CN115196673B - Polycrystalline Bi 2 O 3 Material, preparation method and application - Google Patents

Polycrystalline Bi 2 O 3 Material, preparation method and application Download PDF

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CN115196673B
CN115196673B CN202210786121.8A CN202210786121A CN115196673B CN 115196673 B CN115196673 B CN 115196673B CN 202210786121 A CN202210786121 A CN 202210786121A CN 115196673 B CN115196673 B CN 115196673B
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王英楠
闫楚楚
胡彦昭
刘信彤
田琦
赵武
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NORTHWEST UNIVERSITY
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Abstract

The invention provides a polycrystalline Bi 2 O 3 The preparation method of the material comprises the steps of taking bismuth nitrate pentahydrate as a bismuth source, citric acid as a surfactant, deionized water as a solvent, mixing and stirring, and adding a proper amount of ammonia water to obtain a mixed material liquid; carrying out hydrothermal reaction on the mixed material liquid, and cooling to room temperature to obtain a reaction product; centrifuging, washing and drying the obtained product to obtain flower-like Bi 2 O 2 CO 3 A precursor; calcining and cooling the obtained precursor to obtain the polycrystalline phase Bi 2 O 3 A material. Wherein, the mass of the bismuth nitrate pentahydrate is 0.48g, the mass of the citric acid is 0.38g, and the addition amount of the ammonia water is 5ml; the temperature of the hydrothermal reaction is 180 ℃ and the reaction time is 18 hours; multicrystalline phase Bi 2 O 3 Consists of nano particles, polycrystalline phase Bi 2 O 3 The average particle size of the nanoparticles is about 2 μm.

Description

Polycrystalline Bi 2 O 3 Material, preparation method and application
Technical Field
The invention belongs to the technical field of semiconductor nano material preparation, and relates to Bi 2 O 3 The material, in particular relates to a polycrystalline phase Bi 2 O 3 Materials, preparation methods and applications.
Background
Heterogeneous photocatalysis of metal oxide nanoparticles has received extensive attention in removing organic pollutants from air and in wastewater treatment due to their high efficiency, simplicity and low cost. Semiconductive metal oxides, e.g. titanium dioxide (TiO 2 ) Tin oxide (SnO) 2 ) And bismuth oxide (Bi) 2 O 3 ) Photocatalytic materials that degrade as contaminants are widely studied, however, their use is limited by their inherently large band gap, and poor quantum yields caused by the rapid recombination of photogenerated electrons and holes. Therefore, the preparation of efficient photocatalysts has become a hot topic in photocatalysis.
Bismuth-based compounds are a promising new candidate for visible-light responsive photocatalysts. Bi (Bi) 3+ Showing remarkable stability in different compounds, various bismuth-based substances have been prepared and tested as photocatalysts, such as Bi 2 S 3 、Bi 2 O 3 、Bi 2 WO 6 BiOX (X=Cl, br and I) and Bi 2 O 2 CO 3 Etc. They have been widely studied because they have almost a layered structure and have sufficient chemical stability, cost effectiveness and environmental friendliness. Wherein, the basic typeBismuth carbonate (Bi) 2 O 2 CO 3 ) It is a promising photocatalyst for degrading organic dyes in environmental purification because of its chemical stability, non-toxicity and low cost characteristics.
Bismuth oxide (Bi) 2 O 3 ) Is one of metal oxide semiconductors whose optical band gap energy ranges from 2.1eV to 2.8eV, is considered to be a durable material activated by white light, bi due to its excellent optical and electrical properties such as high refractive index, dielectric constant, photoconductivity and photoluminescence 2 O 3 Become very attractive candidates in the application field. In particular, due to its Bi-O layered crystal or special Bi-O polyhedral structure, a high surface area and active sites are provided for Bi 2 O 3 Has excellent photocatalytic activity.
Disclosure of Invention
In view of the defects and shortcomings of the prior art, the invention aims to provide a polycrystalline Bi phase 2 O 3 Material, preparation method and application thereof to solve Bi prepared by the prior art 2 O 3 The technical problem of poor photocatalytic dye degradation effect.
In order to solve the technical problems, the invention adopts the following technical scheme:
polycrystalline Bi 2 O 3 The preparation method of the material comprises the steps of taking bismuth nitrate pentahydrate as a bismuth source, citric acid as a surfactant, deionized water as a solvent, mixing and stirring, and adding a proper amount of ammonia water to obtain a mixed material liquid; carrying out hydrothermal reaction on the mixed material liquid, and cooling to room temperature to obtain a reaction product; centrifugally washing and drying the obtained product to obtain a target product precursor; calcining and cooling the obtained target product precursor to obtain the polycrystalline Bi 2 O 3 A material;
wherein the mass ratio of the bismuth nitrate pentahydrate to the citric acid is (1.2-1.3): 1, and the volume ratio of the ammonia water to the deionized water is (4.5-5.5).
The invention also has the following technical characteristics:
preferably, the mass ratio of the bismuth nitrate pentahydrate to the citric acid is 1.26:1, and the volume ratio of the ammonia water to the deionized water is 1:5.
Preferably, the temperature of the hydrothermal reaction is 180 ℃ and the reaction time is 12 hours.
Preferably, the reaction temperature of the drying treatment is 60 ℃, and the reaction heat preservation time is 12 hours.
The method specifically comprises the following steps:
step one, preparing a target product precursor solution;
dissolving 0.48g of bismuth nitrate pentahydrate and 0.38g of citric acid in deionized water, stirring until the bismuth nitrate pentahydrate and the citric acid are completely dissolved, and adding a proper amount of ammonia water to obtain a target product precursor solution;
step two, preparing a solid precursor of a target product;
transferring the precursor solution of the target product prepared in the first step into a reaction kettle for hydrothermal reaction, cooling the obtained product to room temperature, centrifuging, washing and drying to obtain flower-shaped Bi 2 O 2 CO 3 ；
Step three, preparing the polycrystalline phase Bi 2 O 3 A material;
preparing the Bi with flower-like morphology from the second step 2 O 2 CO 3 Calcining in 400 deg.c air for 2 hr, and naturally cooling to room temperature to obtain alpha-Bi 2 O 3 Alternatively, the first and second substrates may be coated,
bi with flower-like morphology 2 O 2 CO 3 Calcining in air at 400 ℃ for 2 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the beta-Bi 2 O 3 Alternatively, the first and second substrates may be coated,
bi with flower-like morphology 2 O 2 CO 3 Calcining in air at 800 deg.c for 2 hr, and cooling to room temperature at 10 deg.c/min to obtain gamma-Bi 2 O 3 。
Further, in the first step, the amount of ammonia added was 5ml.
Further, the polycrystalline phase Bi prepared in the third step 2 O 3 The material has an average particle diameter of 2Bi of μm 2 O 3 Nanoparticle composition.
The invention also protects a polycrystalline Bi 2 O 3 A material which uses the polycrystalline Bi as described above 2 O 3 The preparation method of the material is as follows.
The present invention also protects the multicrystalline Bi as described above 2 O 3 The material is used for photocatalytic degradation of rhodamine B, methylene blue, congo red and methyl orange.
The present invention also protects the multicrystalline Bi as described above 2 O 3 Polycrystalline Bi prepared by material preparation method 2 O 3 The material is used for photocatalytic degradation of rhodamine B, methylene blue, congo red and methyl orange.
Compared with the prior art, the invention has the beneficial technical effects that:
the preparation method of the polycrystalline Bi2O3 material of the invention adopts bismuth nitrate pentahydrate as bismuth source and citric acid as surfactant to prepare polycrystalline Bi 2 O 3 A liquid precursor of the material; the polycrystalline phase Bi 2 O 3 Carrying out hydrothermal reaction on the liquid precursor of the material to obtain a target product precursor; calcining and cooling the obtained target product precursor to obtain the polycrystalline Bi 2 O 3 A material. The preparation method is characterized in that the polycrystalline-phase Bi2O3 material with photocatalytic degradation effect on rhodamine B, methylene blue, congo red and methyl orange is prepared by controlling the mass ratio of bismuth nitrate pentahydrate to citric acid and the hydrothermal reaction condition and controlling the calcining temperature and the cooling rate; the preparation method has the advantages of simple process, short preparation period, low cost and the like, and can be used for large-scale synthesis.
(II) the polycrystalline Bi phase obtained by the method of the present invention 2 O 3 The material has stable structure, avoids the problem of difficult storage after material synthesis, and the polycrystalline Bi prepared by the invention 2 O 3 The material has the photocatalytic degradation rate of more than 90 percent for Congo red, the photocatalytic degradation rate of more than 70 percent for methylene blue and the degradation rate of more than 51 percent for rhodamine B, and has great application value in the aspect of pollution control。
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure.
FIG. 1 shows the flower-like Bi obtained in example 1 2 O 3 CO 3 XRD pattern of precursor;
FIG. 2 shows the flower-like Bi obtained in example 1 2 O 3 CO 3 SEM images of the precursor;
FIG. 3 shows the flower-like Bi obtained in example 1 2 O 3 CO 3 TEM image of precursor;
FIG. 4 shows the α -Bi obtained in example 1 2 O 3 XRD pattern of the material;
FIG. 5 shows the α -Bi obtained in example 1 2 O 3 SEM images of the material;
FIG. 6 shows the α -Bi obtained in example 1 2 O 3 A TEM image of the material;
FIG. 7 shows the α -Bi obtained in example 1 2 O 3 Raman analysis spectrum of the material;
FIG. 8 shows the beta-Bi produced in example 2 2 O 3 XRD pattern of the material;
FIG. 9 is a view showing the beta-Bi obtained in example 2 2 O 3 SEM images of the material;
FIG. 10 is a view showing the beta-Bi produced in example 2 2 O 3 A TEM image of the material;
FIG. 11 shows the beta-Bi produced in example 2 2 O 3 Raman analysis spectrum of the material;
FIG. 12 shows the gamma-Bi obtained in example 3 2 O 3 XRD pattern of the material;
FIG. 13 shows the gamma-Bi obtained in example 3 2 O 3 SEM images of the material;
FIG. 14 shows the gamma-Bi obtained in example 3 2 O 3 Raman analysis spectrum of the material;
FIG. 15 is a Bi-based prepared 2 O 3 CO 3 Precursor and polycrystalline Bi 2 O 3 Degradation effect diagram of dye rhodamine B (RhB), wherein (a) is Bi 2 O 2 CO 3 ；(b)α-Bi 2 O 3 ；(c)β-Bi 2 O 3 ；(d)γ-Bi 2 O 3 ；
FIG. 16 (a) is Bi 2 O 3 CO 3 Precursor and polycrystalline Bi 2 O 3 A photo-degradation effect graph of rhodamine B (RhB);
FIG. 16 (b) is Bi 2 O 3 CO 3 Precursor and polycrystalline Bi 2 O 3 Ln (C/C) 0 ) A graph of time dependence on irradiation;
FIG. 17 is a precursor Bi-based preparation 2 O 3 CO 3 And polycrystalline phase Bi 2 O 3 A graph of the degradation effect on the dye Methylene Blue (MB); wherein (a) is Bi 2 O 2 CO 3 ；(b)α-Bi 2 O 3 ；(c)β-Bi 2 O 3 ；(d)γ-Bi 2 O 3 ；
FIG. 18 (a) is based on a precursor Bi 2 O 2 CO 3 And polycrystalline phase Bi 2 O 3 A graph of the photodegradation effect on Methylene Blue (MB);
FIG. 18 (b) is Bi 2 O 3 CO 3 Precursor and polycrystalline Bi 2 O 3 Ln (C/C) 0 ) A graph of time dependence on irradiation;
FIG. 19 is a precursor Bi-based preparation 2 O 3 CO 3 And polycrystalline phase Bi 2 O 3 A graph of the degradation effect on dye Congo Red (CR); wherein (a) is Bi 2 O 2 CO 3 ；(b)α-Bi 2 O 3 ；(c)β-Bi 2 O 3 ；(d)γ-Bi 2 O 3 ；
FIG. 20 (a) is based on the precursor Bi 2 O 2 CO 3 And polycrystalline phase Bi 2 O 3 A graph of the effect of photodegradation on Congo Red (CR);
FIG. 20 (b) shows Bi 2 O 3 CO 3 Precursor and polycrystalline Bi 2 O 3 In (C/C0) versus irradiation time;
FIG. 21 is a precursor Bi-based preparation 2 O 3 CO 3 And polycrystalline phase Bi 2 O 3 A graph of the degradation effect on dye Methyl Orange (MO); wherein (a) is Bi 2 O 2 CO 3 ；(b)α-Bi 2 O 3 ；(c)β-Bi 2 O 3 ；(d)γ-Bi 2 O 3 ；
FIG. 22 (a) is based on the precursor Bi 2 O 2 CO 3 And polycrystalline phase Bi 2 O 3 A photo-degradation effect graph of Methyl Orange (MO);
FIG. 22 (b) shows Bi 2 O 3 CO 3 Precursor and polycrystalline Bi 2 O 3 Ln (C/C) 0 ) A graph of time dependence on irradiation;
FIG. 23 shows the reaction temperature of the precursor Bi 2 O 2 CO 3 XRD pattern of the effect.
FIG. 24 shows the result of the calcination of alpha-Bi based on the different calcination temperatures 2 O 3 SEM image of the material.
FIG. 25 is a graph of beta-Bi based on different calcination temperatures 2 O 3 SEM image of the material.
FIG. 26 shows the result of different calcination temperatures for gamma-Bi 2 O 3 SEM image of the material.
The technical scheme of the invention is further described below by referring to examples.
Detailed Description
The apparatus and the medicine of the present invention are commercially available, unless otherwise specified.
The polycrystalline phase Bi of the present invention 2 O 3 The preparation method of the material comprises the steps of taking bismuth nitrate pentahydrate as a bismuth source, citric acid as a surfactant, deionized water as a solvent, mixing and stirring, and adding a proper amount of ammonia water to obtain a mixed material liquid; carrying out hydrothermal reaction on the mixed material liquid, and cooling to room temperature to obtain a reaction product; centrifugally washing and drying the obtained product to obtain a target product precursor; calcining and cooling the obtained target product precursor to obtain the polycrystalline Bi 2 O 3 A material;
wherein the mass of the bismuth nitrate pentahydrate is 0.48g, the mass of the citric acid is 0.38g, and the volume ratio of the ammonia water to the deionized water is 1:5.
Multicrystalline phase Bi 2 O 3 The characterization test methods of the materials include XRD (X-ray diffraction), SEM (scanning electron microscope), TEM (Transmission Electron Microscope) and RAMAN.
The hydrothermal reaction process refers to the general term of chemical reactions performed in fluids such as water, aqueous solution or steam at a certain temperature and pressure, and in this application, specifically refers to preparing materials by dissolving and recrystallizing raw material powder in a sealed pressure vessel using deionized water as a solvent. The material prepared by the hydrothermal reaction has the advantages of complete grain development and uniform distribution.
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
the present example shows an alpha-Bi 2 O 3 The preparation method of the material specifically comprises the following steps:
step one, preparing a target product precursor solution;
dissolving 0.48g of bismuth nitrate pentahydrate and 0.38g of citric acid in 25ml of deionized water, stirring for 30 minutes until the bismuth nitrate pentahydrate and the citric acid are completely dissolved, and adding 5ml of ammonia water to obtain a target product precursor solution;
step two, preparing flower-shaped Bi 2 O 2 CO 3 A precursor;
transferring the precursor solution of the target product prepared in the first step into a 50ml polytetrafluoroethylene lining stainless steel autoclave, treating for 12 hours at the hydrothermal temperature of 180 ℃, naturally cooling to room temperature, centrifugally washing with ethanol and deionized water to remove impurities, and finally drying at 60 ℃ for 12 hours to obtain flower-shaped Bi 2 O 2 CO 3 ；
Step threeTo obtain alpha-Bi 2 O 3 A material;
bi with flower-like morphology 2 O 2 CO 3 Calcining in 400 deg.c air for 2 hr, and naturally cooling to room temperature to obtain alpha-Bi 2 O 3 。
In this embodiment, first, the precursor Bi is 2 O 2 CO 3 XRD, SEM, TEM and RAMAN analyses were performed and the results were as follows:
as shown in FIG. 1, when the XRD pattern of FIG. 1 is compared with the standard PDF pattern, bi with good crystallinity can be obtained by hydrothermal treatment 2 O 2 CO 3 The angles 2 theta corresponding to all diffraction peaks of the material are respectively 12.93 degrees, 23.90 degrees, 26.03 degrees, 30.25 degrees, 32.73 degrees, 35.31 degrees, 39.51 degrees, 40.36 degrees, 42.29 degrees, 46.96 degrees, 48.93 degrees, 52.23 degrees, 52.39 degrees, 53.41 degrees, 54.51 degrees, 56.89 degrees and 63.01 degrees, and the angles are consistent with standard cards ICSD PDF#41-1488. All diffraction peaks can be well indexed as tetragonal phase Bi 2 O 2 CO 3 At the same time, sharp and strong diffraction peak indicates Bi 2 O 2 CO 3 Is very high.
SEM results under different magnification are shown in figure 2, and the obtained material is in a flower shape, uniform in distribution, regular in size and structure, good in dispersibility, smooth in surface and clear in boundary.
TEM as shown in FIG. 3, it can be seen from FIG. 3 that the precursor Bi 2 O 2 CO 3 The average size of the particles was about 2. Mu.m, which is consistent with the SEM image results.
Then XRD, SEM, TEM and RAMAN analyses were performed on the calcined product obtained in step three, with the following results:
XRD results of the calcined product are shown in FIG. 4, and XRD patterns of the calcined product at 400℃can be well directed to Bi 2 O 3 Is a monoclinic phase of (c). Peaks observed in the XRD pattern were observed at 2 theta values of 25.84 deg., 27.01 deg., 28.11 deg., 33.15 deg., 33.35 deg., 35.17 deg., and 46.49 deg. and (002), (-111), (120), (012), (-121), (200), (210), (223) crystal planes and standard card PDF#76-1730 are consistent. This shows that heat treatment at 400℃for 2 hours is advantageous for alpha-Bi 2 O 3 Complete formation of the material, while sharp and intense diffraction peaks show a high degree of crystallization.
SEM results at different magnifications are shown in fig. 5, and it can be seen that the calcined product basically inherits the flower-like structure of the precursor, and is still uniformly distributed in a monodispersion manner. And a precursor Bi 2 O 2 CO 3 The central cavity is enlarged compared with the precursor, the size of the calcined product is slightly smaller than that of the precursor due to densification in the calcining process, the average size is 2 mu m, and meanwhile, the calcined product shows a large number of hollow shapes and has good optical performance.
The TEM is shown in fig. 6, and can be seen from fig. 6: the thick nanoplatelets constituting the compact flower-like structure confirm that the size of the calcined product becomes small, and the result is consistent with SEM, while each flower exhibits a mesopore that can improve photocatalytic efficiency.
The result of the RAMAN is shown in FIG. 7, and the Raman data is recorded at 10-600cm -1 Within the range. Due to alpha-Bi 2 O 3 Many of the peak characteristics observed are birefringent biaxial crystals with lower monoclinic symmetry. Herein below 120cm -1 The mode of (2) is the vibration of Bi atoms, which is higher than 150cm -1 The mode of (2) is due to displacement of O atoms, 120-150cm -1 The mode in the above is that the displacement of Bi and O atoms is 300-600cm -1 The modes in the region are due to the fact that they are derived from BiO 6 The hexahedral unit angularly constrains the symmetrical stretching anion motion in the Bi-O-Bi structure. Spectra at 530, 445, 313 and 287cm -1 Five broad bands due to Bi-O stretching are shown, and are located at 210, 183, 150, 138, 117, and 93cm -1 The other six sharp bands at that point are assigned to lattice vibrations. The above data illustrate that the present example ultimately produces a-Bi 2 O 3 A material.
Example 2:
this example shows a beta-Bi 2 O 3 The preparation method of the material is basically the same as the preparation method of the embodiment 1 and the proportion of the raw materials, except that Bi with flower-like morphology is prepared in the third step 2 O 2 CO 3 Calcining for 2 hours in air at 400 ℃ and then cooling to room temperature at a cooling rate of 5 ℃/min.
Then XRD, SEM, TEM and RAMAN analyses were performed on the calcined product obtained in step three, with the following results:
as shown in FIG. 8, it can be seen that all peaks present in the XRD pattern are assigned and indexed according to standard card PDF#78-1793, i.e., all detectable peaks can be well indexed as beta-Bi 2 O 3 The structure had main peaks at 27.94 °, 32.69 °, 33.83 °, 46.21 °, 46.91 °, 55.49 °, 55.63 °, 57.75 °. The results show that the diffraction peaks of the calcined product are sharper, indicating that the crystal type is better than other bismuth groups. In addition, other hetero peaks not observed from XRD patterns indicate pure beta-Bi 2 O 3 Is a successful preparation of (a).
SEM results at different magnifications as shown in fig. 9, low magnification images show that the calcined product still has a uniform flower-like structure, but is more compact than the flower-like structure before calcination. By further observing the morphology of the powder at high magnification, when the temperature is kept unchanged and the cooling rate is controlled, it can be seen that the calcined product basically inherits the morphology of the precursor and is still a flower-like structure with an average of about 2 μm, but at this time, the nanoplatelets constituting the flower-like structure become thicker and also have a tendency to shift to the morphology of the nanorods. Thus, a large number of mesopores remain in the layered structure, which can serve as transport paths for dye molecules and active substances.
TEM as shown in FIG. 10, it can be seen that the thick nanoplatelets, which constitute the compact flower-like structure, confirm that the calcined product size becomes smaller, and as a result, is consistent with SEM, while leaving a large number of mesopores in the layered structure on each flower, which can serve as a transport path for dye molecules and active substances.
The results for the RAMAN are shown in FIG. 11, with vibration bands at 87, 124, 312 and 465 showing β -Bi 2 O 3 The material belongs to tetragonal phase. Of which 87cm -1 The peak at the position is represented by the normal vibration mode A 1g The peak caused is referred to as beta-Bi 2 O 3 Vibration of Bi atoms in the structure, 124312 and 465cm -1 The peak at this point is characteristic of Bi-O stretching. The above data illustrate that the present example ultimately produces beta-Bi 2 O 3 A material.
Example 3:
this example shows a polycrystalline Bi 2 O 3 The preparation method of the material is basically the same as the preparation method of example 1 and the proportion of the raw materials, except that Bi with flower-like morphology 2 O 2 CO 3 Calcining for 2 hours in air at 800 ℃, and then cooling to room temperature at a cooling rate of 10 ℃/min.
Then XRD, SEM, TEM and RAMAN analyses were performed on the calcined product obtained in step three, with the following results:
the XRD results are shown in FIG. 12, where the precursor is transformed into a highly crystalline phase with sharp and intense diffraction peaks, all of which can be well indexed as gamma-Bi 2 O 3 Structures (PDF # 74-1375) with main peaks mainly at 2θ=24.96, 27.96, 30.70, 33.23, 37.84, 42.01, 52.92, 54.58, 56.21, 62.44 °. At the same time, no other impurity peak is observed in the diffraction peak, indicating gamma-Bi 2 O 3 The purity of the crystals is very high. At the same time, the heat treatment at 800 ℃ for 2 hours is beneficial to the gamma-Bi 2 O 3 Is formed entirely of (a).
The SEM results at different magnifications are shown in fig. 13, and the SEM results at low magnifications show that the calcined material is changed from the original nanoflower to a cubic structure formed by stacking nanoparticles, and at this time, no hollow flower-like structure is observed, indicating complete transition of morphology at high temperature. At higher magnification, it is clearly observed that the nanoparticle size is less than 1 μm, the cube size is different, possibly due to recrystallization caused by high temperature.
The results of the RAMAN are shown in FIG. 14, γ -Bi 2 O 3 Is recorded in a range of 10 to 800cm -1 Between, gamma-Bi 2 O 3 Exhibits 9 modes of vibration below 650cm -1 Is generally assigned to the internal Bi-O framework, which suggests several stretching, bending, vibration of the Bi-O polyhedraDynamic and respiratory modes, 50-100cm can be observed -1 Is very sharp and 100-700cm -1 Most modes of (a) are relatively broad. The above data illustrate that this example ultimately produces gamma-Bi 2 O 3 A material.
Example 4:
this example shows a polycrystalline Bi 2 O 3 The preparation method of the material is basically the same as that of example 1, except that the mass ratio of bismuth nitrate pentahydrate to citric acid is 1.3:1, and finally the alpha-Bi is prepared 2 O 3 A material.
Example 5:
this example shows a polycrystalline Bi 2 O 3 The preparation method of the material is basically the same as that of example 2, except that the mass ratio of bismuth nitrate pentahydrate to citric acid is 1.3:1, and finally the beta-Bi is prepared 2 O 3 A material.
Example 6:
this example shows a polycrystalline Bi 2 O 3 The preparation method of the material is basically the same as that of example 3, except that the mass ratio of bismuth nitrate pentahydrate to citric acid is 1.3:1, and the gamma-Bi is finally prepared 2 O 3 A material.
Example 7:
in this example, the polycrystalline Bi produced in examples 1 to 3 was used 2 O 3 The material is used for photocatalytic degradation of rhodamine B, methylene blue, congo red and methyl orange.
For photocatalysis, the same amount of Bi is added to the same concentration of different dye solutions used in the present example 2 O 3 CO 3 Precursor, alpha-Bi 2 O 3 Material, beta-Bi 2 O 3 Material and gamma-Bi 2 O 3 The material then simulates sunlight in a multi-site photochemical reaction instrument to catalyze the degradation of the dye.
In the photocatalysis process, a fluorescent lamp with the power of 99w is used as a stable light source at room temperature, and Bi is used 2 O 3 CO 3 、α-Bi 2 O 3 、β-Bi 2 O 3 And gamma-Bi 2 O 3 The material is used as a photocatalyst to study the photocatalytic degradation performance of four dyes (rhodamine B, methylene blue, methyl orange and Congo red) respectively. First, different dye solutions were prepared at the same concentration (concentration: 10 mg/L), and each time photocatalysis was performed, the amount of dye used was 50ml, and the amount of material used was 0.1g.
On the basis, firstly, a dark treatment experiment is carried out, namely, the material and the dye are mixed and then are put into a photochemical reaction instrument, and the mixture is continuously stirred for 1h under the condition of no illumination, so that the dye is prepared in the presence of Bi 2 O 3 CO 3 、α-Bi 2 O 3 、β-Bi 2 O 3 And gamma-Bi 2 O 3 The surface reaches adsorption/desorption equilibrium. Then the light source is turned on, the power is regulated to 99w, the timing is started, and sampling is carried out according to the set time interval. Dye concentration at the beginning of photodegradation (t=0) was C 0 The sampling interval is initially set to 20min, and the dye and Bi are collected after centrifugation 2 O 3 CO 3 、α-Bi 2 O 3 、β-Bi 2 O 3 And gamma-Bi 2 O 3 A material.
First, the dye concentration C was determined by measuring the absorbance of the different dyes at the specific wavelengths of the dyes (rhodamine B:554nm, methylene blue: 664nm, congo red: 497nm, methyl orange: 464 nm).
As can be seen from FIG. 15, bi 2 O 2 CO 3 Precursor and polycrystalline Bi 2 O 3 After the material irradiates rhodamine B (RhB) for 120min, beta-Bi 2 O 3 Shows the best photocatalytic activity, the degradation rate is 83.50%, which is higher than other products, the order of degradation rate is: beta-Bi 2 O 3 (85.30％)>Bi 2 O 2 CO 3 (74.30％)>α-Bi 2 O 3 (55.50％)>γ-Bi 2 O 3 (51.50%). The decrease in absorbance is caused by cleavage of the conjugated chromophore structure, while the progressively lower color shift of absorbance maximum is caused by progressive N-deethylation of rhodamine B (RhB) during irradiation.
As shown in FIG. 16, gamma-Bi during the dark reaction 2 O 3 The adsorption rate to RhB is high (32.70%), while the photoreaction is only 51.50%. Other bismuth-based photocatalysts have low adsorption efficiency in the dark reaction process and can be ignored. By contrast, from the slope k the following can be concluded: beta-Bi 2 O 3 The nano material has the fastest degradation rate, shows the best photocatalysis performance, and has the k value of 1.39 multiplied by 10 -2 min -1 . In contrast, other bismuth oxide semiconductors have slower degradation rates of only 0.53×10, respectively -2 And 0.27X10 -2 min -1 。
As can be seen from FIG. 17, the synthesized Bi 2 O 2 CO 3 Precursor and polycrystalline Bi 2 O 3 The photocatalysts all exhibit excellent photocatalytic activity. Bi (Bi) 2 O 2 CO 3 Precursor and polycrystalline Bi 2 O 3 After the material is irradiated with Methylene Blue (MB) for 120min, alpha-Bi 2 O 3 Up to 88.37%, beta-Bi 2 O 3 Up to 94.10%, gamma-Bi 2 O 3 Up to 88.40%, bi 2 O 2 CO 3 Only 70.20% was degraded. This may be caused by differences in crystal structure. The degradation rate of the dye increased with time and no color shift was observed, indicating structural disruption of the Methylene Blue (MB) molecule and its subsequent degradation by the bismuth-based semiconductor catalyst.
As shown in FIG. 18, bi of different crystal phases increases with the increase of the light irradiation time 2 O 3 Exhibits a similar degradation rate, while Bi 2 O 2 CO 3 The initial degradation rate was slow and after 60min the degradation rate began to increase. alpha-Bi 2 O 3 And gamma-Bi 2 O 3 The dynamic constants of the two phases respectively reach 1.75X10 -2 And 1.79×10 -2 min -1 . However, for beta-Bi 2 O 3 The dynamic constant k of the nano material is improved to 2.29 multiplied by 10 -2 min -1 。
As shown in fig. 19. The characteristic absorption peak at 497nm is significantly reduced, and all materials are shown in the tableExhibit high photocatalytic activity. Wherein, beta-Bi 2 O 3 The absorption peak disappears within 30min, the degradation rate can reach 96.97%, and the surprising photocatalytic activity is shown. After 120min of irradiation with visible light, the other three bismuth-based semiconductor photocatalysts show similar degradation rates, bi 2 O 2 CO 3 、α-Bi 2 O 3 And gamma-Bi 2 O 3 The photodegradation efficiencies for Congo Red (CR) were 94.44%, 95.58% and 90.91%, respectively.
As shown in FIG. 20 (a), after a dark reaction for 60min, the polycrystalline Bi phase 2 O 3 Higher adsorption to Congo Red (CR) dye, wherein beta-Bi 2 O 3 The adsorption rate of the catalyst can reach 60.61 percent, and in the photoreaction process, the beta-Bi 2 O 3 Only 36.36% degraded in 30 min. Description for Congo Red (CR) dye, beta-Bi 2 O 3 The adsorption performance of (a) is higher than the catalytic performance. For gamma-Bi 2 O 3 After irradiation of visible light for 80min, the degradation rate reaches a saturated state, and at the same time, alpha-Bi can be observed 2 O 3 The same trend is also exhibited. As shown in fig. 20 (b), it can be seen that the quasi-first order kinetic formula is still substantially satisfied. For first order linear fitting, bi 2 O 2 CO 3 、α-Bi 2 O 3 、β-Bi 2 O 3 And gamma-Bi 2 O 3 The apparent reaction rate constants of (2.28×10) were respectively -2 、2.07×10 -2 、7.06×10 -2 And 2.94×10 -2 min -1 . From the rate constant (k), it can be deduced that the order of photodegradation rates is: beta-Bi 2 O 3 ＞γ-Bi 2 O 3 ＞Bi 2 O 2 CO 3 ＞α-Bi 2 O 3 . This means β -Bi 2 O 3 Exhibiting more effective degradation to congo red.
As can be seen from FIG. 21, bi 2 O 2 CO 3 And gamma-Bi 2 O 3 Very poor degradation efficiency was exhibited for Methyl Orange (MO), 13.50% and 8.10%, respectively, with little decrease in absorbance. It can be observed that beta-Bi 2 O 3 Under irradiation of visible lightThe highest photocatalytic activity is shown, and the degradation rate reaches 92.59% in 120 min. alpha-Bi 2 O 3 The rate of catalytic degradation of methyl orange by nanomaterials is about 65.70%, although lower than beta-Bi 2 O 3 Nanomaterial, but still far higher than other bismuth-based oxide photocatalysts.
FIG. 22 (a) shows the photodegradation efficiency of Methyl Orange (MO) on different photocatalysts as a function of irradiation time. The low adsorption of the dye solution within 60 minutes of the dark reaction indicates the low adsorption capacity of the bismuth-based oxide catalyst for Methyl Orange (MO). For beta-Bi 2 O 3 The degradation rate was seen to be slow for the first 40min and increased rapidly after 40min, indicating that the chromonic structure of Methyl Orange (MO) was destroyed. alpha-Bi 2 O 3 Degradation from photoreaction occurs at nearly constant speed over time. While the other two photocatalysts have almost no degradation reaction. As shown in FIG. 22 (b), β -Bi 2 O 3 Apparent reaction rate constant k (1.79×10) -2 min -1 ) Is Bi 2 O 2 CO 3 (0.11×10 -2 min -1 ) Is 16 times that of alpha-Bi 2 O 3 (0.77×10 -2 min-1) 2.3 times higher than gamma-Bi 2 O 3 (0.07×10 -2 min -1 ) 25 times of (A), which confirms beta-Bi 2 O 3 The nanomaterial exhibits the highest photocatalytic activity.
In summary, the polycrystalline Bi phase prepared by the method of the invention 2 O 3 The material has good photocatalytic activity on rhodamine B, methylene blue, congo red and methyl orange.
Comparative example 1
The formulation and preparation method in this comparative example were substantially the same as those of example 1, except that the hydrothermal reaction temperature was 140℃and the reaction time was 12 hours.
As can be seen from the XRD results shown in fig. 23, in this comparative example, the XRD diffraction peaks showed a large peak packet, which could not correspond to PDF cards, indicating that the product was amorphous at this time.
Comparative example 2
The formulation and preparation method in this comparative example were substantially the same as those of example 1, except that the temperature of the hydrothermal reaction was 160℃and the reaction time was 12 hours.
As can be seen from the XRD results shown in FIG. 23, in this comparative example, the diffraction peak of XRD points to tetragonal phase Bi 2 O 2 CO 3 (PDF # 41-1488), but a broad and low diffraction peak indicates poor crystallinity at this time, and the generation of (002) crystal face was not observed. .
Comparative example 3
The formulation and preparation method in this comparative example were substantially the same as those of example 1, except that the temperature of the hydrothermal reaction was 200℃and the reaction time was 12 hours.
As shown in fig. 23, it can be seen that in this comparative example, when the temperature was increased to 200 ℃, it was observed that the intensity of the XRD diffraction peak was weaker and broader than that of 180 ℃, indicating that the crystallinity of the product was again deteriorated at this temperature.
Comparative example 4
The formulation and preparation method of this comparative example are substantially the same as those of example 1, except that Bi having a flower-like morphology is prepared 2 O 2 CO 3 Calcining in 500 ℃ air for 2 hours, and then naturally cooling to room temperature.
As shown in FIG. 24, it can be seen that in this comparative example, when the calcination temperature was increased to 500 ℃, the calcined product was observed to be compared with the α -Bi obtained in example 1 2 O 3 Compared with the prior art, the product is not uniform enough, the morphology is accompanied by the fragmentation of flower-like morphology, and meanwhile, the calcined product does not show a large amount of hollow morphology any more, which indicates that the calcining temperature is relative to flower-like alpha-Bi 2 O 3 Has a great influence on the synthesis of (a).
Comparative example 5
The formulation and preparation method of this comparative example are substantially the same as those of example 2, except that Bi having a flower-like morphology is prepared 2 O 2 CO 3 Calcining for 2 hours in air at 500 ℃, and then cooling to room temperature at a cooling rate of 5 ℃/min.
From the SEM results shown in FIG. 25, it can be seen that in this comparative example, when the calcination temperature was raised to 500℃it was observed that the calcined product was obtained with example 2The obtained beta-Bi 2 O 3 In contrast, the calcination product does not show a large amount of hollow morphology with the crushing of flower morphology, and the hollow structure is no longer obvious, so that the calcination temperature is shown for flower-like beta-Bi 2 O 3 Has a great influence on the synthesis of (a).
Comparative example 6
The formulation and preparation method of this comparative example are substantially the same as those of example 3, except that Bi having a flower-like morphology is prepared 2 O 2 CO 3 Calcining in air at 700 ℃ for 2 hours, and then cooling to room temperature at a cooling rate of 10 ℃/min.
As shown in FIG. 26, it can be seen that in this comparative example, when the calcination temperature was increased to 700 ℃, the calcined product was observed to be compared with the gamma-Bi obtained in example 3 2 O 3 In contrast, the product was in a bulk form, while the calcined product no longer exhibited a significant amount of cubic structure, indicating the calcination temperature versus cubic gamma-Bi 2 O 3 Has a great influence on the synthesis of (a).
From examples 1 to 3 and comparative examples 1 to 3, the following can be concluded:
(A) From example 1, example 2 and example 3, it can be seen that:
in example 1, alpha-Bi was finally produced 2 O 3 Material, example 2 finally obtaining beta-Bi 2 O 3 Material, example 3. Gamma. -Bi is finally obtained 2 O 3 Materials, the above examples illustrate that Bi according to the present invention 2 O 3 In the preparation method of the material, bi with different polycrystal phases can be obtained by controlling the calcination temperature and the cooling rate of the precursor of the target product 2 O 3 The material and the preparation method are simple and easy to operate.
(B) From examples 1 to 3, comparative examples 1 to 3, it can be seen that:
in the preparation method of the polycrystalline Bi2O3 material, the reaction temperature of the hydrothermal reaction influences the morphology of the product, and when the reaction temperature of the hydrothermal reaction is 180 ℃, the alpha-Bi with good optical performance flower morphology can be prepared 2 O 3 Material, beta-Bi 2 O 3 Material, gamma-Bi 2 O 3 A material.
From examples 1 to 3 and comparative examples 4 to 6, the following can be concluded:
(A) From example 1, example 2 and example 3, it can be seen that:
in example 1, alpha-Bi was finally produced 2 O 3 Material, example 2 finally obtaining beta-Bi 2 O 3 Material, example 3. Gamma. -Bi is finally obtained 2 O 3 Materials, the above examples illustrate that Bi according to the present invention 2 O 3 In the preparation method of the material, bi with different polycrystal phases can be obtained by controlling the calcination temperature and the cooling rate of the precursor of the target product 2 O 3 The material and the preparation method are simple and easy to operate.
(B) From examples 1 to 3 and comparative examples 4 to 6, it can be seen that:
the polycrystalline phase Bi of the present invention 2 O 3 In the preparation method of the material, the calcining temperature and the cooling rate have influence on the morphology of the product, and when the calcining temperature is 400 ℃ and then naturally cooled to room temperature, the alpha-Bi with flower-like morphology with good optical performance can be prepared 2 O 3 A material; when the calcining temperature is 400 ℃ and then the calcining temperature is cooled to room temperature at the cooling rate of 5 ℃/min, the beta-Bi with good optical performance and flower-like morphology can be prepared 2 O 3 A material; when the calcination temperature is 800 ℃ and then cooled to room temperature at a cooling rate of 10 ℃ per minute, the gamma-Bi with good optical properties can be prepared 2 O 3 A material.

Claims (3)

1. Polycrystalline Bi 2 O 3 The application of the material in photocatalytic degradation of rhodamine B, methylene blue, congo red and methyl orange is characterized in that the polycrystalline phase Bi 2 O 3 The material is prepared by the following steps:
step one, preparing a target product precursor solution;
dissolving 0.48g of bismuth nitrate pentahydrate and 0.38g of citric acid in deionized water, stirring until the bismuth nitrate pentahydrate and the citric acid are completely dissolved, and adding a proper amount of ammonia water to obtain a target product precursor solution;
step two, preparing flower-shaped Bi 2 O 2 CO 3 A precursor;
transferring the precursor solution of the target product prepared in the first step into a reaction kettle for hydrothermal reaction, cooling the obtained product to room temperature, centrifuging, washing and drying to obtain flower-shaped Bi 2 O 2 CO 3 ；
Step three, preparing the polycrystalline phase Bi 2 O 3 A material;
bi with flower-like morphology 2 O 2 CO 3 Calcining in air at 400 ℃ for 2 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the beta-Bi 2 O 3 ；
The temperature of the hydrothermal reaction is 180 ℃, and the reaction time is 12 hours;
the reaction temperature of the drying is 60 ℃, and the reaction heat preservation time is 12 hours.
2. The multicrystalline Bi according to claim 1 2 O 3 The preparation method of the material is characterized in that in the first step, the addition amount of ammonia water is 5ml.
3. The multicrystalline Bi according to claim 1 2 O 3 The preparation method of the material is characterized in that the polycrystalline phase Bi prepared in the step three 2 O 3 The material is prepared from Bi with an average particle size of 2 mu m 2 O 3 Nanoparticle composition.
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