CN109939673A - A kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material and preparation method thereof - Google Patents
A kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material, including bismuth molybdate catalysis material, the surface of the bismuth molybdate catalysis material is assisted and is roasted by NaOH to introduce ultra-thin bismuth oxide nanometer sheet.The invention also discloses ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material preparation methods, are specifically implemented according to the following steps: step 1, preparing molybdic acid bismuthino catalysis material；Step 2, the surface for assisting and roasting the molybdic acid bismuthino catalysis material for obtaining ultra-thin bismuth oxide nanometer sheet introducing step 1 by NaOH, is prepared ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material.The material soilless sticking, it is seen that optical response range is wide, and catalytic activity is significantly improved compared to pure bismuth molybdate, and repeat performance is good, and preparation process is simple, mild condition, and controllability is good, easy to operate.
Description
Technical field
The invention belongs to Industrial Catalysis preparation technical fields, more particularly to a kind of ultra-thin bismuth oxide/bismuth molybdate hetero-junctions
Catalysis material further relates to a kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material preparation method.
Background technique
Bi2MoO6(bismuth molybdate) as a kind of structure the simplest Aurivillius (in difficult to understand viral this), be by
(Bi2O2)2+Layer and (MoO4)2-Layer is superimposed to form the composite oxides of layer structure, Bi2MoO6Valence band be by Bi6sWith
O2pOrbital hybridization forms, and conduction band is Mo3dTrack is formed, and forbidden bandwidth is about 2.5~2.8eV, and maximum absorption wavelength is about
490nm can be absorbed some visible light and be excited, therefore, Bi2MoO6The research and development of catalysis material will be for raising too
The utilization rate of sunlight provides new thinking, has potential application in the depollution of environment and new energy development field, it has also become
One of the photochemical catalyst studied extensively at present.However, Bi2MoO6There are still visible light-responded relatively narrow, photo-generate electron-holes pair
It is easy to the defects of compound, the service life is shorter and migration rate is slower, significantly limits Bi2MoO6The practical application of catalysis material.
For Bi2MoO6Defect or deficiency existing for catalysis material are modified it using modification strategies, then develop visible light
The new material that catalytic activity is high and performance is stable is the key that practical application.
Summary of the invention
The first purpose of the invention is to provide a kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material, the materials
With good visible light-responded performance, and the separation of photo-generate electron-hole pair can be promoted, therefore it is visible to solve bismuth molybdate
The not high problem of photocatalytic activity.
A second object of the present invention is to provide a kind of preparation sides of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material
Method, to manufacture above-mentioned ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material.
In order to realize above-mentioned first purpose, the technical scheme adopted by the invention is that, a kind of ultra-thin bismuth oxide/bismuth molybdate
Heterojunction photocatalysis material, including bismuth molybdate, the surface of bismuth molybdate are assisted and are roasted by NaOH to introduce ultra-thin bismuth oxide nanometer
Piece.
In order to realize that above-mentioned second purpose, second of technical solution of the present invention be, a kind of ultra-thin bismuth oxide/
The preparation method of bismuth molybdate heterojunction photocatalysis material, is specifically implemented according to the following steps:
Step 1, bismuth molybdate catalysis material is prepared；
Step 2, the table for the bismuth molybdate for obtaining ultra-thin bismuth oxide nanometer sheet introducing step 1 is assisted and roasted by NaOH
Ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material is prepared in face.
Second of technical solution of the invention, also has the following characteristics that
The step 1 specifically includes:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
It is transferred to sealing in reaction kettle, is again put into reaction kettle is reacted to obtain mixed solution in electric heating constant-temperature blowing drying box later
A, to after reaction by mixed solution A cooled to room temperature, then be centrifuged, wash and vacuum drying treatment after obtain
Bismuth molybdate catalysis material.
In the step 1.2, the temperature reacted in electric heating constant-temperature blowing drying box is 160 DEG C, and the time is
12h。
In the step 1.2, the temperature for carrying out vacuum drying treatment is 60 DEG C, time 5h.
In the step 1.2, the reaction kettle is the stainless steel cauldron of liner Teflon.
The step 2 specifically includes:
Step 2.1, it disperses the powder for the bismuth molybdate catalysis material that step 1 obtains in deionized water and carries out ultrasound
Processing, obtains mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is no more than 0.5:1；
Step 2.3, temperature constant magnetic stirring is carried out to the mixed solution C that step 2.2 is prepared, is evaporated until by water, to
Mixed solution C is roasted after temperature constant magnetic stirring, finally obtains ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material
Material.
In the step 2.3, the temperature for carrying out temperature constant magnetic stirring is 60 DEG C -80 DEG C, time 6h-8h.
In the step 2.3, the temperature roasted is 150 DEG C -350 DEG C, time 1h-3h.
The beneficial effects of the present invention are: a kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material through the invention
The obtained ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material of preparation method, soilless sticking, it is seen that optical response range is wide, urges
To change activity to significantly improve compared to pure bismuth molybdate, repeat performance is good, and preparation process is simple, mild condition, and controllability is good,
It is easy to operate.
Detailed description of the invention
Fig. 1 is bismuth molybdate catalysis material and the ultra-thin heterogeneous light of bismuth oxide/bismuth molybdate that preparation method of the invention obtains
The X-ray powder diffraction figure of catalysis material；
Fig. 2 is bismuth molybdate catalysis material and the ultra-thin heterogeneous light of bismuth oxide/bismuth molybdate that preparation method of the invention obtains
The scanning electron microscope (SEM) photograph and EDS element of catalysis material map image；
Fig. 3 is bismuth molybdate catalysis material and the ultra-thin heterogeneous light of bismuth oxide/bismuth molybdate that preparation method of the invention obtains
The TEM of catalysis material schemes；
Fig. 4 is bismuth molybdate catalysis material and the ultra-thin heterogeneous light of bismuth oxide/bismuth molybdate that preparation method of the invention obtains
The solid UV-visible absorption spectrum of catalysis material；
Fig. 5 is bismuth molybdate catalysis material and the ultra-thin heterogeneous light of bismuth oxide/bismuth molybdate that preparation method of the invention obtains
The visible light catalysis activity comparison diagram of catalysis material；
Fig. 6 is for embodiment 1, embodiment 2, the 2 ultra-thin bismuth oxide/molybdenum of gained of embodiment 3, embodiment 4 and comparative example
The visible light catalysis activity comparison diagram of the sour heterogeneous catalysis material of bismuth；
Fig. 7 is that the ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate that preparation method of the invention obtains uses after 4 times
Visible light catalysis activity comparison diagram.
In figure, BMO represents the resulting bismuth molybdate catalysis material of comparative example 1, and BMO-Na0 represents comparative example 2
Obtained in roast after bismuth molybdate catalysis material, Etched BMO-Na1.5 represents etching obtained in comparative example 3
Bismuth molybdate catalysis material, BMO-Na1 represent the ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate obtained in embodiment 1,
BMO-Na1.5 represents the ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate obtained in embodiment 2.BMO-Na2 represents embodiment
The ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate, BMO-Na2.5 obtained in 3 represent ultra-thin oxidation obtained in embodiment 4
The heterogeneous catalysis material of bismuth/bismuth molybdate.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with Detailed description of the invention and specific embodiment.
A kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material of the invention, including bismuth molybdate, the surface of bismuth molybdate
It assists and roasts to introduce ultra-thin bismuth oxide nanometer sheet by NaOH.
The preparation method of the above-mentioned ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate of one kind of the invention, specifically according to
Lower step is implemented:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is no more than 0.5:1；
Step 2.3, temperature constant magnetic stirring 6h- is carried out to the mixed solution C that step 2.2 is prepared at 60 DEG C -80 DEG C
8h is evaporated until by water, to temperature constant magnetic stirring after mixed solution C is carried out to the roasting of 1h-3h at 150 DEG C -350 DEG C
It burns, finally obtains ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material.
Embodiment 1
The preparation method of the above-mentioned ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate of one kind of the invention, specifically according to
Lower step is implemented:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is 0.286:1；
Step 2.3, temperature constant magnetic stirring 6h is carried out to the mixed solution C that step 2.2 is prepared at 60 DEG C, until inciting somebody to action
Water is evaporated, to temperature constant magnetic stirring after mixed solution C is carried out to the roasting of 1h at 150 DEG C, finally obtain ultra-thin oxidation
Bismuth/bismuth molybdate heterojunction photocatalysis material.
Embodiment 2
The preparation method of the above-mentioned ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate of one kind of the invention, specifically according to
Lower step is implemented:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is 0.357:1；
Step 2.3, temperature constant magnetic stirring 7h is carried out to the mixed solution C that step 2.2 is prepared at 70 DEG C, until inciting somebody to action
Water is evaporated, to temperature constant magnetic stirring after mixed solution C is carried out to the roasting of 2h at 200 DEG C, finally obtain ultra-thin oxidation
Bismuth/bismuth molybdate heterojunction photocatalysis material.
Embodiment 3
The preparation method of the above-mentioned ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate of one kind of the invention, specifically according to
Lower step is implemented:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is 0.429:1；
Step 2.3, temperature constant magnetic stirring 7h is carried out to the mixed solution C that step 2.2 is prepared at 60 DEG C -80 DEG C,
Be evaporated until by water, to temperature constant magnetic stirring after mixed solution C is carried out to the roasting of 2.5h at 250 DEG C, finally obtain
Ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material.
Embodiment 4
The preparation method of the above-mentioned ultra-thin heterogeneous catalysis material of bismuth oxide/bismuth molybdate of one kind of the invention, specifically according to
Lower step is implemented:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is 0.5:1；
Step 2.3, temperature constant magnetic stirring 8h is carried out to the mixed solution C that step 2.2 is prepared at 80 DEG C, until inciting somebody to action
Water is evaporated, to temperature constant magnetic stirring after mixed solution C is carried out to the roasting of 3h at 350 DEG C, finally obtain ultra-thin oxidation
Bismuth/bismuth molybdate heterojunction photocatalysis material.
Comparative example 1
In order to facilitate comparison, it is heterogeneous that the above-mentioned ultra-thin bismuth oxide/bismuth molybdate of one kind of the invention is improved for embodiment 2
The preparation method of catalysis material, is specifically implemented according to the following steps:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Comparative example 2
In order to facilitate comparison, it is heterogeneous that the above-mentioned ultra-thin bismuth oxide/bismuth molybdate of one kind of the invention is improved for embodiment 2
The preparation method of catalysis material, is specifically implemented according to the following steps:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.3, temperature constant magnetic stirring 7h is carried out to the mixed solution B that step 2.1 is prepared at 70 DEG C, until inciting somebody to action
Water is evaporated, to temperature constant magnetic stirring after mixed solution C is carried out to the roasting of 2h at 200 DEG C, after finally obtaining roasting
Bismuth molybdate catalysis material.
Comparative example 3
In order to facilitate comparison, it is heterogeneous that the above-mentioned ultra-thin bismuth oxide/bismuth molybdate of one kind of the invention is improved for embodiment 2
The preparation method of catalysis material, is specifically implemented according to the following steps:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by measurement
Bi(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, most
After be stirred until obtain clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again will
Reaction kettle, is put into electric heating constant-temperature blowing drying box by sealing again later in its stainless steel cauldron for being transferred to liner Teflon,
Reaction 12h is carried out at 160 DEG C and obtains mixed solution A, to after reaction by mixed solution A cooled to room temperature, then is passed through
After centrifuge separation, washing, bismuth molybdate catalysis material is obtained after vacuum drying treatment 5h at 60 DEG C；
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, obtain
Mixed solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein
The molar ratio of NaOH and bismuth molybdate catalysis material is 0.357:1；
Step 2.3, temperature constant magnetic stirring 7h is carried out to the mixed solution C that step 2.2 is prepared at 70 DEG C, until inciting somebody to action
Water is evaporated, to temperature constant magnetic stirring after, finally obtain etching bismuth molybdate catalysis material.
Fig. 1 is the powder diagram of BMO and BMO-Na1.5.As can be seen from Figure 1 the XRD occurred in BMO-Na1.5 is special
It levies diffraction maximum and BMO is about the same, show that low-temperature bake has no effect on the crystal structure of BMO.Furthermore it can be seen that it is a series of new
Characteristic diffraction peak appearance, position is about 30.33 °, 37.62 °, 47.15 ° and 55.58 °, shows Bi2O3Presence.
Fig. 2 is the scanning electron microscope (SEM) photograph of BMO and BMO-Na1.5, wherein (a), (b) and (c) indicate BMO, (b), (c) be (a)
Enlarged drawing, (d), (e) and (f) indicate BMO-Na1.5, (e), (f) be (d) enlarged drawing.By (a), (b) and (c) in Fig. 2
As can be seen that BMO is the spherical hierarchical structure of three-dimensional assembled by a large amount of nanometer sheet, average diameter is 1 μm~2 μm, and
The thickness of nanometer sheet is about 10nm-20nm (figure (c))；The shape of (d), (e) and BMO-Na1.5 it can be seen from (f) in Fig. 2
Looks and size and BMO are essentially identical, while observing BMO Surface Creation Bi2O3Ultrathin nanometer piece (figure (e) and (f)).By Fig. 2
In (h) indicate the layered image of BMO-Na1.5, (i) indicate Bi, (j) indicate that Mo and (k) indicate O.
(a) and (b) indicates the TEM photo of BMO in Fig. 3；(c) the HR-TEM photo of BMO is indicated；(d) and (e) indicates BMO-
The TEM photo of Na1.5；(f) the HR-TEM figure of BMO-Na1.5 is indicated.The BMO and BMO- it can be seen from (a) and (d) in Fig. 3
Na1.5 is three-dimensional micro-sphere structure.BMO-Na1.5 is BMO three-dimensional micro-sphere structure and Bi it can be seen from (e) in Fig. 32O3It is ultra-thin
Nanometer sheet composition.Interplanar distance is 0.315nm and 0.331nm respectively at rhombic system BMO's it can be seen from (f) in Fig. 3
(131) interplanar distance and Bi2O3(111) interplanar distance it is corresponding the part of label (curve), the results showed that Bi2O3/
Bi2MoO6Hetero-junctions is successfully prepared.
Fig. 4 is the solid uv-visible absorption spectra of BMO and BMO-Na1.5.Figure 4, it is seen that the absorption of BMO
While be about 490nm, and BMO-Na1.5 catalysis material shows absorption edge similar with BMO, band gap slightly broadens.
Ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material prepared by the present invention can be used for the photocatalytic degradation of phenol.
Phenol, also known as carbolic acid (Carbolic acid) are a kind of common chemicals, are the certain resins of production, fungicide, anti-corrosion
The important source material of agent and drug (such as aspirin), and be the main intermediate production of macromolecule aromatic hydrocarbons oxidation
Object.The source of phenol wastewater is very extensive, mostlys come from the enterprise such as coal chemical industry, petrochemical industry, pesticide, phenolic resin and coking
The Phenol for Waste Water class concentration of industry, the industries such as chemical industry and oil refining is all larger than 1000mg/L, the water of the phenols routine in such waste water
Processing method is difficult to remove, and constitutes serious threat to human health and the ecological balance.Phenolic substances can pass through skin, mouth
Chamber, respiratory tract and mucous membrane enter in vivo, inhibit central nervous system, damage liver and kidney, and sucking high concentration steam can cause dizzy, head
Bitterly, the out of strength, dimness of vision and pulmonary edema etc..Human body excess intake phenol can cause to be poisoned, or even dead, seriously threaten the mankind
Health and living environment.Not only the health of the mankind can be caused to seriously threaten containing cruel waste water, can also generate harm to animals and plants.Water
In containing when drinking content and reaching, fish just will appear poisoning symptom, more than when can cause fish mortality, or even disappearance.Containing cruel
The toxicity of waste water may also suppress the natural speed of growth of other biologies in water body, destroy the ecological balance.Therefore, in China's surface water
The maximum permissible concentration that middle regulation volatilization is drunk is 0.1 milligrams per liter (V class water).Volatilization is provided in China's Drinking Water water standard
Intoxicated class is no more than 0.002 milligrams per liter.Therefore, it for the protection of the health of the mankind, animals and plants and environment, can effectively remove
Phenolic substances in waste water is of great significance.
Experiment condition is as follows: it is 10mgL that phenol, which is dissolved in water compound concentration,-1Degradation solution, be added catalyst powder it is (dense
Degree is 1000mgL-1), and place it in dark and stir after 30min reaches adsorption equilibrium, light degradation liquid is placed in photocatalysis
Illumination is carried out in reaction unit, experimental light sources are Metal halogen lamp, and (380~800nm of emission spectrum adds optical filter mistake to simulated visible light
Filter 420nm light below).It samples and is centrifuged every 30min, take supernatant liquor, using 4-AA spectrophotometry,
The absorbance that phenol is measured at maximum absorption wavelength 507nm using photometry measurement concentration variation, and is catalyzed with this to evaluate
The photocatalytic activity of agent.
(a) indicates the concentration variation of phenol in degradation process in Fig. 5, (b) indicates the degradation observed rate constant of phenol.By
(a) in Fig. 5 can be seen that the photocatalytic activity highest of BMO-Na1.5, and the photocatalytic activity of BMO is minimum, illumination 180min
Afterwards, phenol degrading rate is respectively 96.5% and 3.71%.
Fig. 6 is embodiment 1-4, and the concentration of the Photocatalytic Degradation of Phenol of 2 gained output of comparative example changes comparison diagram.By
Fig. 6 can be seen that the photocatalytic activity highest of BMO-Na1.5.
Fig. 7 is that BMO-Na1.5 uses the visible light catalysis activity comparison diagram after 4 times.As seen from Figure 7,4 are reused
After secondary, the activity of BMO-Na1.5 is declined slightly, and illustrates that the material property is stablized, there is good reusability.
Claims (9)
1. a kind of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material, which is characterized in that including bismuth molybdate, the table of bismuth molybdate
It assists and roasts by NaOH to introduce ultra-thin bismuth oxide nanometer sheet in face.
2. a kind of preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material, which is characterized in that specifically according to following
Step is implemented:
Step 1, bismuth molybdate catalysis material is prepared；
Step 2, the surface for the bismuth molybdate for obtaining ultra-thin bismuth oxide nanometer sheet introducing step 1, system are assisted and roasted by NaOH
It is standby to obtain ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material.
3. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 2, feature exist
In the step 1 specifically includes:
Step 1.1, Bi (NO is measured respectively according to the molar ratio of 2:13)3·5H2O and Na2MoO4·2H2O, first by the Bi of measurement
(NO3)3·5H2O is dissolved in ethylene glycol solution, and the Na of measurement is then added into ethylene glycol solution again2MoO4·2H2O, finally
It is stirred until obtaining clear solution；
Step 1.2, first dehydrated alcohol is added into the clear solution that step 1.1 obtains and is stirred evenly, then again by its turn
Enter sealing in reaction kettle, reaction kettle is put into again is reacted to obtain mixed solution A in electric heating constant-temperature blowing drying box later, to
After reaction by mixed solution A cooled to room temperature, then be centrifuged, wash and vacuum drying treatment after obtain molybdic acid
Bismuth catalysis material.
4. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 3, feature exist
In in the step 1.2, the temperature reacted in electric heating constant-temperature blowing drying box is 160 DEG C, time 12h.
5. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 4, feature exist
In in the step 1.2, the temperature for carrying out vacuum drying treatment is 60 DEG C, time 5h.
6. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 5, feature exist
In in the step 1.2, the reaction kettle is the stainless steel cauldron of liner Teflon.
7. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 3, feature exist
In the step 2 specifically includes:
Step 2.1, it disperses the powder for the bismuth molybdate that step 1 obtains in deionized water and is ultrasonically treated, mixed
Solution B；
Step 2.2, NaOH solution is added dropwise in mixed solution B step 2.1 being prepared, obtains mixed solution C, wherein NaOH
Molar ratio with bismuth molybdate catalysis material is no more than 0.5:1；
Step 2.3, temperature constant magnetic stirring is carried out to the mixed solution C that step 2.2 is prepared, is evaporated until by water, to constant temperature
Mixed solution C is roasted after magnetic agitation, finally obtains ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material.
8. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 7, feature exist
In in the step 2.2, the temperature for carrying out temperature constant magnetic stirring is 60 DEG C -80 DEG C, time 6h-8h.
9. the preparation method of ultra-thin bismuth oxide/bismuth molybdate heterojunction photocatalysis material according to claim 4, feature exist
In in the step 2.2, the temperature roasted is 150 DEG C -350 DEG C, time 1h-3h.
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