CN109939673B - Ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and preparation method thereof - Google Patents
Ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and preparation method thereof Download PDFInfo
- Publication number
- CN109939673B CN109939673B CN201910233240.9A CN201910233240A CN109939673B CN 109939673 B CN109939673 B CN 109939673B CN 201910233240 A CN201910233240 A CN 201910233240A CN 109939673 B CN109939673 B CN 109939673B
- Authority
- CN
- China
- Prior art keywords
- photocatalytic material
- bismuth
- bismuth molybdate
- ultrathin
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses an ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material which comprises a bismuth molybdate photocatalytic material, wherein ultrathin bismuth oxide nanosheets are introduced into the surface of the bismuth molybdate photocatalytic material through NaOH assistance and roasting. The invention also discloses a preparation method of the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material, which is implemented according to the following steps: step 1, preparing a bismuth molybdate-based catalytic material; and 2, introducing ultrathin bismuth oxide nanosheets to the surface of the bismuth molybdate-based catalytic material obtained in the step 1 through NaOH assistance and roasting to prepare the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material. The material has the advantages of no agglomeration, wide visible light response range, obviously improved catalytic activity compared with pure bismuth molybdate, good reusability, simple preparation process, mild condition, good controllability and convenient operation.
Description
Technical Field
The invention belongs to the technical field of industrial catalytic preparation, and particularly relates to an ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and a preparation method of the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
Background
Bi2MoO6(bismuth molybdate), one of the simplest Aurivillius structures, is composed of (Bi)2O2)2+Layer and (MoO)4)2-Composite oxide of layered structure formed by alternately laminating layers, Bi2MoO6The valence band of (A) is represented by Bi6sAnd O2pThe track is hybridized to form the compound,the conduction band being Mo3dA track is formed, the forbidden band width is about 2.5-2.8 eV, the maximum absorption wavelength is about 490nm, and the track can absorb part of visible light to be excited, therefore, Bi2MoO6Research and development of the photocatalytic material can provide a new idea for improving the utilization rate of sunlight, has potential application value in the fields of environmental purification and new energy development, and becomes one of the photocatalysts widely researched at present. However, Bi2MoO6Still has the defects of narrow visible light response, easy recombination of photo-generated electron-hole pairs, short service life, slow migration rate and the like, and greatly limits Bi2MoO6Practical application of the photocatalytic material. For Bi2MoO6The defects or shortcomings of the photocatalytic material are that the photocatalytic material is modified by a modification strategy, and then a new material with high visible light catalytic activity and stable performance is developed, which is the key of practical application.
Disclosure of Invention
The first purpose of the invention is to provide an ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material, which has good visible light response performance and can promote the separation of photo-generated electron-hole pairs, thereby solving the problem of low visible light catalytic activity of bismuth molybdate.
The second purpose of the invention is to provide a preparation method of the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material, which is used for manufacturing the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
In order to achieve the first object, the invention adopts the technical scheme that the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material comprises bismuth molybdate, wherein ultrathin bismuth oxide nanosheets are introduced on the surface of the bismuth molybdate through NaOH assistance and roasting.
In order to achieve the second object, the second technical scheme adopted by the invention is a preparation method of the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material, which is implemented according to the following steps:
and 2, introducing ultrathin bismuth oxide nanosheets to the surface of the bismuth molybdate obtained in the step 1 through NaOH assistance and roasting to prepare the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
The second technical scheme of the invention also has the following characteristics:
the step 1 specifically comprises:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
and step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, transferring the solution into a reaction kettle, sealing, putting the reaction kettle into an electric heating constant-temperature air blowing drying box, reacting to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, and carrying out centrifugal separation, washing and vacuum drying treatment to obtain the bismuth molybdate photocatalytic material.
In the step 1.2, the temperature for reaction in the electrothermal constant-temperature air-blast drying oven is 160 ℃, and the time is 12 hours.
In the step 1.2, the temperature for vacuum drying treatment is 60 ℃ and the time is 5 h.
In the step 1.2, the reaction kettle is a stainless steel reaction kettle with a teflon liner.
The step 2 specifically comprises:
step 2.1, dispersing the powder of the bismuth molybdate photocatalytic material obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, adding a NaOH solution into the mixed solution B prepared in the step 2.1 dropwise to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is not more than 0.5: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 until water is evaporated to dryness, and roasting the mixed solution C after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
In the step 2.3, the temperature for constant-temperature magnetic stirring is 60-80 ℃ and the time is 6-8 h.
In the step 2.3, the roasting temperature is 150-350 ℃, and the roasting time is 1-3 h.
The invention has the beneficial effects that: the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material prepared by the preparation method of the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material has the advantages of no agglomeration, wide visible light response range, obviously improved catalytic activity compared with pure bismuth molybdate, good reusability, simple preparation process, mild conditions, good controllability and convenient operation.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a bismuth molybdate photocatalytic material and an ultra-thin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained by the preparation method of the present invention;
FIG. 2 is a scanning electron micrograph and an EDS elemental mapping image of a bismuth molybdate photocatalytic material and an ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained by the preparation method of the present invention;
FIG. 3 is a TEM image of a bismuth molybdate photocatalytic material and an ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained by the preparation method of the present invention;
FIG. 4 is a solid UV-VIS absorption spectrum of a bismuth molybdate photocatalytic material and an ultra-thin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained by the preparation method of the present invention;
FIG. 5 is a graph comparing the visible light catalytic activity of a bismuth molybdate photocatalytic material and an ultra-thin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained by the preparation method of the present invention;
FIG. 6 is a graph showing the comparison of the visible light catalytic activity of the ultra-thin bismuth oxide/bismuth molybdate heterogeneous photocatalytic materials obtained in example 1, example 2, example 3, example 4 and comparative example 2;
FIG. 7 is a graph showing the comparison of the visible light catalytic activity of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained by the preparation method of the present invention after 4 times of use.
In the figure, BMO represents the bismuth molybdate photocatalytic material obtained in comparative example 1, BMO-Na0 represents the calcined bismuth molybdate photocatalytic material obtained in comparative example 2, Ethed BMO-Na1.5 represents the Etched bismuth molybdate photocatalytic material obtained in comparative example 3, BMO-Na1 represents the ultra-thin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained in example 1, and BMO-Na1.5 represents the ultra-thin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained in example 2. BMO-Na2 represents the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained in example 3, and BMO-Na2.5 represents the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material obtained in example 4.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
The ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material comprises bismuth molybdate, wherein ultrathin bismuth oxide nanosheets are introduced into the surface of the bismuth molybdate through NaOH assistance and roasting.
The preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, adding a NaOH solution into the mixed solution B prepared in the step 2.1 dropwise to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is not more than 0.5: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 at the temperature of 60-80 ℃ for 6-8 h until water is evaporated to dryness, and roasting the mixed solution C at the temperature of 150-350 ℃ for 1-3 h after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
Example 1
The preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, adding a NaOH solution into the mixed solution B prepared in the step 2.1 dropwise to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is 0.286: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 at 60 ℃ for 6 hours until water is evaporated to dryness, and roasting the mixed solution C at 150 ℃ for 1 hour after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
Example 2
The preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, dropwise adding a NaOH solution into the mixed solution B prepared in the step 2.1 to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is 0.357: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 at 70 ℃ for 7 hours until water is evaporated to dryness, and roasting the mixed solution C at 200 ℃ for 2 hours after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
Example 3
The preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, dropwise adding an NaOH solution into the mixed solution B prepared in the step 2.1 to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is 0.429: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 at the temperature of 60-80 ℃ for 7 hours until water is evaporated to dryness, and roasting the mixed solution C at the temperature of 250 ℃ for 2.5 hours after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
Example 4
The preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, adding a NaOH solution into the mixed solution B prepared in the step 2.1 dropwise to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is 0.5: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 at 80 ℃ for 8 hours until water is evaporated to dryness, and roasting the mixed solution C at 350 ℃ for 3 hours after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material.
Comparative example 1
For comparison, the preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is improved in example 2, and is specifically implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
comparative example 2
For comparison, the preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is improved in example 2, and is specifically implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution B prepared in the step 2.1 at 70 ℃ for 7 hours until water is evaporated to dryness, and roasting the mixed solution C at 200 ℃ for 2 hours after the constant-temperature magnetic stirring is finished to finally obtain the roasted bismuth molybdate photocatalytic material.
Comparative example 3
For comparison, the preparation method of the ultrathin bismuth oxide/bismuth molybdate heterogeneous photocatalytic material is improved in example 2, and is specifically implemented according to the following steps:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a stainless steel reaction kettle with a teflon lining, sealing, then placing the reaction kettle into an electric heating constant-temperature air blowing drying oven, reacting for 12 hours at 160 ℃ to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, carrying out centrifugal separation and washing, and carrying out vacuum drying treatment for 5 hours at 60 ℃ to obtain a bismuth molybdate photocatalytic material;
step 2.1, dispersing the powder of bismuth molybdate obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, dropwise adding a NaOH solution into the mixed solution B prepared in the step 2.1 to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is 0.357: 1;
and 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 at 70 ℃ for 7 hours until water is evaporated to dryness, and finally obtaining the etched bismuth molybdate photocatalytic material after the constant-temperature magnetic stirring is finished.
FIG. 1 is a powder diffraction pattern of BMO and BMO-Na1.5. It can be seen from fig. 1 that the XRD characteristic diffraction peak appearing in BMO — na1.5 is almost the same as that of BMO, indicating that low-temperature calcination does not affect the crystal structure of BMO. In addition, a new series of characteristic diffraction peaks can be seen, at positions of approximately 30.33 °,37.62 °,47.15 °And 55.58 deg., indicating Bi2O3Is present.
FIG. 2 is a scanning electron micrograph of BMO and BMO-Na1.5, wherein (a), (b) and (c) show BMO, (b) and (c) are enlarged views of (a), (d), (e) and (f) show BMO-Na1.5, (e) and (f) are enlarged views of (d). As can be seen from (a), (b) and (c) in fig. 2, BMO is a three-dimensional spherical hierarchical structure assembled from a large number of nanosheets, with an average diameter of 1 μm to 2 μm, and the thickness of the nanosheets being about 10nm to 20nm (fig. (c)); as can be seen from (d), (e) and (f) in FIG. 2, the morphology and size of BMO-Na1.5 are substantially the same as those of BMO, and Bi formation on the surface of BMO is observed2O3Ultrathin nanosheets (figures (e) and (f)). The layered image of BMO-Na1.5 is represented by (h) in FIG. 2, (i) represents Bi, (j) represents Mo, and (k) represents O.
In fig. 3, (a) and (b) show TEM photographs of BMOs; (c) HR-TEM photographs showing BMO; (d) and (e) TEM photograph showing BMO-Na1.5; (f) HR-TEM image of BMO-Na1.5 is shown. As can be seen from (a) and (d) in FIG. 3, BMO and BMO-Na1.5 are three-dimensional microsphere structures. As can be seen from (e) in FIG. 3, BMO-Na1.5 is a BMO three-dimensional microsphere structure and Bi2O3And (3) an ultrathin nanosheet. As can be seen from (f) in FIG. 3, the interplanar spacings of 0.315nm and 0.331nm are respectively at the interplanar spacing of (131) and Bi of the orthorhombic BMO2O3Corresponding to the (111) interplanar spacing (curve marked part), the results show that Bi2O3/Bi2MoO6And (4) successfully preparing the heterojunction.
FIG. 4 is the solid UV-Vis absorption spectra of BMO and BMO-Na1.5. As can be seen from fig. 4, the absorption edge of BMO is about 490nm, while BMO-na1.5 photocatalytic material exhibits an absorption edge similar to BMO, with a slightly broadened band gap.
The ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material prepared by the invention can be used for photocatalytic degradation of phenol. Phenol, also known as Carbolic acid (Carbolic acid), is a common chemical, an important raw material for the production of certain resins, bactericides, preservatives and pharmaceuticals (such as aspirin), and is a major intermediate in the oxidation of high molecular aromatic hydrocarbons. The phenol-containing wastewater has wide sources, mainly comes from enterprises of coal chemical industry, petrochemical industry, pesticides, phenolic resin, coking and the like, the concentration of phenols in wastewater of the industries of chemical industry, oil refining and the like is more than 1000mg/L, phenols in the wastewater are difficult to remove by using a conventional water treatment method, and the phenol-containing wastewater poses serious threats to human health and ecological balance. The phenols can enter into body via skin, oral cavity, respiratory tract and mucosa, inhibit central nervous system, damage liver and kidney, and cause dizziness, headache, asthenia, blurred vision and pulmonary edema by inhaling high concentration steam. The excessive intake of phenol in human body can cause poisoning and even death, and seriously threatens human health and living environment. The cool waste water not only poses serious threat to human health, but also causes harm to animals and plants. When the content of the water reaches the appropriate content, the fishes can have poisoning symptoms, and the fishes can die in large quantities and even be completely eradicated after the poisoning symptoms are exceeded. The toxicity of the cool wastewater can also inhibit the natural growth rate of other organisms in the water body and destroy the ecological balance. Therefore, the maximum allowable concentration of volatile matter in the ground water in China is 0.1 milligram liter (V-class water). The volatile snore specified in the water quality standard of domestic drinking water in China is not more than 0.002 milligram liter. Therefore, the method has important significance for the health of human beings, animals and plants and the protection of the environment, and the phenolic substances in the wastewater can be effectively removed.
The experimental conditions were as follows: dissolving phenol in water to obtain a solution with a concentration of 10 mg.L-1Adding catalyst powder (with a concentration of 1000 mg. L)-1) And placing the solution in the dark, stirring for 30min to reach adsorption balance, placing the photodegradation solution in a photocatalytic reaction device for illumination, wherein an experimental light source is a metal halide lamp and simulates visible light (the emission spectrum is 380-800 nm, and a filter is added to filter light below 420 nm). Sampling and centrifuging at intervals of 30min, taking supernatant, determining the absorbance of phenol at the maximum absorption wavelength of 507nm by adopting a 4-aminoantipyrine spectrophotometry, determining the concentration change by adopting a photometry, and evaluating the photocatalytic activity of the catalyst.
In FIG. 5, (a) shows the change in the concentration of phenol during degradation, and (b) shows the apparent rate constant of degradation of phenol. As can be seen from (a) in fig. 5, BMO — na1.5 has the highest photocatalytic activity and BMO has the lowest photocatalytic activity, and after 180min of illumination, the phenol degradation rates are 96.5% and 3.71%, respectively.
FIG. 6 is a graph comparing the concentration change of the produced photocatalytically degraded phenol of examples 1 to 4 and comparative example 2. As can be seen from FIG. 6, BMO-Na1.5 has the highest photocatalytic activity.
FIG. 7 is a graph comparing the visible light catalytic activity of BMO-Na1.5 after 4 applications. As can be seen from FIG. 7, after 4 times of repeated use, the activity of BMO-Na1.5 is slightly reduced, which shows that the material has stable performance and good reusability.
Claims (5)
1. A preparation method of an ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material is characterized by comprising the following steps:
step 1, preparing a bismuth molybdate photocatalytic material;
step 2, introducing ultrathin bismuth oxide nanosheets to the surface of the bismuth molybdate obtained in the step 1 through NaOH assistance and roasting to prepare an ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material;
the step 1 specifically comprises:
step 1.1, according to 2: bi (NO) is measured in a molar ratio of 13)3·5H2O and Na2MoO4·2H2O, first measured Bi (NO)3)3·5H2Dissolving O in ethylene glycol solution, and adding Na into the ethylene glycol solution2MoO4·2H2O, finally stirring until a transparent solution is obtained;
step 1.2, firstly adding absolute ethyl alcohol into the transparent solution obtained in the step 1.1, uniformly stirring, then transferring the transparent solution into a reaction kettle, sealing, then placing the reaction kettle into an electric heating constant-temperature air blast drying box for reaction to obtain a mixed solution A, naturally cooling the mixed solution A to room temperature after the reaction is finished, and then carrying out centrifugal separation, washing and vacuum drying treatment to obtain a bismuth molybdate photocatalytic material;
the step 2 specifically comprises:
step 2.1, dispersing the bismuth molybdate photocatalytic material obtained in the step 1 in deionized water and carrying out ultrasonic treatment to obtain a mixed solution B;
step 2.2, adding a NaOH solution into the mixed solution B prepared in the step 2.1 dropwise to obtain a mixed solution C, wherein the molar ratio of NaOH to the bismuth molybdate photocatalytic material is not more than 0.5: 1;
step 2.3, performing constant-temperature magnetic stirring on the mixed solution C prepared in the step 2.2 until water is evaporated to dryness to obtain a solid, and roasting the obtained solid after the constant-temperature magnetic stirring is finished to finally obtain the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material; the roasting temperature is 150-350 ℃, and the roasting time is 1-3 h.
2. The method for preparing the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material as claimed in claim 1, wherein in the step 1.2, the temperature for carrying out the reaction in an electrothermal constant-temperature air-blast drying oven is 160 ℃ and the time is 12 hours.
3. The method for preparing the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material as claimed in claim 2, wherein in the step 1.2, the temperature for vacuum drying is 60 ℃ and the time is 5 h.
4. The method for preparing the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material as claimed in claim 3, wherein in the step 1.2, the reaction kettle is a stainless steel reaction kettle lined with Teflon.
5. The method for preparing the ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material as claimed in claim 4, wherein in the step 2.3, the temperature for constant-temperature magnetic stirring is 60-80 ℃ and the time is 6-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910233240.9A CN109939673B (en) | 2019-03-26 | 2019-03-26 | Ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910233240.9A CN109939673B (en) | 2019-03-26 | 2019-03-26 | Ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109939673A CN109939673A (en) | 2019-06-28 |
| CN109939673B true CN109939673B (en) | 2020-08-18 |
Family
ID=67011616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910233240.9A Active CN109939673B (en) | 2019-03-26 | 2019-03-26 | Ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109939673B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227526B (en) * | 2019-06-25 | 2020-11-13 | 延安大学 | Bismuth oxide/bismuth oxycarbonate/bismuth molybdate composite photocatalytic material and preparation method thereof |
| CN110937610B (en) * | 2019-11-14 | 2022-10-11 | 中国科学院金属研究所 | Method for improving efficiency of preparing ammonia by reducing nitrogen with photocatalytic material |
| CN114939406B (en) * | 2022-03-24 | 2024-01-30 | 淮北师范大学 | Bi2MoO6 photocatalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748484A (en) * | 2008-12-11 | 2010-06-23 | 南京理工大学 | Method for solvent-thermally synthesizing nano bismuth oxide single-crystal chips |
| JP2012091991A (en) * | 2010-09-30 | 2012-05-17 | Ohara Inc | Glass ceramic, method for producing the same, photocatalyst containing the same, slurry mixture, photocatalyst member, purifying device, filter, sintered compact and glass ceramic composite |
| CN102658121A (en) * | 2012-02-14 | 2012-09-12 | 南昌航空大学 | Catalyst Bi2O3/Bi2MoO6 for photodegradation of organic matters and method for preparing the same |
| CN107486199A (en) * | 2017-09-05 | 2017-12-19 | 中国石油大学(华东) | A kind of bismuth oxide bismuth tungstate heterojunction photocatalyst and preparation method thereof |
-
2019
- 2019-03-26 CN CN201910233240.9A patent/CN109939673B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748484A (en) * | 2008-12-11 | 2010-06-23 | 南京理工大学 | Method for solvent-thermally synthesizing nano bismuth oxide single-crystal chips |
| JP2012091991A (en) * | 2010-09-30 | 2012-05-17 | Ohara Inc | Glass ceramic, method for producing the same, photocatalyst containing the same, slurry mixture, photocatalyst member, purifying device, filter, sintered compact and glass ceramic composite |
| CN102658121A (en) * | 2012-02-14 | 2012-09-12 | 南昌航空大学 | Catalyst Bi2O3/Bi2MoO6 for photodegradation of organic matters and method for preparing the same |
| CN107486199A (en) * | 2017-09-05 | 2017-12-19 | 中国石油大学(华东) | A kind of bismuth oxide bismuth tungstate heterojunction photocatalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Nanosize α-Bi2O3 decorated Bi2MoO6 via an alkali etching process for enhanced photocatalytic performance;Zhiqiang Hao, et al;《RSC ADVANCES》;20150115;第5卷(第16期);第12347页第2.1-2.2节 * |
| 水热法制备 Bi2O3纳米片及其电化学性能的研究;梁 英;《化 学 学 报》;20101014;第68卷(第19期);第1978页左栏第1-2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109939673A (en) | 2019-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110227526B (en) | Bismuth oxide/bismuth oxycarbonate/bismuth molybdate composite photocatalytic material and preparation method thereof | |
| Cheng et al. | One-step microwave hydrothermal preparation of Cd/Zr-bimetallic metal–organic frameworks for enhanced photochemical properties | |
| CN109939673B (en) | Ultrathin bismuth oxide/bismuth molybdate heterojunction photocatalytic material and preparation method thereof | |
| Li et al. | Facile synthesized low-cost MoS2/CdS nanodots-on-nanorods heterostructures for highly efficient pollution degradation under visible-light irradiation | |
| CN111250135B (en) | Graphite-phase carbon nitride nanosheet material and preparation method and application thereof | |
| CN108993502B (en) | Silver and oxygen defect co-modified bismuth molybdate-based composite photocatalytic material and preparation method thereof | |
| Luo et al. | g-C3N4-based photocatalysts for organic pollutant removal: a critical review | |
| CN107519897B (en) | Ternary Z-shaped structured photocatalyst and preparation method and application thereof | |
| CN113134381B (en) | Bi 4 O 5 I 2 Carbon nitride boron quantum dot photocatalytic material and preparation method and application thereof | |
| CN108906089B (en) | Preparation method of BiOI homojunction composite photocatalyst | |
| Jiang et al. | Construction of a hierarchical NiFe2O4/CuInSe2 (pn) heterojunction: Highly efficient visible-light-driven photocatalyst in the degradation of endocrine disruptors in an aqueous medium | |
| CN111330648A (en) | MIL-101(Fe)/g-C3N4Composite visible light photocatalyst and preparation method and application thereof | |
| Zhang et al. | A 2D/3D g-C3N4/BiOI heterostructure nano-sphere with oxygen-doped for enhanced visible light− driven photocatalytic activity in environmental remediation | |
| Niu et al. | Salt-sealing-pyrolysis derived Ag/ZnO@ C hollow structures towards efficient photo-oxidation of organic dye and water-born bacteria | |
| Li et al. | CeVO4 nanofibers hybridized with g-C3N4 nanosheets with enhanced visible-light-driven photocatalytic activity | |
| CN112090438A (en) | BiOCl/g-C3N4/CeO2Synthesis method of three-phase photocatalytic material | |
| Tan et al. | Highly efficient photocatalytic degradation over rose-like 1D/2D La (OH) 3/(BiO) 2 OHCl heterostructures boosted by rich oxygen vacancies and enhanced interfacial charge transfer | |
| CN110227515B (en) | Bi2MoO6/BiPO4P-n heterojunction photocatalyst, preparation method and application thereof | |
| CN115283015A (en) | Organic metal framework composite photocatalyst BiVO 4 @NH 2 Process for producing (E) -MIL-125 (Ti) | |
| Cao et al. | Effectively compound the heterojunction formed by flower-like Bi2S3 and g-C3N4 to enhance photocatalytic activity | |
| Xu et al. | Hydrothermal synthesis and photocatalytic performance of hierarchical Bi2MoO6 microspheres using BiOI microspheres as self-sacrificing templates | |
| Jin et al. | Preparation of flower-like Bi 2 WO 6/ZnO heterojunction photocatalyst with improved photocatalytic performance | |
| CN110227517B (en) | CuBi2O4/BiPO4P-n type heterojunction photocatalyst, preparation method and application thereof | |
| CN110624574B (en) | Double Bi4O5I2Preparation method of photocatalytic material and application of photocatalytic material in degrading MC-LR | |
| CN107961785A (en) | A kind of preparation method and applications of high activity bismuth chromate nano-photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |