite material.It is other same as Example 1.
RGO/TiO2The application of HS double shells hollow sphere composite photocatalyst material processing methyl orange dyeing waste water.Ultraviolet light
Source is 250 W mercury lamps, and dyeing waste water is 100 mL of methyl orange solution of 10 mg/L, and control water temperature is 25 DEG C, adjusts pH value of solution
Value is 6.5, and the RGO/TiO that 0.01 g embodiment 5 is prepared then is added2HS, 30 min of dark reaction reach adsorption equilibrium,
After 30 min of light reaction, measures remaining methyl orange absorbance in solution and calculate to obtain chroma removal rate.It the results are shown in Table 1.
Chroma removal rate and reaction rate constant value in 1 embodiment 1 to 4 of table
Seen from table 1, the RGO/TiO that the method for the present invention is prepared2HS double shells hollow sphere composite photocatalyst material is applied to
Pure TiO is compared in the processing of the dyeing waste water containing methyl orange2For, removal rate and reaction rate to methyl orange significantly improve.
RGO/TiO in embodiment 1 ~ 5230 min ultraviolet light Methyl Orange coloration of HS double shells hollow sphere composite photocatalyst material
Removal rate reaches 99 % or more, the coloration that Methyl Orange in Wastewater content that treated generates, lower than " textile dyeing and finishing industry water is dirty
Contaminate object discharge standard " requirement of (GB4287-2012) to coloration.
It is also known by table 1, the RGO/TiO prepared under conditions of embodiment 12HS double shells hollow sphere composite photocatalyst
Material is best to the removal effect of methyl orange in water, and SEM characterization (being tested with JEOL JSM-7800F instrument) is shown in Fig. 1.
Fig. 1 is that RGO/TiO is prepared in embodiment 12The SEM of HS double shells Hollow Sphere Composites schemes.It can from figure
To find out, RGO/TiO2The average diameter of HS is 300 nm, shell thickness ~ 55 nm(RGO thickness degree ~ 5 nm, TiO2Shell
Thickness ~ 50 nm), the partial size with good distribution.Wherein broken sample can be seen that the hollow sphere property of composite material.RGO
With TiO2Strong interaction and RGO/TiO between surface2The double layer hollow spherical structure of HS, can increase the surface of composite material
Product inhibits the compound of photo-generate electron-hole pair, to enhance the photocatalysis performance of composite material, shows prepared by the method for the present invention
Obtained RGO/TiO2HS composite photocatalyst material is the ideal material for preparing high-performance optical catalysis material.
Claims (10)
1. a kind of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material preparation method, feature
It is, in turn includes the following steps:
1) amination SiO is prepared2Powder template；
2) graphene oxide and configuration graphene oxide stock solution are prepared；
3) by amination SiO2Powder template and graphene oxide stock solution prepare the SiO of clad structure2/ graphene oxide ball；
4) by the SiO of clad structure2/ graphene oxide ball and butyl titanate and strong sulfuric acid response, prepare secondary clad structure
SiO2/ graphene oxide/TiO2Ball；
5) by the SiO of secondary clad structure2/ graphene oxide/TiO2Ball calcining thermal reduction, removes SiO2Template, preparation target produce
Object redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material.
2. redox graphene according to claim 1/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that the operating method of step 1) is, is 20~30 %'s by dehydrated alcohol, distilled water, mass fraction
Ammonium hydroxide is uniformly mixed for 37:7:1 according to volume ratio, is then slowly added into the ethyl orthosilicate of appropriate 99.9 % of mass fraction >,
4 ~ 8 h of magnetic agitation under the stirring rate of 800 ~ 1200 r/min, dehydrated alcohol wash, dry at 60 ~ 100 DEG C, obtain
SiO2Powder template；Then again by SiO2The ethanol solution of powder template and the trimethoxy siloxane of aminopropyl containing 3- according to
Volume ratio is uniformly mixed for 10:1 ~ 2:1,4 ~ 8 h of reflux operation under the conditions of 60 ~ 80 DEG C, dehydrated alcohol washing, and 60 ~ 100 DEG C
Lower drying, obtains amination SiO2Powder template.
3. redox graphene according to claim 1/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that the operating method of step 2 is that 2.5 parts of mass parts are added in the concentrated sulfuric acid of 115 parts of parts by volume
Sodium nitrate, add 5 parts of graphite after mixing, under the rate conditions of 800 ~ 1200 r/min stir 1 ~ 3 h, then exist
Reaction temperature be lower than 5 DEG C under the conditions of be slowly added to 15 parts of potassium permanganate, reaction vessel is placed in water bath with thermostatic control after starting reaction
In, after heating the reaction was continued a period of time, appropriate amount of deionized water is added after heating up again, is added again after reacting 10~20 min
The reaction was continued for the hydrogenperoxide steam generator that appropriate amount of deionized water and mass fraction are 20 ~ 40 % to reaction terminating, then with quality point
The dilute hydrochloric acid that number is 1 ~ 10 % carries out centrifuge washing to reaction product, then is washed with distilled water to neutrality, dry, obtains oxidation stone
Then black alkene disperses distilled water for the graphene oxide of preparation again, through ultrasonic Separation, centrifugal mixer, and be diluted with water configuration
Concentration is the graphene oxide stock solution of 5 ~ 15 mg/mL.
4. a kind of redox graphene according to claim 3/titanium dioxide double shells hollow sphere composite photocatalyst material
The preparation method of material, which is characterized in that before 15 parts of potassium permanganate of addition are reacted, reaction vessel is placed in ice water bath environment
In；In the preparation process of graphene oxide, after reaction vessel is placed in water bath with thermostatic control, it is warming up to 30 ~ 40 DEG C for the first time, heating
The reaction time is 1 ~ 3 h afterwards, is warming up to 90 ~ 100 DEG C again；In the preparation process of graphene oxide stock solution, when ultrasonic Separation
Between be 2 ~ 4 h, centrifugal mixer rate be 5000 ~ 7000 r/min, the centrifugal mixer time be 4 ~ 10 min.
5. redox graphene according to claim 1/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that the operating method of step 3) is the amination SiO for obtaining step 1)2Powder template and step
2) the graphene oxide stock solution difference ultrasonic disperse obtained obtains amination SiO in appropriate amount of deionized water2Mixed liquor and dense
Degree is the graphene oxide liquid mixture of 0.02 ~ 0.08 mg/mL, and amination is then added dropwise dropwise in graphene oxide liquid mixture
SiO2Mixed liquor continues 30 ~ 60 min of ultrasound, magnetic agitation, and ageing is washed with distilled water, dry, obtains clad structure
SiO2/ graphene oxide ball.
6. a kind of redox graphene according to claim 5/titanium dioxide double shells hollow sphere composite photocatalyst material
The preparation method of material, which is characterized in that amination SiO2The mass ratio of the quality of powder template and graphene oxide be 100:1 ~
100:4；Amination SiO is added dropwise dropwise in graphene oxide liquid mixture2After mixed liquor, the stirring rate of magnetic force is 800 ~ 1000
R/min, 1 ~ 2 h of mixing time, 12 ~ 36 h of digestion time.
7. redox graphene according to claim 1/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that the operating method of step 4) is the SiO for the clad structure for obtaining step 3)2/ graphite oxide
Alkene ball ultrasonic disperse is added butyl titanate and the concentrated sulfuric acid, stirs evenly, gained mixed liquor is in 60 in suitable dehydrated alcohol
Suitable quantity of water is slowly added under the conditions of ~ 80 DEG C of temperature, flow back 8 ~ 12 h, dehydrated alcohol washing, and it is dry, obtain secondary cladding
SiO2/ graphene oxide/TiO2Ball.
8. redox graphene according to claim 7/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that in the operating process of step 4), dehydrated alcohol: water: the volume ratio of butyl titanate be (7 ~
10): 1:(0.03 ~ 0.04)；(SiO2/ graphene oxide ball): the mass ratio of butyl titanate is 1:(0.8 ~ 1.2)；The concentrated sulfuric acid
Additive amount be overall solution volume 0.1 ~ 0.3 %(V/V).
9. redox graphene according to claim 1/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that the operating method of step 5) is, by step 4) resulting materials in N2Under atmosphere, in 500 ~ 700
Thermal reduction is calcined at DEG C, and removal SiO is then etched under the conditions of 80 ~ 100 DEG C with NaOH solution2Template, distillation water washing, 60 ~
100 DEG C of dryings obtain target product redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material.
10. redox graphene according to claim 9/titanium dioxide double shells hollow sphere composite photocatalyst material
Preparation method, which is characterized in that use tube furnace during calcining thermal reduction；Etching removal SiO2During template, NaOH
The concentration of solution is 1 ~ 3 mol/L, 3 ~ 4 h of reaction time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354835A (en) * | 2019-06-26 | 2019-10-22 | 东旭光电科技股份有限公司 | Hollow sphere graphene oxide carrier, hollow sphere graphene carrier, photochemical catalyst and application |
| CN112275272A (en) * | 2020-09-08 | 2021-01-29 | 广州户户通科技发展有限公司 | Preparation method and application of reduced graphene oxide titanium dioxide composite material |
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| CN113036137A (en) * | 2021-03-05 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Lithium ion battery cathode material and preparation method and application thereof |
| CN113354104A (en) * | 2021-07-01 | 2021-09-07 | 云南华谱量子材料有限公司 | Ecological system suitable for deepwater environment restoration and construction method thereof |
| CN115746652A (en) * | 2022-11-16 | 2023-03-07 | 华鸿画家居股份有限公司 | Coating with air purification and self-cleaning functions, coating and preparation method thereof |
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