CN114042469B - Preparation method of bismuth oxycarbonate-based photocatalytic material - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
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- B01J35/39—
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- B01J35/51—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention relates to a preparation method of a bismuth oxycarbonate-based photocatalytic material, belonging to the field of photocatalytic materials. The preparation method of the bismuth oxycarbonate-based photocatalytic material comprises the following steps: dispersing the carbon nanospheres into an organic solvent, and marking as A; dissolving bismuth nitrate in mixture of nitric acid and organic solventMixing the solution to obtain B; slowly dripping the B into the A under the stirring condition, and mixing to obtain C; wherein the mass ratio of the carbon nanospheres to the bismuth nitrate is 0.05-4%; c, carrying out solvothermal reaction, washing and drying the obtained product to obtain the 3D hollow Bi/Bi 2 O 2 CO 3 (ii) a Wherein the reaction temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 4-16 h; mixing Bi/Bi 2 O 2 CO 3 Roasting at 200-550 deg.c for 1.8-2.2 hr to obtain bismuth oxycarbonate base photocatalytic material. The invention prepares the 3D hollow Bi 2 O 2 CO 3 The base photocatalysis material is environment-friendly, pollution-free, simple and controllable in operation.
Description
Technical Field
The invention relates to a preparation method of a bismuth oxycarbonate-based photocatalytic material, belonging to the field of photocatalytic materials.
Background
Bi 2 O 2 CO 3 As a bismuth compound semiconductor having an Aurivillius-type oxide structure, extraction of the valence band position is achieved by orbital hybridization of Bi6s and O2pHigh, and thus has better light response performance in a manner of reducing the forbidden bandwidth. Bi 2 O 2 CO 3 Has (Bi) 2 O 2 ) 2+ Layer and CO 3 2- The internal electric field between the layers is beneficial to photo-generated electron-hole separation, and the photocatalyst shows excellent photocatalytic activity. A great deal of research has proved that Bi 2 O 2 CO 3 Has great potential in the aspect of removing environmental pollutants, and can effectively degrade organic pollutants in waste water and atmosphere. Unique layered structure, excellent photocatalytic activity, good photostability and the like, so that the Bi 2 O 2 CO 3 Becomes a photocatalyst with great development potential. Bi of different morphologies 2 O 2 CO 3 Shows different photocatalytic activities, and the reports at present comprise zero-dimensional, one-dimensional, two-dimensional and three-dimensional structures, wherein Bi in three dimensions 2 O 2 CO 3 The compound is mainly in the shape of ball, flower, persimmon, egg, etc. The three-dimensional structure has larger specific surface area and is beneficial to light absorption, and the layered structure is obviously beneficial to full contact of light and reactants with the catalyst and increases the reactive sites. Although Bi 2 O 2 CO 3 Has a plurality of advantages, but the defects of large forbidden band width (3.3 eV), high electron-hole recombination rate and the like limit Bi 2 O 2 CO 3 The method is applied in practice. Bismuth oxide is considered to be a good visible light catalyst due to its narrow band gap energy, good photoconductivity and safety, among which β -Bi 2 O 3 The best photocatalytic activity is shown due to the narrow gap energy and the high visible light absorption capacity. But is pure beta-Bi 2 O 3 The photocatalytic performance of (2) is limited by photo-corrosion and high photoelectron-hollow recombination rate. Using p-type beta-Bi 2 O 3 And n-type Bi 2 O 2 CO 3 The p-n heterojunction is constructed, so that the defects of the p-n heterojunction can be effectively overcome, visible light response is realized, the photoinduced carrier separation efficiency is high, and the stability is goodA composite photocatalyst. The method for preparing the hollow material mainly adopts a template method, and has a plurality of defects by adopting a hard template and a soft template, such as SiO 2 The microspheres are used as a template, and are dissolved by adopting hydrofluoric acid and the like to form a hollow structure; high-molecular polymers such as F127 are used as a soft template to introduce organic matters, and the organic matters are washed at the later stage to obtain a hollow structure.
Disclosure of Invention
The invention solves the first technical problem of providing an in-situ prepared 3D hollow Bi which is environment-friendly, pollution-free, simple and controllable to operate 2 O 2 CO 3 A method of base photocatalytic material.
The preparation method of the bismuth oxycarbonate-based photocatalytic material comprises the following steps:
a. dispersing the carbon nanospheres into an organic solvent to obtain a uniform suspension, and marking the suspension as a solution A; dissolving bismuth nitrate in a mixed solution of a nitric acid solution and an organic solvent to obtain a transparent solution B; slowly dripping the solution B into the solution A under the stirring condition, and mixing to obtain a solution C; wherein, the mass ratio of the carbon nanospheres to the bismuth nitrate is 0.05-4%;
b. carrying out solvothermal reaction on the solution C, washing and drying the obtained product to obtain the 3D hollow Bi/Bi 2 O 2 CO 3 (ii) a Wherein the reaction temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 4-16 h;
c. the obtained Bi/Bi 2 O 2 CO 3 Roasting at 200-550 deg.c for 1.8-2.2 hr to obtain bismuth oxycarbonate base photocatalytic material.
In one embodiment: in step a, the organic solvent is DMF.
In one embodiment: in the step a, the carbon nanospheres are prepared by hydrothermal reaction of glucose; the preferable hydrothermal reaction temperature is 160-180 ℃, and the reaction time is 3.5-10 h; more preferably, the hydrothermal reaction temperature is 180 ℃ and the reaction time is 8h.
In one embodiment: in the step a, the surface of the carbon nanosphere contains-OH and-COOH, and the particle size of the carbon nanosphere is 400 nm-1400 nm; the preferred particle size of the carbon nanoball is 600nm.
In one embodiment: in the step a, the mass ratio of the carbon nanospheres to the bismuth nitrate is 2.5%.
In one embodiment: in the step a, in the mixed solution, the volume ratio of the nitric acid solution to the organic solvent is 1-3:1, wherein the nitric acid solution accounts for 10% of the volume fraction; preferably, the volume ratio of the nitric acid solution to the organic solvent in the mixed solution is 1:1.
In one embodiment: in the step b, the reaction temperature of solvothermal reaction is 140-180 ℃; the preferred solvothermal reaction temperature is 180 ℃.
In one embodiment: in the step b, the reaction time is 8h.
In one embodiment: in the step c, the roasting temperature is 200-400 ℃; preferably, the roasting temperature is 200-370 ℃; more preferably from 200 to 260 ℃.
In one embodiment: in the step c, the roasting time is 2 hours.
The invention has the beneficial effects that:
1) The invention adopts a novel method which is not reported at home and abroad to prepare the three-dimensional hollow multi-shell Bi in situ 2 O 2 CO 3 The material has the capability of degrading organic pollutants under the irradiation of visible light and has strong photocatalytic capability.
2) The three-dimensional hollow multi-shell Bi obtained by the method of the invention 2 O 2 CO 3 The base photocatalytic material has the advantages of good crystallinity, uniform appearance, controllable size, high purity, good photocatalytic activity and high stability. Analysis by XRD: the obtained product has characteristic diffraction peak and PDF #41-1488 (Bi) 2 O 2 CO 3 )、PDF#27-0050(β-Bi 2 O 3 )、PDF#44-1246(Bi)、PDF#41-1499(α-Bi 2 O 3 ) One or more of the compositions are completely matched, and different products can be obtained by adjusting the material ratio, the solvothermal temperature, the solvothermal time and the roasting temperature.
3) The method adopts the carbon nanospheres as the sacrificial template, and the surface groups adsorb Bi in the reaction process 3+ Form a three-dimensional structure of sheet-like assembly, and the carbon core takes part in oxidation-reduction reactionThe hollow structure is formed by sacrifice, and a template removing process is not needed, so that the preparation is green and environment-friendly, the cost is low, and the operation is simple and controllable.
Drawings
In fig. 1, a is an SEM image of the carbon nanoball, b is an XRD of the carbon nanoball, c is an infrared spectrum of the carbon nanoball, and d is a thermal stability image of the carbon nanoball.
FIG. 2 is an XRD pattern and an SEM pattern of the product obtained in example 1 at different solvothermal temperatures for a solvothermal time of 8h.
FIG. 3 is an XRD pattern and an SEM pattern of the product obtained in example 1 at a solvothermal temperature of 180 ℃ and different solvothermal times.
FIG. 4 is an XRD (X-ray diffraction), infrared spectrum and thermal stability chart of the product obtained in example 1 when the solvothermal temperature is 180 ℃ and the solvothermal time is 8 hours.
FIG. 5a is an XRD pattern of the calcined product obtained in example 2-1 and example 2-2; b is an SEM photograph of the calcined product of example 2-1.
FIG. 6 is an XRD pattern of a calcined product obtained in example 3.
FIG. 7 is an XRD pattern of a calcined product obtained in example 4.
FIG. 8 is a graph showing the effect of example 2-1 on degradation of rhodamine B (RhB).
FIG. 9 is a graph showing the effect of calcined products on Tetracycline (TC) degradation in example 2-1.
FIG. 10 is a graph showing the effect of the calcined product on Ciprofloxacin (CIP) degradation in example 2-1.
FIG. 11 is a photoelectron spectrum of the calcined product of example 2-1.
Detailed Description
The preparation method of the bismuth oxycarbonate-based photocatalytic material comprises the following steps:
a. dispersing the carbon nanospheres into an organic solvent to obtain a uniform suspension, and marking the suspension as a solution A; dissolving bismuth nitrate in a mixed solution of a nitric acid solution and an organic solvent to obtain a transparent solution B; slowly dripping the solution B into the solution A under the stirring condition, and mixing to obtain a solution C; wherein the mass ratio of the carbon nanospheres to the bismuth nitrate is 0.05-4%;
b. carrying out solvothermal reaction on the solution C, washing and drying the obtained product to obtain the 3D hollow Bi/Bi 2 O 2 CO 3 (ii) a Wherein the reaction temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 4-16 h;
c. the obtained Bi/Bi 2 O 2 CO 3 Roasting at 200-550 deg.c for 1.8-2.2 hr to obtain bismuth oxycarbonate-base photocatalytic material.
The method firstly prepares the 3D hollow Bi/Bi 2 O 2 CO 3 And then roasting to obtain the bismuth oxycarbonate-based photocatalytic material, wherein the obtained bismuth oxycarbonate-based photocatalytic material has a 3D hollow structure without collapse.
The principle of the method of the invention is as follows: the carbon nanosphere is used as a sacrificial template, and a large amount of-OH and-COOH groups contained on the surface of the carbon nanosphere can adsorb Bi in a large amount 3+ So as to enrich Bi source on the surface of the carbon nanosphere, and the carbon core participates in the oxidation-reduction reaction along with the hydrothermal reaction, so as to lead Bi to be generated 3+ Reducing the Bi into simple substance and oxidizing the Bi to provide a carbon source, removing the template to form a hollow structure, and adsorbing the Bi on the surface of the carbon sphere 3+ The group is heated and decomposed to finally obtain the three-dimensional hollow structure bismuth-based photocatalytic material, which is the key point for forming the hollow structure.
Wherein, in the step b, when the solvothermal temperature is higher than 180 ℃, the prepared Bi/Bi 2 O 2 CO 3 Is a solid spherical structure.
In the step c, when the roasting temperature is 200-260 ℃, the obtained product is Bi/beta-Bi 2 O 3 /Bi 2 O 2 CO 3 (ii) a When the roasting temperature is 270-370 ℃, the obtained product is beta-Bi 2 O 3 /Bi 2 O 2 CO 3 (ii) a When the roasting temperature is 400 ℃, the obtained product is beta-Bi 2 O 3 (ii) a When the roasting temperature is 450-550 ℃, the obtained product is alpha-Bi 2 O 3 。
According to the experiment of the invention, the photocatalytic performance of the product is sequenced as follows: bi/beta-Bi 2 O 3 /Bi 2 O 2 CO 3 ＞β-Bi 2 O 3 /Bi 2 O 2 CO 3 ＞β-Bi 2 O 3 ＞α-Bi 2 O 3 。
In one embodiment: in step a, the organic solvent is DMF.
In one embodiment: in the step a, the carbon nanospheres are prepared by glucose hydrothermal reaction; the preferable hydrothermal reaction temperature is 160-180 ℃, and the reaction time is 3.5-10 h; more preferably, the hydrothermal reaction temperature is 180 ℃ and the reaction time is 8h.
The concentration of glucose may be 0.5 to 1M when preparing the carbon nanoball. After the glucose aqueous thermal reaction, the carbon nanospheres can be obtained by washing and drying. The washing was carried out with water and ethanol.
In one embodiment: in the step a, the surface of the carbon nanosphere contains-OH and-COOH, and the particle size of the carbon nanosphere is 400 nm-1400 nm; the preferred particle size of the carbon nanoball is 600nm.
In one embodiment: in the step a, the mass ratio of the carbon nanospheres to the bismuth nitrate is 2.5%.
In one embodiment: in the step a, in the mixed solution, the volume ratio of the nitric acid solution to the organic solvent is 1-3:1, wherein the nitric acid solution accounts for 10% of the volume fraction; preferably, the volume ratio of the nitric acid solution to the organic solvent in the mixed solution is 1:1.
To improve the photocatalytic performance of the product, in one embodiment: in the step b, the reaction temperature of solvothermal reaction is 140-180 ℃; the preferred solvothermal reaction temperature is 180 ℃.
In one embodiment: in the step b, the reaction time is 8h.
To improve the photocatalytic performance of the product, in one embodiment: in the step c, the roasting temperature is 200-400 ℃; preferably, the roasting temperature is 200-370 ℃; more preferably from 200 to 260 ℃.
In one embodiment: in the step c, the roasting time is 2 hours.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The carbon nanospheres used in the following experiments were all the same and were prepared by the following method:
and (3) putting 80mL of glucose 0.5M solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 180 ℃, naturally cooling, centrifuging, collecting precipitate, washing with deionized water and ethanol for three times, and drying at 80 ℃ to obtain a brown product, namely the carbon nanosphere.
The SEM, XRD, infrared and thermal stability of the resulting brown carbon nanospheres are shown in fig. 1a, 1b, 1c and 1d, respectively. As can be seen from the SEM image, the particle size of the carbon nanoball is about 600nm.
Example 1Bi/Bi 2 O 2 CO 3 Preparation of
(1) Preparing materials: dispersing 0.05g of carbon nanospheres into 10mL of DMF, and performing ultrasonic treatment to obtain a uniformly dispersed suspension liquid which is marked as a solution A; dissolving 5mmol of bismuth nitrate in a mixed solution of 10mL of nitric acid (1:9) and 10mL of DMF, and stirring to obtain a transparent solution which is marked as a solution B; slowly dropwise adding the solution B into the solution A under the stirring condition, continuously stirring for 30min, transferring into a 50mL polytetrafluoroethylene lining reaction kettle, and adding water until the filling degree is 70%;
(2) Solvent heat: and placing the reaction kettle in a vacuum atmosphere furnace for reaction for T hours at the temperature of T ℃, centrifugally collecting a product, washing the product for three times by using deionized water and ethanol, and dispersing the obtained gray product in a crucible by using ethanol and drying the gray product.
The XRD patterns and SEM patterns of the products obtained by using different solvothermal times and different solvothermal temperatures are shown in table 1 below.
| Reaction temperature/. Degree.C | Reaction time/h | XRD pattern | SEM image | Morphology of |
| 120 | 8 | FIG. 2a | FIG. 2b | 3D hollow microspheres |
| 140 | 8 | FIG. 2a | FIG. 2c | 3D |
| 160 | 8 | FIG. 2a | FIG. 2d | 3D hollow microspheres |
| 180 | 8 | FIG. 2a | FIG. 2e | 3D hollow microspheres |
| 190 | 8 | FIG. 2a | FIG. 2f | Solid microspheres |
| 180 | 1 | FIG. 3a | FIG. 3b | Solid microspheres |
| 180 | 2 | FIG. 3a | FIG. 3c | Solid microspheres |
| 180 | 4 | FIG. 3a | FIG. 3d | 3D hollow microspheres |
| 180 | 12 | FIG. 3a | FIG. 3e | 3D hollow microspheres |
| 180 | 16 | FIG. 3a | FIG. 3f | 3D hollow microspheres |
As can be seen from FIG. 2, when the reaction temperature is 120-180 ℃ and the reaction time is 8h, bi/Bi can be prepared 2 O 2 CO 3 Hollow microspheres; as can be seen from FIG. 3, when the reaction temperature is 180 ℃ and the reaction time is 4-16 h, bi/Bi can be prepared 2 O 2 CO 3 Hollow microspheres.
When the reaction temperature is 180 ℃, the XRD pattern of the obtained product is shown as figure 4a, the infrared spectrum is shown as figure 4b, and the thermal stability is shown as figure 4c when the reaction time is 8h.
Example 2-1 Bi/. Beta. -Bi 2 O 3 /Bi 2 O 2 CO 3 Preparation of
(1) Preparing materials: the same compounding method as in example 1;
(2) Solvent heat: and placing the reaction kettle in a vacuum atmosphere furnace for reacting for 8 hours at 180 ℃, centrifugally collecting a product, washing the product for three times by using deionized water and ethanol, and dispersing the obtained gray product in a crucible by using ethanol and drying the gray product.
(3) Roasting: putting the dried sample and the crucible into a ceramic fiber muffle furnace together to be roasted for 2h at 240 ℃, and obtaining a product which is Bi/beta-Bi 2 O 3 /Bi 2 O 2 CO 3 As shown in FIG. 5, it can be seen that Bi/beta-Bi is produced 2 O 3 /Bi 2 O 2 CO 3 Is a hollow spherical structure.
Examples 2 to 2
The gray product prepared in the step (2) of the example 2-1 is taken and put into a ceramic fiber muffle furnace together with a crucible, and the gray product is roasted for 2 hours at 200 ℃ and 260 ℃ respectively to obtain Bi/beta-Bi 2 O 3 /Bi 2 O 2 CO 3 The XRD pattern is shown in figure 5a, and the products are detected to be hollow spherical structures.
Example 3 beta-Bi 2 O 3 /Bi 2 O 2 CO 3 Preparation of
(1) Preparing materials: the same compounding method as in example 1;
(2) Solvent heat: the same solvothermal method as in example 2-1;
(3) Roasting: putting the dried sample and the crucible into a ceramic fiber muffle furnace, and roasting at 270 deg.C, 280 deg.C, 290 deg.C, 300 deg.C, 310 deg.C, 320 deg.C, 350 deg.C, 370 deg.C for 2h to obtain the product of beta-Bi with different ratios 2 O 3 /Bi 2 O 2 CO 3 The XRD is shown in figure 6; the products are characterized by SEM images and are all confirmed to be hollow microsphere structures.
Example 4 beta-Bi 2 O 3 And alpha-Bi 2 O 3 Preparation of
(1) Preparing materials: the same compounding method as in example 1;
(2) Solvent heat: the same solvothermal method as in example 2-1;
(3) Roasting: placing the dried sample in a ceramic fiber muffle furnace together with a crucible, and respectively roasting at 400 deg.C, 450 deg.C, 500 deg.C, and 550 deg.C for 2h to obtain a product with a structure shown in FIG. 7, wherein the product obtained by roasting at 400 deg.C for 2h is beta-Bi 2 O 3 Roasting at 450 deg.c, 500 deg.c and 550 deg.c for 2 hr to obtain alpha-Bi product 2 O 3 . The obtained product is characterized by an SEM chart and is proved to be in a hollow microsphere structure.
Comparative example
(1) Preparing materials: the same compounding method as in example 1;
(2) Solvent heat: and placing the reaction kettle in a vacuum atmosphere furnace for reacting for 8 hours at 190 ℃, centrifugally collecting a product, washing the product for three times by using deionized water and ethanol, and dispersing the obtained gray product in a crucible by using ethanol and drying the gray product.
(3) Roasting: and putting the dried sample and the crucible into a ceramic fiber muffle furnace together to be roasted for 2 hours at 240 ℃, wherein the obtained product is the solid spherical product D1.
Test examples
1. Rhodamine B (RhB) degradation assay.
Adding 50mg of sample into 50mL of RhB solution, stirring in the dark for 30min, centrifuging 4mL of mixed solution to obtain the upper layer solution, turning on a xenon lamp for irradiation, centrifuging 4mL of mixed solution every 20min to obtain the upper layer solution, measuring the absorbance in the range of 200-800nm by using a TU-1950 ultraviolet-visible spectrometer (see figure 8), and obtaining the degradation rate of the RhB solution by using an absorptiometer at 554nm according to the Lambert-beer law.
2. Degradation experiments of Tetracycline (TC)
Adding 50mg of sample into 50mL of TC solution, stirring in the dark for 30min, centrifuging 4mL of mixed solution to obtain upper solution, starting a xenon lamp for irradiation, centrifuging 4mL of mixed solution every 20min to obtain upper solution, measuring absorbance within the range of 200-800nm by using a TU-1950 ultraviolet-visible spectrometer (see figure 9), and measuring the absorbance at 357nm by using an absorptiometer according to the Lambert-beer law to obtain the degradation rate of the TC solution.
3. Ciprofloxacin (CIP) degradation experiments,
adding 50mg of sample into 50mL of CIP solution, stirring in the dark for 30min, centrifuging 4mL of mixed solution to obtain upper solution, starting a xenon lamp for irradiation, centrifuging 4mL of mixed solution every 20min to obtain upper solution, measuring the absorbance in the range of 200-800nm by using a TU-1950 ultraviolet-visible spectrometer (see figure 10), and obtaining the degradation rate of the CIP solution by using an absorptiometer at 275nm according to the Lambert-beer law.
Taking the prepared Bi/beta-Bi 2 O 3 /Bi 2 O 2 CO 3 (T1 in tables 2 to 4), beta-Bi 2 O 3 /Bi 2 O 2 CO 3 (T2 in tables 2 to 4), beta-Bi 2 O 3 (T3 in tables 2 to 4), alpha-Bi 2 O 3 (T4 in tables 2 to 4) and the solid product D1 (D1 in tables 2 to 4) obtained in the comparative example were subjected to degradation tests, and the results are shown in tables 2 to 4 below. Wherein the sampled Bi/beta-Bi 2 O 3 /Bi 2 O 2 CO 3 Is the product prepared in the embodiment 2-1 by a roasting process at 240 ℃ for 2 h; the degradation rates of the product on rhodamine B, tetracycline and ciprofloxacin are shown in figures 8-10 in sequence. The sampled beta-Bi 2 O 3 /Bi 2 O 2 CO 3 Is the product obtained in example 3 by a roasting process at 290 ℃ for 2 h; the sampled product beta-Bi 2 O 3 The product is prepared by the roasting process of example 4 at 400 ℃ for 2 h; the sampled alpha-Bi 2 O 3 The product obtained in example 4 at a calcination temperature of 450 ℃ for 2h.
TABLE 2 degradation experiment (absorbance at 554 nm) for rhodamine B (RhB) for different samples
TABLE 3 degradation of Tetracycline (TC) by different samples (absorbance at 357 nm)
TABLE 4 degradation of Ciprofloxacin (CIP) with different samples (absorbance at 275 nm)
Claims (13)
1. The preparation method of the bismuth oxycarbonate-based photocatalytic material is characterized by comprising the following steps of:
a. dispersing the carbon nanospheres into an organic solvent to obtain a uniform suspension, and marking the suspension as a solution A; dissolving bismuth nitrate in a mixed solution of a nitric acid solution and an organic solvent to obtain a transparent solution B; slowly dripping the solution B into the solution A under the stirring condition, and mixing to obtain a solution C; the carbon nanospheres are prepared by glucose hydrothermal reaction, the mass ratio of the carbon nanospheres to bismuth nitrate is 0.05-4%, and the organic solvent is DMF;
b. carrying out solvothermal reaction on the solution C, washing and drying the obtained product to obtain the 3D hollow Bi/Bi 2 O 2 CO 3 (ii) a Wherein the reaction temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 4-1697 h;
c. the obtained Bi/Bi 2 O 2 CO 3 And (3) roasting at the temperature of 200-370 ℃ for 1.8-2.2h to obtain the bismuthyl carbonate-based photocatalytic material.
2. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 1, characterized in that: in the step a, the hydrothermal reaction temperature is 160 to 180 ℃, and the reaction time is 3.5 to 10 hours.
3. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 1, characterized in that: in the step a, the method comprises the following steps of,
the hydrothermal reaction temperature is 180 ℃, and the reaction time is 8h.
4. The method for producing a bismuthyl carbonate-based photocatalytic material according to claim 1, characterized in that: in the step a, the surface of the carbon nanosphere contains-OH and-COOH, and the particle size of the carbon nanosphere ranges from 400nm to 1400nm.
5. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 4, characterized in that: the particle size of the carbon nanoball is 600nm.
6. The method for producing a bismuthyl carbonate-based photocatalytic material according to claim 1, characterized in that: in the step a, the mass ratio of the carbon nanospheres to the bismuth nitrate is 2.5%.
7. The method for producing a bismuthyl carbonate-based photocatalytic material according to claim 1, characterized in that: in the step a, in the mixed solution, the volume ratio of the nitric acid solution to the organic solvent is 1 to 3, wherein the nitric acid solution accounts for 10% by volume fraction.
8. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 7, characterized in that: in the mixed solution, the volume ratio of the nitric acid solution to the organic solvent is 1:1.
9. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 1, characterized in that: in the step b, the solvothermal reaction temperature is 140-180 ℃.
10. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 9, characterized in that: in step b, the solvothermal reaction temperature is 180 ℃.
11. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 1, characterized in that: in the step b, the reaction time is 8h.
12. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 1, characterized in that: in the step c, the roasting temperature is 200 to 260 ℃.
13. The method for producing a bismuth oxycarbonate-based photocatalytic material according to claim 1, characterized in that: in the step c, the roasting time is 2 hours.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527420A (en) * | 2012-02-17 | 2012-07-04 | 重庆工商大学 | Bismuth subcarbonate photocatalyst and preparation method thereof |
| CN103447052A (en) * | 2013-03-25 | 2013-12-18 | 湖南大学 | Preparation and application of hollow tree-like bismuth oxide-bismuth sulfide complex |
| CN103950985A (en) * | 2014-04-29 | 2014-07-30 | 西南科技大学 | Nanometer bismuth tungstate with hollow square ball structure and preparation method thereof |
| CN107042103A (en) * | 2016-02-05 | 2017-08-15 | 高丽大学校产学协力团 | The photochemical catalyst of bioxin is removed, the method that the method and photoactivation agent for preparing photochemical catalyst handle bioxin contaminated soil |
| CN108212186A (en) * | 2018-01-18 | 2018-06-29 | 蚌埠学院 | A kind of method that room temperature solid-state reaction prepares bismuth oxide-bismuthyl carbonate nano-complex |
| CN108275722A (en) * | 2018-04-16 | 2018-07-13 | 陕西科技大学 | A kind of method of hydro-thermal and the synthesising mesoporous bismuth oxide of thermal decomposition method |
| CN108525689A (en) * | 2018-04-16 | 2018-09-14 | 陕西科技大学 | A kind of method of hydrothermal synthesis of carbon acid oxygen bismuth photochemical catalyst |
| CN108927188A (en) * | 2018-07-26 | 2018-12-04 | 桂林电子科技大学 | A kind of bismuth subcarbonate photocatalyst and preparation method thereof |
| CN110605126A (en) * | 2019-09-18 | 2019-12-24 | 成都理工大学 | Cavity BiOCl @ CeO2Preparation method and application of nano composite material |
| CN113668244A (en) * | 2021-08-20 | 2021-11-19 | 四川轻化工大学 | Polyvinyl alcohol/methylene blue/nano silver composite sensing membrane and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754834B (en) * | 2017-10-26 | 2023-02-28 | 苏州大学 | Iodine-doped bismuthyl carbonate nanosheet and molybdenum disulfide-modified carbon nanofiber composite material and preparation method and application thereof |
-
2021
- 2021-12-02 CN CN202111462671.6A patent/CN114042469B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527420A (en) * | 2012-02-17 | 2012-07-04 | 重庆工商大学 | Bismuth subcarbonate photocatalyst and preparation method thereof |
| CN103447052A (en) * | 2013-03-25 | 2013-12-18 | 湖南大学 | Preparation and application of hollow tree-like bismuth oxide-bismuth sulfide complex |
| CN103950985A (en) * | 2014-04-29 | 2014-07-30 | 西南科技大学 | Nanometer bismuth tungstate with hollow square ball structure and preparation method thereof |
| CN107042103A (en) * | 2016-02-05 | 2017-08-15 | 高丽大学校产学协力团 | The photochemical catalyst of bioxin is removed, the method that the method and photoactivation agent for preparing photochemical catalyst handle bioxin contaminated soil |
| CN108212186A (en) * | 2018-01-18 | 2018-06-29 | 蚌埠学院 | A kind of method that room temperature solid-state reaction prepares bismuth oxide-bismuthyl carbonate nano-complex |
| CN108275722A (en) * | 2018-04-16 | 2018-07-13 | 陕西科技大学 | A kind of method of hydro-thermal and the synthesising mesoporous bismuth oxide of thermal decomposition method |
| CN108525689A (en) * | 2018-04-16 | 2018-09-14 | 陕西科技大学 | A kind of method of hydrothermal synthesis of carbon acid oxygen bismuth photochemical catalyst |
| CN108927188A (en) * | 2018-07-26 | 2018-12-04 | 桂林电子科技大学 | A kind of bismuth subcarbonate photocatalyst and preparation method thereof |
| CN110605126A (en) * | 2019-09-18 | 2019-12-24 | 成都理工大学 | Cavity BiOCl @ CeO2Preparation method and application of nano composite material |
| CN113668244A (en) * | 2021-08-20 | 2021-11-19 | 四川轻化工大学 | Polyvinyl alcohol/methylene blue/nano silver composite sensing membrane and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| Hui Zhou et al..Composite soft template-assisted construction of a flower-like β-Bi2O3/ Bi2O2CO3 heterojunction photocatalyst for the enhanced simulated sunlight photocatalytic degradation of tetracycline.《Ceramics International》.2019,第45卷第15036-15047页. * |
| Reza Abazari et al..Photocatalytic wastewater purification under visible light irradiation using bismuth molybdate hollow microspheres with high surface area.《Journal of Cleaner Production》.2019,第221卷第582-586页. * |
| Sheng Yin et al..In situ preparation of Bi2O3/( BiO)2CO3 composite photocatalyst with enhanced visible‑light photocatalytic activity.《Research on Chemical Intermediates》.2021,第47卷第1601–1613页. * |
| Yong Huang et al..Controlled synthesis of β-Bi2O3/Bi2O2CO3 hollow microspheres with enhanced photocatalytic degradation of tetracycline under visible light.《Materials Today Communications》.2022,第33卷第1-6页. * |
| 董帆等. 微结构优化与GO耦合大幅提高（BiO）2CO3可见光催化性能.《科学通报》.2015,第60卷(第20期),第1915 -1923页. * |
| 薛文兴 ; 谢丽燕 ; 王万军 ; 刘明华 ; 黄建辉 ; .多级结构形貌β-Bi_2O_3/BiOCOOH复合光催化剂的制备及其光催化性能.材料研究学报.2020,(第04期),第73-82页. * |
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