CN103877971A - Efficient visible-light-induced photocatalyst and preparation method thereof - Google Patents

Efficient visible-light-induced photocatalyst and preparation method thereof Download PDF

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CN103877971A
CN103877971A CN201410083039.4A CN201410083039A CN103877971A CN 103877971 A CN103877971 A CN 103877971A CN 201410083039 A CN201410083039 A CN 201410083039A CN 103877971 A CN103877971 A CN 103877971A
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solution
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microballoon
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graphene oxide
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于洪文
翟佳丽
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Northeast Institute of Geography and Agroecology of CAS
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Northeast Institute of Geography and Agroecology of CAS
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Abstract

The invention discloses an efficient visible-light-induced photocatalyst and a preparation method thereof, aiming to solve the problems of low adsorption performance of a photocatalyst to dye, poor catalytic activity and complex operation of the existing preparation method. The efficient visible-light-induced photocatalyst provided by the invention contains a substance A and Bi2WO6 microspheres, wherein the substance A accounts for 5%-15% of the mass of the visible-light-induced phtocatalyst, and is oxidized graphene or graphene. The preparation method provided by the invention comprises the steps: 1, preparing Bi2WO6 microspheres; 2, preparing an oxidized graphene/Bi2WO6 composite material; and 3, preparing an efficient visible-light-induced catalyst, thereby obtaining the graphene/Bi2WO6 composite material. The efficient visible-light-induced photocatalyst can be applied to the field of environmental pollution treatment and restoration.

Description

Efficient visible light Catalysts and its preparation method
Technical field
The present invention relates to a kind of visible light catalyst and preparation method thereof.
Background technology
Environmental problem and energy problem are the ultimate challenges of facing mankind.Photocatalitic Technique of Semiconductor, for we provide a kind of effective way of effectively curbing environmental pollution and efficiently utilizing solar energy, in numerous photochemical catalysts, due to titanium dioxide (TiO 2) there is nontoxic, good stability and catalytic activity advantages of higher, be widely used in catalytic field.But, due to TiO 2only can be by ultraviolet excitation as a kind of wide bandgap semiconductor materials, and ultraviolet light quantity only accounts for the 3%-4% of overall sunshine, the efficiency of light energy utilization of ultraviolet light is lower, as strict as possible recasting approximately TiO 2practical application and development.Therefore, the research and development of visible-light photocatalyst have become this area, world scientist's important scientific research proposition.
As everyone knows, graphene oxide (graphene oxide, english abbreviation is GO), as the oxide morphology of Graphene, a large amount of oxy radicals on its surface and marginal existence, as hydroxyl, carbonyl, epoxy radicals and carboxyl.The sp2-conjugated structure of this C-C and a large amount of oxy radicals make graphene oxide become a kind of semi-conducting material and have visible light-responded, can be for catalysis material.But graphene oxide, as a kind of electron acceptor, will be become reduced graphene (RGO) by photo-reduction in photocatalytic process; The generation of RGO will make the band gap width of this material change, and becomes conductor from semi-conducting material, then loses photocatalytic activity.Therefore, we research and develop emphatically a kind of composite based on graphene oxide, make graphene oxide become electron donor, promote the light stability of graphene oxide as visible light catalyst.
Research discovery, in many semi-conducting materials, Bi 2wO 6be best suited for the hydridization object with composite formation with graphene oxide.Bi 2wO 6have the following advantages: (1) Bi 2wO 6it is a kind of continuable photochemical catalyst.Have nontoxic, bio-compatibility is good, and has visible light activity; (2) graphene oxide and Bi 2wO 6position of energy band show, the light induced electron in graphene oxide conduction band will be transferred to Bi 2wO 6conduction band, thereby strengthen the photogenerated charge separative efficiency of photochemical catalyst, improve photocatalytic activity.Meanwhile, reduce the quantity of light induced electron in graphene oxide, promoted the oxidation resistance of graphene oxide.
Summary of the invention
The object of the invention is that visible light catalyst is low to the absorption property of dyestuff in order to solve, the problem of poor catalytic activity and existing preparation method's complicated operation, and provide efficient visible light Catalysts and its preparation method.
Efficient visible light catalyst of the present invention contains substance A and Bi 2wO 6microballoon, wherein, the quality of substance A accounts for 5%～15% of efficient visible light catalyst quality, and described substance A is graphene oxide or Graphene;
Described Bi 2wO 6microballoon, prepare as follows:
One, Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
Two, Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
Three, mixed liquor A: the Bi (NO that step 2 is obtained 3) 3the Na that the step 1 that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (NO described in step 3 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
Four, Bi 2wO 6the preparation of microballoon: step 3 mixed liquor A is joined in reactor, is to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, takes out, and is cooled to room temperature, obtains solid matter, then alternately washs 4～5 times centrifugal solid matter, obtains Bi 2wO 6microballoon;
Centrifugal replacing described in step 4 washed as solid matter is first used to absolute ethyl alcohol centrifuge washing 1 time, then uses deionized water centrifuge washing 1 time, is 1 centrifugal alternately washing.
The preparation method of efficient visible light catalyst in the present invention, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3the Na that 1. step that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (the NO of step described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in reactor, be to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, the preparation of efficient visible light catalyst:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 40 ℃～50 ℃ in temperature, dries 10h～24h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6in the deionized water that microballoon is dissolved into, ultrasonic mixing 30min～40min, obtains Bi 2wO 6microspheres solution, wherein, the Bi of the oven dry of step described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are (0.1g～0.15g): 100mL;
2., graphene oxide is dissolved in to deionized water,, after mixing, obtain graphene oxide solution;
Wherein, the quality of graphite oxide and the volume ratio of deionized water are (0.005g～0.015g): 100mL;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
The preparation method of efficient visible light catalyst in the present invention, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3the Na that 1. step that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (the NO of step described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in reactor, be to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, graphene oxide/Bi 2wO 6the preparation of composite:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 40 ℃～50 ℃ in temperature, dries 10h～24h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6microballoon is dissolved in deionized water, and ultrasonic mixing 30min～40min, obtains Bi 2wO 6microspheres solution, wherein, the Bi of the oven dry of step described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are (0.1g～0.15g): 100mL;
2., graphene oxide is dissolved in to deionized water,, after mixing, obtain graphene oxide solution;
Wherein, the quality of graphite oxide and the volume ratio of deionized water are (0.005g～0.015g): 100mL;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite;
Three, the preparation of efficient visible light catalyst:
Utilize freeze drier by the graphene oxide/Bi obtaining in step 3 2wO 6composite carries out freeze drying, and then by cryodesiccated graphene oxide/Bi 2wO 6composite joins in Muffle furnace, under temperature is 500 ℃～600 ℃, the condition of argon gas as protective gas, calcines 2h～3h, obtains Graphene/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
Principle of the present invention: utilize semi-conductive band theory, select the semi-conducting material mating with Graphene, make the conduction band of Graphene higher than selected semi-conductive conduction band, realize the light induced electron producing in Graphene and can transfer to smoothly semi-conducting material under the exciting of light, the quantity that reduces light induced electron in Graphene suppresses its photo-reduction, meanwhile, strengthen the separative efficiency of photo-generated carrier, improve photocatalytic activity.The semi-conducting material mating with Graphene of selecting is in the present invention Bi 2wO 6microballoon, then a kind of non-functionalization, eco-friendly cryodesiccated method realize Graphene at Bi 2wO 6surface coated.Technical scheme one in the present invention is to have obtained graphene oxide/Bi 2wO 6composite, technical scheme two is by the graphene oxide/Bi obtaining 2wO 6graphite oxide reduction in composite, obtains Graphene/Bi 2wO 6composite.
Beneficial effect of the present invention:
1, because graphene coated is at Bi 2wO 6on the surface of microballoon, Graphene/Bi that the present invention obtains 2wO 6composite, with the simple Bi not being wrapped by 2wO 6the specific area of microballoon is compared, Graphene/Bi 2wO 6the surface area of composite increases, so the adsorption capacity of dyestuff has been improved to 3 times, the separative efficiency of photo-generated carrier strengthens, thus with simple Bi 2wO 6the photocatalytic activity of microballoon is compared, Graphene/Bi 2wO 6composite photocatalytic activity has promoted 6 times.
2, the Graphene/Bi making of the present invention 2wO 6composite has very high stability as photochemical catalyst.In stability confirmatory experiment, the Graphene/Bi making of the present invention 2wO 6composite is continuing in the process of 14h continuous degradation dyestuff, Graphene/Bi 2wO 6composite has no obvious catalytic activity deactivation phenomenom.
3, preparation method of the present invention is simple, and the cost of whole preparation process is low.
Accompanying drawing explanation
Fig. 1 is the Bi that embodiment 2 step 1 obtain 2wO 6the ESEM picture of microballoon;
Fig. 2 is embodiment 2 step 1 Bi 2wO 6the transmission electron microscope picture of microballoon, multiplication factor 0.5 μ m;
Fig. 3 is embodiment 2 step 1 Bi 2wO 6the transmission electron microscope picture of microballoon, multiplication factor 0.2 μ m;
Fig. 4 is graphene oxide/Bi that the mass percent of the graphene oxide that obtains of embodiment 2 is 10% 2wO 6the surface sweeping Electronic Speculum picture of composite;
Fig. 5 is graphene oxide/Bi that the mass percent of the graphene oxide that obtains of embodiment 2 is 10% 2wO 6the transmission electron microscope picture of composite, multiplication factor 0.2 μm;
Fig. 6 is graphene oxide/Bi that the mass percent of the graphene oxide that obtains of embodiment 2 is 10% 2wO 6the transmission electron microscope picture at composite edge, multiplication factor 0.2 μm;
Fig. 7 is Bi 2wO 6microballoon and graphene oxide/Bi 2wO 6the curve map of composite degradation of dye under the exciting of visible ray, wherein, line 1 is not for there is no the curve map of degradation of dye under the condition of photochemical catalyst, and line 2 is at Bi 2wO 6the curve map of microballoon degradation of dye during as photochemical catalyst, line 3 is the graphene oxide/Bi that is 5% at the mass percent of graphene oxide 2wO 6composite is during as photochemical catalyst, the curve map of degradation of dye, and line 4 is the graphene oxide/Bi that is 15% at the mass percent of graphene oxide 2wO 6composite is during as photochemical catalyst, the curve map of degradation of dye, and line 5 is the graphene oxide/Bi that is 10% at the mass percent of graphene oxide 2wO 6composite is during as photochemical catalyst, the curve map of degradation of dye;
Fig. 8 is Bi 2wO 6microballoon and graphene oxide/Bi 2wO 6the kinetic curve figure of composite, wherein, post 1 is Bi 2wO 6microballoon, graphene oxide/Bi that the mass percent that post 2 is graphene oxide is 5% 2wO 6composite, graphene oxide/Bi that the mass percent that post 3 is graphene oxide is 10% 2wO 6composite, graphene oxide/Bi that the mass percent that post 4 is graphene oxide is 15% 2wO 6composite;
Fig. 9 is graphene oxide/Bi that the mass percent of the graphene oxide that obtains of embodiment 2 is 10% 2wO 6the curve map of composite degradation of dye under the exciting of visible ray.
The specific embodiment
The specific embodiment one: in present embodiment, efficient visible light catalyst contains substance A and Bi 2wO 6microballoon, wherein, the quality of substance A accounts for 5%～15% of efficient visible light catalyst quality, and described substance A is graphene oxide or Graphene;
Described Bi 2wO 6microballoon, prepare as follows:
One, Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
Two, Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mm ol): 40mL;
Three, mixed liquor A: the Bi (NO that step 2 is obtained 3) 3the Na that the step 1 that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (NO described in step 3 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
Four, Bi 2wO 6the preparation of microballoon: step 3 mixed liquor A is joined in reactor, is to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, takes out, and is cooled to room temperature, obtains solid matter, then alternately washs 4～5 times centrifugal solid matter, obtains Bi 2wO 6microballoon;
Centrifugal replacing described in step 4 washed as solid matter is first used to absolute ethyl alcohol centrifuge washing 1 time, then uses deionized water centrifuge washing 1 time, is 1 centrifugal alternately washing.
The specific embodiment two: the difference of present embodiment and the specific embodiment one is that described substance A accounts for 10% of efficient visible light catalyst quality.
The specific embodiment three: the preparation method of efficient visible light catalyst in present embodiment, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3the Na that 1. step that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (the NO of step described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in reactor, be to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, the preparation of efficient visible light catalyst:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 40 ℃～50 ℃ in temperature, dries 10h～24h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6in the deionized water that microballoon is dissolved into, ultrasonic mixing 30min～40min, obtains Bi 2wO 6microspheres solution, wherein, the Bi of the oven dry of step described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are (0.1g～0.15g): 100mL;
2., graphene oxide is dissolved in to deionized water,, after mixing, obtain graphene oxide solution;
Wherein, the quality of graphite oxide and the volume ratio of deionized water are (0.005g～0.015g): 100mL;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
The specific embodiment four: the difference of present embodiment and the specific embodiment three is, the Bi (NO of step 1 described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is 1:1.Other are identical with the specific embodiment three.
The specific embodiment five: the difference of present embodiment and the specific embodiment three or four is, the Bi of the oven dry of step 2 described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are 0.1g:100mL.Other are identical with the specific embodiment three or four.
The specific embodiment six: the difference of one of present embodiment and specific embodiment three to five is, the quality of graphene oxide and the volume ratio of deionized water of step 2 described in is 2. 0.010g:100mL.Other are identical with one of specific embodiment three to five.
The specific embodiment seven: the preparation method of efficient visible light catalyst in present embodiment, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3the Na that 1. step that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (the NO of step described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in reactor, be to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, graphene oxide/Bi 2wO 6the preparation of composite:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 40 ℃～50 ℃ in temperature, dries 10h～24h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6microballoon is dissolved in deionized water, and ultrasonic mixing 30min～40min, obtains Bi 2wO 6microspheres solution, wherein, the Bi of the oven dry of step described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are (0.1g～0.15g): 100mL;
2., graphene oxide is dissolved in to deionized water,, after mixing, obtain graphene oxide solution;
Wherein, the quality of graphite oxide and the volume ratio of deionized water are (0.005g～0.015g): 100mL;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite;
Three, the preparation of efficient visible light catalyst:
Utilize freeze drier by the graphene oxide/Bi obtaining in step 3 2wO 6composite carries out freeze drying, and then by cryodesiccated graphene oxide/Bi 2wO 6composite joins in Muffle furnace, under temperature is 500 ℃～600 ℃, the condition of argon gas as protective gas, calcines 2h～3h, obtains Graphene/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
The specific embodiment eight: the difference of present embodiment and the specific embodiment seven is, the Bi (NO of step 1 described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is 1:1.Other are identical with the specific embodiment seven.
The specific embodiment nine: the difference of present embodiment and the specific embodiment seven or eight is, the Bi of the oven dry of step 2 described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are 0.1g:100mL.Other are identical with the specific embodiment seven or eight.
The specific embodiment nine: the difference of one of present embodiment and specific embodiment seven to nine is, the quality of graphene oxide and the volume ratio of deionized water of step 2 described in is 2. 0.010g:100mL.Other are identical with one of specific embodiment seven to nine.
Verify effect of the present invention by following examples:
Embodiment 1: a kind of efficient visible light catalyst Graphene/Bi in the present embodiment 2wO 6the preparation method of composite, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by the Na of 1.25mmol 2wO 42H 2o is dissolved in after the deionized water of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Na 2wO 4solution;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by the Bi (NO of 2.5mmol 3) 35H 2o is dissolved in the ethylene glycol of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Bi (NO 3) 3-ethylene glycol solution;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3-ethylene glycol solution 40mL joins the Na that 1. step of 40mL obtains 2wO 42H 2in O solution, be uniformly mixed 3h, obtain mixed liquor A;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in the reactor that volume is 100mL, be to react 24h under the condition of 180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, the preparation of efficient visible light catalyst:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 45 ℃ in temperature, dries 12h, obtains drying Bi 2wO 6microballoon; Then will dry Bi 2wO 6microballoon 0.1g is dissolved in 100mL deionized water, and ultrasonic mixing 40min, obtains Bi 2wO 6microspheres solution;
2., 0.005g graphene oxide is dissolved in to 100mL water,, after mixing, obtain graphene oxide solution;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
The efficient visible light catalyst obtaining in the present embodiment is graphene oxide/Bi 2wO 6composite, described graphene oxide/Bi 2wO 6in composite, the mass percent of graphene oxide is 10%.
As shown in Figure 7: line 2 is at Bi 2wO 6the curve of microballoon degradation of dye during as photochemical catalyst, graphene oxide/Bi that the mass percent of the graphene oxide that line 3 obtains for the present embodiment is 5% 2wO 6composite is during as photochemical catalyst, and the curve of degradation of dye, has Fig. 7 known: in the time that light application time is 90min, and graphene oxide/Bi prepared by the present embodiment 2wO 6composite is Bi as visible light catalyst to the degradation efficiency of dyestuff 2wO 61.3 times of microballoon.
There is Fig. 8 known: post 1 is at Bi 2wO 6microballoon degradation rate constant during as photochemical catalyst, graphene oxide/Bi that the mass percent of the graphene oxide that post 2 obtains for the present embodiment is 5% 2wO 6composite degradation rate constant during as photochemical catalyst, has Fig. 8 known: graphene oxide/Bi prepared by the present embodiment 2wO 6the degradation rate constant of composite during as visible light catalyst is than Bi 2wO 6microballoon is 1.4 times.
Embodiment 2: a kind of efficient visible light catalyst Graphene/Bi in the present embodiment 2wO 6the preparation method of composite, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by the Na of 1.25mmol 2wO 42H 2o is dissolved in after the deionized water of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Na 2wO 4solution;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by the Bi (NO of 2.5mmol 3) 35H 2o is dissolved in the ethylene glycol of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Bi (NO 3) 3-ethylene glycol solution;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3-ethylene glycol solution 40mL joins the Na that 1. step of 40mL obtains 2wO 42H 2in O solution, be uniformly mixed 3h, obtain mixed liquor A;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in the reactor that volume is 100mL, be to react 24h under the condition of 180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, the preparation of efficient visible light catalyst:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 45 ℃ in temperature, dries 12h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6microballoon 0.1g is dissolved in the deionized water of 100mL, and ultrasonic mixing 40min, obtains Bi 2wO 6microspheres solution;
2., 0.010g graphene oxide is dissolved in to 100mL water,, after mixing, obtain graphene oxide solution;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
Fig. 1 is the present embodiment step 1 Bi 2wO 6the ESEM picture of microballoon, Fig. 2 and Fig. 3 are embodiment 2 step 1 Bi 2wO 6the transmission electron microscope picture of microballoon, graphene oxide/Bi that the mass percent of the graphene oxide that Fig. 4 the present embodiment obtains is 10% 2wO 6the surface sweeping Electronic Speculum picture of composite, Fig. 5 and Fig. 6 are graphene oxide/Bi that the mass percent of the graphene oxide that obtains of the present embodiment is 10% 2wO 6the projection Electronic Speculum picture at composite and edge thereof.Can see and be coated on Bi by Fig. 4, Fig. 5 and Fig. 6 2wO 6the graphene oxide of microsphere surface.
The efficient visible light catalyst obtaining in the present embodiment is graphene oxide/Bi 2wO 6composite, described graphene oxide/Bi 2wO 6in composite, the mass percent of graphene oxide is 10%.
As shown in Figure 7: line 2 is at Bi 2wO 6the curve of microballoon degradation of dye during as photochemical catalyst, line 5 obtains graphene oxide/Bi that the mass percent of graphene oxide is 10% for the present embodiment 2wO 6composite is during as photochemical catalyst, and the curve of degradation of dye, has Fig. 7 known: in the time that light application time is 90min, and graphene oxide/Bi prepared by the present embodiment 2wO 6if composite is the degradation efficiency Bi to dyestuff as visible light catalyst 2wO 62 times of microballoon.
There is Fig. 8 known: post 1 is at Bi 2wO 6microballoon degradation rate constant during as photochemical catalyst, post 3 is the graphene oxide/Bi that is 10% at the mass percent of graphene oxide 2wO 6composite degradation rate constant during as photochemical catalyst, has Fig. 8 known: graphene oxide/Bi prepared by the present embodiment 2wO 6the degradation rate constant of composite during as visible light catalyst is Bi 2wO 65 times of microballoons.
Fig. 9 is graphene oxide/Bi that the mass percent of the graphene oxide that obtains of embodiment 2 is 10% 2wO 6the curve map of composite degradation of dye under the exciting of visible ray.As shown in Figure 9: graphene oxide/Bi that the present embodiment obtains 2wO 6in the process of composite continuous degradation dyestuff in 14h, Graphene/Bi 2wO 6composite has no obvious catalytic activity deactivation phenomenom.
Embodiment 3: the preparation method of efficient visible light catalyst in the present embodiment, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by the Na of 1.25mmol 2wO 42H 2o is dissolved in after the deionized water of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Na 2wO 4solution;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by the Bi (NO of 2.5mmol 3) 35H 2o is dissolved in the ethylene glycol of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Bi (NO 3) 3-ethylene glycol solution;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3-ethylene glycol solution 40mL joins the Na that 1. step of 40mL obtains 2wO 42H 2in O solution, be uniformly mixed 3h, obtain mixed liquor A;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in the reactor that volume is 100mL, under the condition that is 180 in temperature, react 24h, take out, be cooled to room temperature, obtain solid matter, then alternately wash 5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, graphene oxide/Bi 2wO 6the preparation of composite:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 45 ℃ in temperature, dries 12h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6microballoon 0.1g is dissolved in the deionized water of 100mL, and ultrasonic mixing 40min, obtains Bi 2wO 6microspheres solution;
2., 0.015g graphene oxide is dissolved in to 100mL water,, after mixing, obtain graphene oxide solution;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
The efficient visible light catalyst obtaining in the present embodiment is graphene oxide/Bi 2wO 6composite, described graphene oxide/Bi 2wO 6in composite, the mass percent of graphene oxide is 15%.
As shown in Figure 7: line 2 is at Bi 2wO 6the curve of microballoon degradation of dye during as photochemical catalyst, line 4 obtains graphene oxide/Bi that the mass percent of graphene oxide is 15% for the present embodiment 2wO 6composite is during as photochemical catalyst, and the curve of degradation of dye, has Fig. 7 known: in the time that light application time is 90min, and graphene oxide/Bi prepared by the present embodiment 2wO 6if composite is the degradation efficiency Bi to dyestuff as visible light catalyst 2wO 63 times of microballoon.
There is Fig. 8 known: post 1 is at Bi 2wO 6microballoon degradation rate constant during as photochemical catalyst, post 3 is the graphene oxide/Bi that is 15% at the mass percent of graphene oxide 2wO 6composite degradation rate constant during as photochemical catalyst, has Fig. 8 known: graphene oxide/Bi prepared by the present embodiment 2wO 6the degradation rate constant of composite during as visible light catalyst is Bi 2wO 62.6 times of microballoon.
Embodiment 4: the preparation method of efficient visible light catalyst in the present embodiment, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by the Na of 1.25mmol 2wO 42H 2o is dissolved in after the deionized water of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Na 2wO 4solution;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by the Bi (NO of 2.5mmol 3) 35H 2o is dissolved in the ethylene glycol of 40mL, ultrasonic and stir till, ultrasonic time is 10min, obtains Bi (NO 3) 3-ethylene glycol solution;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3-ethylene glycol solution 40mL joins the Na that 1. step of 40mL obtains 2wO 42H 2in O solution, be uniformly mixed 3h, obtain mixed liquor A;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in the reactor that volume is 100mL, be to react 24h under the condition of 180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, graphene oxide/Bi 2wO 6the preparation of composite:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 45 ℃ in temperature, dries 12h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6microballoon 0.1g is dissolved in the deionized water of 100mL, and ultrasonic mixing 40min, obtains Bi 2wO 6microspheres solution;
2., 0.010g graphene oxide is dissolved in to 100mL water,, after mixing, obtain graphene oxide solution;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite;
Three, the preparation of efficient visible light catalyst:
By the graphene oxide/Bi obtaining in step 3 2wO 6after composite freeze drying, join in Muffle furnace, under temperature is 500 ℃, the condition of argon gas as protective gas, calcine 2h, obtain efficient visible light catalyst Graphene/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
The efficient visible light catalyst obtaining in the present embodiment is Graphene/Bi 2wO 6composite, described Graphene/Bi 2wO 6in composite, the mass percent of Graphene is 10%.
Fig. 7 is Bi 2wO 6graphene oxide/Bi that microballoon and embodiment 1-3 obtain 2wO 6the curve map of composite degradation of dye under the exciting of visible ray, Fig. 8 is Bi 2wO 6graphene oxide/Bi that microballoon and embodiment 1-3 obtain 2wO 6the kinetic curve figure of composite.
To sum up, because graphene coated is at Bi 2wO 6on the surface of microballoon, Graphene/Bi that the present invention obtains 2wO 6composite, with the simple Bi not being wrapped by 2wO 6the specific area of microballoon is compared, Graphene/Bi 2wO 6the surface area of composite increases, so the adsorption capacity of dyestuff has been improved to 3 times, the separative efficiency of photo-generated carrier strengthens, thus with simple Bi 2wO 6the photocatalytic activity of microballoon is compared, Graphene/Bi 2wO 6composite photocatalytic activity has promoted 6 times.

Claims (10)

1. efficient visible light catalyst, is characterized in that efficient visible light catalyst contains substance A and Bi 2wO 6microballoon, wherein, the quality of substance A accounts for 5%～15% of efficient visible light catalyst quality, and described substance A is graphene oxide or Graphene;
Described Bi 2wO 6microballoon, prepare as follows:
One, Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
Two, Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
Three, mixed liquor A: the Bi (NO that step 2 is obtained 3) 3the Na that the step 1 that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (NO described in step 3 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
Four, Bi 2wO 6the preparation of microballoon: step 3 mixed liquor A is joined in reactor, is to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, takes out, and is cooled to room temperature, obtains solid matter, then alternately washs 4～5 times centrifugal solid matter, obtains Bi 2wO 6microballoon;
Centrifugal replacing described in step 4 washed as solid matter is first used to absolute ethyl alcohol centrifuge washing 1 time, then uses deionized water centrifuge washing 1 time, is 1 centrifugal alternately washing.
2. efficient visible light catalyst according to claim 1, is characterized in that described substance A accounts for 10% of efficient visible light catalyst quality.
3. the preparation method of efficient visible light catalyst, is characterized in that the preparation method of efficient visible light catalyst, as follows preparation:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3the Na that 1. step that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (the NO of step described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in reactor, be to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, the preparation of efficient visible light catalyst:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 40 ℃～50 ℃ in temperature, dries 10h～24h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6in the deionized water that microballoon is dissolved into, ultrasonic mixing 30min～40min, obtains Bi 2wO 6microspheres solution, wherein, the Bi of the oven dry of step described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are (0.1g～0.15g): 100mL;
2., graphene oxide is dissolved in to deionized water,, after mixing, obtain graphene oxide solution;
Wherein, the quality of graphite oxide and the volume ratio of deionized water are (0.005g～0.015g): 100mL;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
4. the preparation method of efficient visible light catalyst according to claim 3, is characterized in that the Bi (NO described in step 1 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is 1:1.
5. the preparation method of efficient visible light catalyst according to claim 3, is characterized in that the Bi of the oven dry described in step 2 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are 0.1g:100mL.
6. the preparation method of efficient visible light catalyst according to claim 3, is characterized in that the quality of graphene oxide described in step 2 2. and the volume ratio of deionized water are 0.010g:100mL.
7. the preparation method of efficient visible light catalyst, prepares as follows:
One, Bi 2wO 6the preparation of microballoon:
1., Na 2wO 4the preparation of solution: by Na 2wO 42H 2o dissolution of solid, after deionized water, after ultrasonic agitation is even, obtains Na 2wO 4solution, the described ultrasonic agitation time is 5min～10min;
Wherein, described Na 2wO 42H 2the amount of substance of O solid and the volume ratio of deionized water are (1.0mmol～1.5mmol): 40mL;
2., Bi (NO 3) 3the preparation of-ethylene glycol solution: by Bi (NO 3) 35H 2o dissolution of solid, in ethylene glycol, after ultrasonic agitation is even, obtains Bi (NO 3) 3-ethylene glycol solution, described stirring ultrasonic time is 5min～10min;
Wherein, described Bi (NO 3) 35H 2the amount of substance of O solid and the volume ratio of ethylene glycol are (2.0mmol～3.0mmol): 40mL;
3., mixed liquor A: the Bi (NO that 2. step is obtained 3) 3the Na that 1. step that-ethylene glycol solution joins obtains 2wO 4in solution, be uniformly mixed 2h～3h, obtain mixed liquor A;
Bi (the NO of step described in 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is (0.5～1.5): 1;
4., Bi 2wO 6the preparation of microballoon: by step 3. mixed liquor A join in reactor, be to react 20h～25h under the condition of 170 ℃～180 ℃ in temperature, take out, be cooled to room temperature, obtain solid matter, then alternately wash 4～5 times centrifugal solid matter, obtain Bi 2wO 6microballoon;
The centrifugal alternately washing of step described in be 4. for first to use absolute ethyl alcohol centrifuge washing 1 time by solid matter, then use deionized water centrifuge washing 1 time, is 1 time and centrifugally alternately washs;
Two, graphene oxide/Bi 2wO 6the preparation of composite:
1. the Bi, step 1 being obtained 2wO 6microballoon is under the condition of 40 ℃～50 ℃ in temperature, dries 10h～24h, obtains drying Bi 2wO 6microballoon; Then by the Bi of drying 2wO 6microballoon is dissolved in deionized water, and ultrasonic mixing 30min～40min, obtains Bi 2wO 6microspheres solution, wherein, the Bi of the oven dry of step described in 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are (0.1g～0.15g): 100mL;
2., graphene oxide is dissolved in to deionized water,, after mixing, obtain graphene oxide solution;
Wherein, the quality of graphite oxide and the volume ratio of deionized water are (0.005g～0.015g): 100mL;
3. the graphene oxide solution, 2. step being obtained joins the Bi that 1. step obtains 2wO 6in microspheres solution, after ultrasonic mixing 1h～2h, obtain mixed solution B, mixed solution B is placed in to liquid nitrogen freezing, obtain graphene oxide/Bi 2wO 6composite;
Three, the preparation of efficient visible light catalyst:
Utilize freeze drier by the graphene oxide/Bi obtaining in step 3 2wO 6composite carries out freeze drying, and then by cryodesiccated graphene oxide/Bi 2wO 6composite joins in Muffle furnace, under temperature is 500 ℃～600 ℃, the condition of argon gas as protective gas, calcines 2h～3h, obtains Graphene/Bi 2wO 6composite, completes the preparation of efficient visible light catalyst.
8. the preparation method of efficient visible light catalyst according to claim 7, is characterized in that the Bi (NO described in step 1 3. 3) 3-ethylene glycol solution and Na 2wO 4the volume ratio of solution is 1:1.
9. the preparation method of efficient visible light catalyst according to claim 7, is characterized in that the Bi of the oven dry described in step 2 1. 2wO 6the quality of microballoon and the volume ratio of deionized water are 0.1g:100mL.
10. the preparation method of efficient visible light catalyst according to claim 7, is characterized in that the quality of graphene oxide described in step 2 2. and the volume ratio of deionized water are 0.010g:100mL.
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CN109967067A (en) * 2019-03-25 2019-07-05 昆明理工大学 A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst
CN110511509A (en) * 2019-09-03 2019-11-29 海南师范大学 It is a kind of can photocatalytic degradation polyvinyl chloride plastic film and preparation method thereof
CN110743536A (en) * 2019-11-13 2020-02-04 盐城工学院 Bi-Bi2WO6Preparation method and application of visible light photocatalyst

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Application publication date: 20140625