CN116351454A - Bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, and preparation and application thereof - Google Patents
Bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, and preparation and application thereof Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/10—Photocatalysts
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, and preparation and application thereof, comprising bismuth oxychloride with a {010} crystal face mainly exposed and nitrogen-doped carbon quantum dots, wherein the nitrogen-doped carbon quantum dots are anchored on the {010} crystal face exposed by bismuth oxychloride. {010} bismuth oxychloride is an ultrathin irregular nano-sheet structure, and the mass percentage of the doped carbon quantum dots is 0.01% -0.08%. The photocatalyst is prepared by mixing bismuth nitrate pentahydrate with nitrogen-doped carbon quantum dot solution, adjusting pH by alkaline solution, and performing hydrothermal reaction, wherein the nitrogen-doped carbon quantum dot solution is prepared by performing hydrothermal reaction on ammonium citrate and ethylenediamine. The catalyst expands the photoresponse range by utilizing the synergistic effect of the high-energy exposed crystal face and the nitrogen doped carbon quantum dots, promotes the migration of photo-generated carriers and accelerates the generation of surface oxidation-reduction reaction, achieves the aim of improving the photocatalytic performance of bismuth oxychloride, has the degradation efficiency of 85.2% in wastewater polluted by antibiotics, and has the advantages of stable photocatalytic performance, strong corrosion resistance and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst, and preparation and application thereof.
Background
Antibiotics are one of the most popular multifunctional drugs because they can be applied not only to disease treatment, infection prevention but also to promotion of growth of animals and plants, etc. The resulting abuse of antibiotics results in significant amounts of antibiotic residues entering the aquatic ecosystem through water and soil loss, animal waste and wastewater discharge, severely threatening ecological safety and human health. The application of the semiconductor photocatalysis technology in degrading toxic and harmful persistent pollutants such as antibiotics in water has great significance in solving the water pollution problem. However, poor photoresponsivity and low utilization of photogenerated carriers remain a design bottleneck for semiconductor photocatalysts. Therefore, the efficient renewable photocatalyst with visible light response is actively developed, the effect of solar energy is fully exerted, and the method has important significance.
Bismuth oxychloride is considered as an effective photocatalyst for degrading pollutants due to its high chemical stability, unique layered structure, corrosion resistance and good photocatalytic performance. However, their further application is hindered by limited light absorption capacity, high recombination rate of photogenerated electron-hole pairs and slow surface reactions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the bismuth oxychloride-based photocatalyst which has the advantages of wide photoresponse range, high photogenerated electron-hole separation efficiency, high photocatalytic activity, good stability and corrosion resistance, and the preparation method and the application thereof.
In order to achieve the aim, the invention firstly provides a bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, which comprises bismuth oxychloride and nitrogen-doped carbon quantum dots, wherein the crystal face of the bismuth oxychloride is mainly exposed {010} crystal face, the nitrogen-doped carbon quantum dots are anchored on the {010} crystal face of the bismuth oxychloride, the mass percentage of the nitrogen-doped carbon quantum dots is 0.01% -0.08%,
preferably, the mass percentage of the nitrogen-doped carbon quantum dots is 0.02%.
Preferably, the diameter of the nitrogen-doped carbon quantum dots is less than 10nm.
Preferably, the bismuth oxychloride with the {010} crystal face mainly exposed is in an ultrathin irregular nano-sheet structure.
Based on a general inventive concept, the invention also provides a preparation method of the nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst, which comprises the following steps:
s1, adding bismuth nitrate pentahydrate and a nitrogen-doped carbon quantum dot solution into a glycerol-water mixed solvent, and ultrasonically stirring until a uniform mixed solution is formed;
s2, dropwise adding a saturated sodium chloride solution into the mixed solution obtained in the step S1, and uniformly stirring by ultrasonic waves;
s3, dropwise adding an alkaline solution with a certain concentration into the mixed solution obtained in the step S2 to adjust the pH to 5-7;
and S4, carrying out hydrothermal treatment on the mixed solution obtained in the step S3 to obtain the {010} bismuth oxychloride anchored by the nitrogen-doped carbon quantum dots.
Preferably, in the step S1, the molar ratio of bismuth nitrate pentahydrate to the nitrogen-doped carbon quantum dot solution is 1: 0.002-0.008; the ultrasonic dispersion time is 15-40 min; the stirring time is 15-40 min.
Preferably, in the step S2, an excessive saturated sodium chloride solution is added; the ultrasonic dispersion time is 15-40 min; the stirring time is 15-40 min.
Preferably, the alkaline solution in the step S3 is any one of sodium hydroxide solution and potassium hydroxide solution.
Preferably, the hydrothermal reaction temperature in the step S4 is 120-180 ℃ and the reaction time is 5-10 h.
Preferably, the preparation method of the nitrogen-doped carbon quantum dot comprises the following steps: mixing ammonium citrate, ethylenediamine and water to obtain a precursor solution; and carrying out hydrothermal reaction on the precursor solution, collecting the reacted solution, and carrying out dialysis reaction to obtain the nitrogen-doped carbon quantum dot solution. Wherein, the mol ratio of the ammonium citrate to the ethylenediamine is 8-15:5-10, and the hydrothermal reaction temperature is 160-200 ℃; the hydrothermal reaction time is 3-8 h; the volume ratio of the solution to the ultrapure water in the dialysis reaction is 1:80-120, and the dialysis time is 20-28 h.
Based on a general inventive concept, the invention also provides an application of the nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst in the catalytic degradation of antibiotics in wastewater, which comprises the following steps:
s1: mixing the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots with wastewater containing antibiotic pollutants, and stirring;
s2: performing photocatalytic reaction under the illumination condition to finish degradation of the antigen pollutants;
preferably, the photocatalyst is added to the organic pollutant-containing wastewater in an amount of 0.2g to 1.0g per liter.
Preferably, the antibiotic contaminant is ciprofloxacin.
Preferably, the initial concentration of the ciprofloxacin pollutant is 5mg/L to 20mg/L; the illumination condition lambda is more than or equal to 420nm; the time of the photocatalytic reaction is more than or equal to 60min.
The photocatalyst provided by the invention has the main action mechanism that:
the crystal plane effect is thought to promote the surface redox reaction by regulating the coordination and arrangement of surface atoms. The up-conversion effect of the nitrogen doped carbon quantum dots can convert low-energy incident light into high-energy light emission, so that the solar energy utilization rate can be improved. Therefore, the synergistic effect of crystal face regulation and nitrogen doped carbon quantum dot anchoring is significant for improving the photocatalytic performance of bismuth oxychloride.
Aiming at the defects of limited photoresponse capacity, high recombination rate of photo-generated electron-hole pairs, slow surface reaction and the like of bismuth oxychloride, the invention creatively regulates and controls the main exposure crystal face of bismuth oxychloride into a {010} high-energy crystal face, anchors nitrogen-doped carbon quantum dots on the crystal face, expands the photoresponse range by utilizing the synergistic effect of the high-energy exposure crystal face and the nitrogen-doped carbon quantum dots, promotes the migration of photo-generated carriers and accelerates the occurrence of surface oxidation-reduction reaction, thereby achieving the aim of improving the photocatalytic performance of bismuth oxychloride. Specifically, bismuth oxychloride with exposed {010} crystal face has larger surface area and open channel characteristics, and can provide larger space for loading of nitrogen-doped carbon quantum dots. Therefore, the nitrogen-doped carbon quantum dots are loaded on the surface of the bismuth oxychloride exposed by the {010} crystal face, so that the formation of an effective heterojunction channel between the nitrogen-doped carbon quantum dots and the bismuth oxychloride can be promoted, and the electron conduction performance of the nitrogen-doped carbon quantum dots can be better exerted. In addition, the {010} crystal face is exposed to more terminal bismuth atoms and can be used as active sites of photocatalytic reaction, and the up-conversion performance of the nitrogen-doped carbon quantum dots can effectively improve the photoresponsive capacity of the photocatalyst. Therefore, the constructed {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots shows very excellent visible light absorption capacity and photocatalytic performance. In addition, the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots has excellent degradation effect when being applied to the degradation of antibiotic pollutants under the condition of simulating visible light (lambda is more than or equal to 420 nm), and can effectively degrade the antibiotic pollutants in wastewater.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a {010} bismuth oxychloride photocatalyst anchored by nitrogen-doped carbon quantum dots, which firstly regulates the main exposed crystal face of a bismuth oxychloride nano-sheet into a {010} crystal face, and then anchors the nitrogen-doped carbon quantum dots on the {010} bismuth oxychloride nano-sheet.
(2) In the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots, the main exposure crystal face of bismuth oxychloride is optimized to be the {010} crystal face, the anchoring of the nitrogen-doped carbon quantum dots on the bismuth oxychloride surface is facilitated, and the full contact between the nitrogen-doped carbon quantum dots and the bismuth oxychloride is promoted, so that more excellent photocatalytic performance can be obtained, and the nitrogen-doped carbon quantum dots can form a crystal edge [ Bi2O2 ] at a heterojunction interface when anchored on the {010} crystal face of bismuth oxychloride]2 + The covalent ring in the direction of N-CQDs-Cl-is beneficial to the directional transfer of electrons to form an interface electric field, so that the transfer of photo-generated charges is beneficial to the prepared photocatalyst with more excellent photocatalytic performance.
(3) In the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots, the mass percentage content of the nitrogen-doped carbon quantum dots is optimized to be 0.01-0.08%. When the content of the nitrogen-doped carbon quantum dots is too small, a small amount of the nitrogen-doped carbon quantum dots are insufficient to form an interface electric field favorable for charge transfer, so that effective separation and migration of photo-generated electrons and holes in the bismuth oxychloride nano-sheet are difficult to realize, and when the content of the nitrogen-doped carbon quantum dots is excessive, an effective heterojunction section can be damaged, so that the photocatalytic activity is reduced. Particularly, when the mass percentage content of the nitrogen-doped carbon quantum dots is 0.01% -0.08%, the obtained {010} bismuth oxychloride photocatalyst anchored by the cobalt-nitrogen-doped carbon quantum dots has more excellent photocatalytic performance.
(4) The invention utilizes alkaline solution to regulate and control the main exposed crystal face of bismuth oxychloride to be {010} high-energy crystal face; the nitrogen-doped carbon quantum dots with wide light absorption range and high light absorption efficiency are prepared by adopting the simple hydrothermal reaction by taking ammonium citrate, ethylenediamine and water as raw materials; the method has the advantages of simple and convenient synthesis method, low raw material cost, low energy consumption, short time consumption, easy control of conditions, no generation of byproducts polluting the environment in the preparation process, suitability for continuous large-scale batch production, and convenient industrial utilization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001) and nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010) in experimental example 1 of the present invention, wherein FIG. 1a is BOC-001, FIG. 1b is BOC-010, and FIG. 1c is 10NBOC-010;
FIG. 2 is a TEM diagram of {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001) and nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010) in experimental example 2 of the present invention, wherein FIG. 2a is BOC-001, FIG. 2b is BOC-010, and FIG. 2c is 10NBOC-010;
FIG. 3 is an ultraviolet-visible diffuse reflectance spectrum of {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010), and nitrogen doped carbon quantum dot anchored {001} bismuth oxychloride nanosheets (10 NBOC-001) in experimental example 3 of the present invention;
FIG. 4 is a transient photoelectric flow chart of {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010), and nitrogen doped carbon quantum dot anchored {001} bismuth oxychloride nanosheets (10 NBOC-001) in Experimental example 4 of the present invention;
FIG. 5 is a graph showing the synergistic effect of the nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride nanoplatelets (10 NBOC-010) in experimental example 5 of the present invention, wherein FIG. 5a is a three-dimensional differential charge density plot of 10NBOC-010 and FIG. 5b is a planar average differential charge density plot of 10NBOC-010;
FIG. 6 is a graph showing the results of the efficiency of degradation of antibiotic pollutants by BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 in experimental example 6 of the present invention, wherein FIG. 6a is a graph showing the time-degradation efficiency corresponding to photocatalytic degradation of ciprofloxacin wastewater under irradiation of visible light by {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (6 NBOC-010, 10NBOC-010, 14 NBOC-010) and nitrogen doped carbon quantum dot anchored {001} bismuth oxychloride nanosheets (10 NBOC-001); FIG. 6b shows degradation coefficients for different materials BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 treatments.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated; the reagents used in the examples were all commercially available unless otherwise specified.
Example 1
Preparation of nitrogen-doped carbon quantum dots
The preparation process of the specific nitrogen-doped carbon quantum dot comprises the following steps: 10mmol of ammonium citrate was added to 20mL of ultrapure water and stirred to dissolve, followed by dropwise addition of 670. Mu.L of ethylenediamine. After stirring for 30min, the mixed solution was sealed in a stainless steel reaction kettle and placed in a 200 ℃ oven for reaction for 5h. After the reaction kettle is naturally cooled to room temperature, the solution is prepared according to the volume ratio: the resulting solution was dialyzed (MWCO 1000) against ultrapure water=1:100 for 24 hours to finally produce an aqueous solution of N-CQDs having a concentration of about 0.5M.
Example 2
Preparation of bismuth oxychloride photocatalyst with {010} surface as main exposed crystal face
S1, under the stirring condition, sequentially adding 0.486g bismuth nitrate pentahydrate and 25mL ultrapure water into 25mL glycerol solution, and ultrasonically stirring to form a uniform mixed solution;
s2, dropwise adding 5mL of saturated NaCl solution into the mixed solution prepared in the step S1, and ultrasonically stirring until a uniform mixed solution is formed;
s3, adjusting the pH value of the mixed solution obtained in the step S2 to 6 by using a sodium hydroxide solution;
s4, transferring the mixed solution with the pH value of 6 obtained in the step S3 into a 100mL stainless steel autoclave, performing hydrothermal reaction for 6 hours at 160 ℃, cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the bismuth oxychloride photocatalyst with the main exposed crystal face of {010} face, which is named as BOC-010.
Comparative example 1
Preparation of bismuth oxychloride photocatalyst with {001} surface as main exposed crystal face
S1, under the stirring condition, sequentially adding 0.486g bismuth nitrate pentahydrate and 25mL ultrapure water into 25mL glycerol solution, and ultrasonically stirring to form a uniform mixed solution;
s2, dropwise adding 5mL of saturated NaCl solution into the mixed solution prepared in the step S1, and ultrasonically stirring until a uniform mixed solution is formed;
s3, transferring the mixed solution obtained in the step S2 into a 100mL stainless steel autoclave, performing hydrothermal reaction for 6 hours at 160 ℃, cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the bismuth oxychloride photocatalyst with the main exposed crystal face of {001} face, which is named as BOC-001.
Example 3
Preparation of nitrogen-doped carbon Quantum dot anchored {010} bismuth oxychloride photocatalyst 6NBOC-010
In the embodiment, the mass percentage of the nitrogen-doped carbon quantum dots in the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots is 0.01%, and the mass percentage of the {010} bismuth oxychloride nanosheets is 99.99%.
The preparation method is characterized in that a bismuth oxychloride nano-sheet with a {010} surface as a main exposed crystal surface is used as a carrier, and nitrogen-doped carbon quantum dots are anchored on the {010} bismuth oxychloride nano-sheet, and the preparation method comprises the following steps:
s1, under the stirring condition, sequentially adding 0.486g of bismuth nitrate pentahydrate, 6mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water into 25mL of glycerol solution, and ultrasonically stirring to form a uniform mixed solution;
s2, dropwise adding 5mL of saturated NaCl solution into the mixed solution prepared in the step S1, and ultrasonically stirring until a uniform mixed solution is formed;
s3, adjusting the pH value of the mixed solution obtained in the step S2 to 6 by using a sodium hydroxide solution;
s4, transferring the mixed solution with the pH value of 6 obtained in the step S3 into a 100mL stainless steel autoclave, performing hydrothermal reaction for 6 hours at 160 ℃, cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the bismuth oxychloride photocatalyst with the main exposed crystal face of {010} face, which is named as 6NBOC-010.
Example 4
Preparation of nitrogen-doped carbon Quantum dot anchored {010} bismuth oxychloride photocatalyst 10NBOC-010
In this embodiment, the mass percentage of the nitrogen-doped carbon quantum dots in the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots is 0.02%, and the mass percentage of the {010} bismuth oxychloride nanosheets is 99.98%, and the preparation method is as follows:
s1, under the stirring condition, sequentially adding 0.486g of bismuth nitrate pentahydrate, 10mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water into 25mL of glycerol solution, and ultrasonically stirring to form a uniform mixed solution;
s2, dropwise adding 5mL of saturated NaCl solution into the mixed solution prepared in the step S1, and ultrasonically stirring until a uniform mixed solution is formed;
s3, adjusting the pH value of the mixed solution obtained in the step S2 to 6 by using a sodium hydroxide solution;
s4, transferring the mixed solution with the pH value of 6 obtained in the step S3 into a 100mL stainless steel autoclave, performing hydrothermal reaction for 6 hours at 160 ℃, cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the bismuth oxychloride photocatalyst with the main exposed crystal face of {010} face, which is named as 10NBOC-010.
Example 5
Preparation of nitrogen-doped carbon Quantum dot anchored {010} bismuth oxychloride photocatalyst 14NBOC-010
In this embodiment, the mass percentage of the nitrogen-doped carbon quantum dots in the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots is 0.03%, and the mass percentage of the {010} bismuth oxychloride nanosheets is 99.97%, and the preparation method is as follows:
s1, under the stirring condition, sequentially adding 0.486g of bismuth nitrate pentahydrate, 14mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water into 25mL of glycerol solution, and ultrasonically stirring to form a uniform mixed solution;
s2, dropwise adding 5mL of saturated NaCl solution into the mixed solution prepared in the step S1, and ultrasonically stirring until a uniform mixed solution is formed;
s3, adjusting the pH value of the mixed solution obtained in the step S2 to 6 by using a sodium hydroxide solution;
s4, transferring the mixed solution with the pH value of 6 obtained in the step 3 into a 100mL stainless steel autoclave, performing hydrothermal reaction at 160 ℃ for 6 hours, cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the bismuth oxychloride photocatalyst with the main exposed crystal face of {010} face, which is named as 14NBOC-010.
Comparative example 2
Preparation of nitrogen-doped carbon Quantum dot anchored {001} bismuth oxychloride photocatalyst 10NBOC-001
In the comparative example, the nitrogen-doped carbon quantum dot anchored {001} bismuth oxychloride photocatalyst comprises 0.02% of the nitrogen-doped carbon quantum dot and 99.98% of the {010} bismuth oxychloride nano-sheet.
The preparation method is characterized in that a bismuth oxychloride nanosheet with a {001} surface as a main exposed crystal surface is used as a carrier, and nitrogen-doped carbon quantum dots are anchored on the {001} bismuth oxychloride nanosheet, and the preparation method comprises the following steps:
s1, under the stirring condition, sequentially adding 0.486g of bismuth nitrate pentahydrate, 10mL of nitrogen-doped carbon quantum dot solution and 25mL of ultrapure water into 25mL of glycerol solution, and ultrasonically stirring to form a uniform mixed solution;
s1, dropwise adding 5mL of saturated NaCl solution into the mixed solution prepared in the step S1, and ultrasonically stirring until a uniform mixed solution is formed;
s1, transferring the mixed solution obtained in the step S2 into a 100mL stainless steel autoclave, performing hydrothermal reaction for 6 hours at 160 ℃, cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the bismuth oxychloride photocatalyst with the main exposed crystal face of {010} face, which is named as 10NBOC-001.
Experimental example 1
Examine the structural characteristics of BOC-001, BOC-010 and 10NBOC-010
As a result of scanning the three materials by electron microscope with respect to {001} bismuth oxychloride photocatalyst (BOC-001), {010} bismuth oxychloride photocatalyst (BOC-010), and nitrogen-doped carbon quantum dots anchored to {010} bismuth oxychloride nanosheets (10 NBOC-010), as shown in fig. 1, fig. 1 (a) shows that the structure of {001} bismuth oxychloride photocatalyst is a two-dimensional sheet-like tetragonal structure, fig. 1 (b) shows that the structure of {010} bismuth oxychloride photocatalyst is an ultrathin irregular nanosheet structure, and as shown in fig. 1 (c), nitrogen-doped carbon quantum dots are anchored to the surface of {010} bismuth oxychloride nanosheets, and the load of nitrogen-doped carbon quantum dots does not change the structure of {010} bismuth oxychloride nanosheets as compared with the {010} bismuth oxychloride nanosheets shown in fig. 1 (b).
Experimental example 2
Investigation of the Crystal face exposure characteristics of BOC-010, BOC-001, 10NBOC-010
The crystal face exposure characteristics of {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001) and the nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010) were examined by transmission electron microscopy.
The results are shown in FIG. 2, where a is BOC-001, b is BOC-010, and c is 10NBOC-010. As can be seen from FIG. 2a, the clear lattice fringes with BOC-001 interplanar spacing of 0.275nm correspond to {110} atom planes perpendicular to the {001} atom planes, i.e., the main exposed crystal planes of BOC-001 are {001} crystal planes; as is clear from FIG. 2b, it is apparent that the (002) atomic plane having a lattice spacing of 0.37nm, that is, BOC-010 is mainly surrounded by {010} planes. As can be seen from FIG. 2c, nitrogen-doped carbon quantum dots with a diameter of about 8nm are distributed on the surface of {010} bismuth oxychloride.
Experimental example 3
Examine the light response properties of BOC-010, BOC-001, 10NBOC-010, and 10NBOC-001
And carrying out light response performance detection on the {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), the nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010) and the nitrogen doped carbon quantum dot anchored {001} bismuth oxychloride nanosheets (10 NBOC-001) by utilizing an ultraviolet-visible diffuse reflection spectrum.
The results are shown in FIG. 3. The light absorption edges of BOC-010 and BOC-001 were 351nm and 375nm, respectively. After the nitrogen-doped carbon quantum dots are anchored, the absorption edge of 10NBOC-001 has slight red shift (360 nm), and meanwhile 10NBOC-010 also has slight red shift (390 nm), so that the nitrogen-doped carbon quantum dots can widen the light response range of bismuth oxychloride but have limited effect. However, focusing on the light response of the catalyst to wavelengths of 280nm to 800nm, it is known that 10NBOC-010 has significantly enhanced light absorption intensity in this range compared with 10NBOC-001 after loading the nitrogen-doped carbon quantum dots. This is mainly because the nitrogen-doped carbon quantum dot can be used as a photosensitizer and as a light absorption center of a photocatalyst, and at the same time, the interfacial charge transfer effect between the nitrogen-doped carbon quantum dot and the {010} crystal face of bismuth oxychloride can also promote the improvement of light absorption performance.
Experimental example 4
Examine the photogenerated carrier mobility properties of BOC-010, BOC-001, 10NBOC-010, 10NBOC-001
And (3) carrying out photogenerated carrier migration performance detection on the prepared {010} bismuth oxychloride nanosheets (BOC-010), {001} bismuth oxychloride nanosheets (BOC-001), the nitrogen doped carbon quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010) and the nitrogen doped carbon quantum dot anchored {001} bismuth oxychloride nanosheets (10 NBOC-001) by utilizing an electrochemical experiment.
The results are shown in FIG. 4. The carrier separation efficiency of BOC-010 is inferior to that of BOC-001, however, the carrier separation efficiency of 10NBOC-010 is superior to that of 10NBOC-001 after loading the same amount of nitrogen-doped carbon quanta. The phenomenon shows that the {010} crystal face of the nitrogen-doped carbon quantum dot and bismuth oxychloride has a synergistic effect in promoting carrier separation.
Experimental example 5
Investigation of the synergistic action of the nitrogen-doped carbon Quantum dots and the {010} crystal faces of bismuth oxychloride in the nitrogen-doped carbon Quantum dot anchored {010} bismuth oxychloride nanosheets (10 NBOC-010)
The synergy of the nitrogen-doped carbon quantum dots and the {010} crystal faces of bismuth oxychloride was analyzed by calculating the three-dimensional and planar average differential charge density of the nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride nanoplatelets (10 NBOC-010).
The results are shown in FIG. 5, and FIG. 5a shows that the following [ Bi ] 2 O 2 ] 2+ →N-CQDs→Cl - Directional covalent rings, which facilitate the directional transfer of electrons to form an interfacial electric field; as can be seen from fig. 5b, electrons of the nitrogen-doped carbon quantum dots in the 10NBOC-010 composite material interface are transferred to the bismuth oxychloride {010} crystal face, so that an interface electric field pointing to the bismuth oxychloride {010} crystal face from the nitrogen-doped carbon quantum dots is formed, which is favorable for transferring photogenerated charges at the 10NBOC-010 heterogeneous interface under the illumination condition.
Experimental example 6
Examine the efficiency of BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 in degrading antibiotic pollutants
Degrading Ciprofloxacin (CIP) in a water body by using materials BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001, comprising the following steps:
s1, weighing {010} bismuth oxychloride photocatalyst (BOC-010), {001} bismuth oxychloride photocatalyst (BOC-001), nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride (6 NBOC-010, 10NBOC-010, 14 NBOC-010) and nitrogen-doped carbon quantum dot anchored {001} bismuth oxychloride (10 NBOC-001), respectively 0.02g, adding into 50mL Ciprofloxacin (CIP) wastewater with the concentration of 10mg/L, and magnetically stirring in the dark for one hour to reach adsorption balance
S2, turning on a light source (xenon lamp), and irradiating under visible light (lambda is more than or equal to 420 nm) to perform photocatalytic reaction for 60min, so that degradation of CIP in the wastewater is completed.
S3, sucking photocatalytic degradation liquid in the 3mL reaction container every 10min, filtering with a 0.45 mu m filter head, and detecting degradation efficiency of the filtrate with an ultraviolet-visible spectrophotometer instrument.
As a result, FIG. 6a is a graph showing the time-degradation efficiency of BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 when CIP wastewater was photo-catalytically degraded under the irradiation of visible light, as shown in FIG. 6. In the figure Ct represents the concentration of CIP after degradation and C represents the initial concentration of CIP.
As can be seen from fig. 6: the degradation efficiency of the {010} bismuth oxychloride photocatalyst (BOC-010) on CIP after 60min of photocatalytic reaction is 33.9%.
The degradation efficiency of the nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride photocatalyst (6 NBOC-010) on CIP after 60min of photocatalytic reaction is 76.9%.
The degradation efficiency of the nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride photocatalyst (10 NBOC-010) on CIP after 60min of photocatalytic reaction is 85.2%.
The degradation efficiency of the nitrogen-doped carbon quantum dot anchored {010} bismuth oxychloride photocatalyst (14 NBOC-010) on CIP after 60min of photocatalytic reaction is 80.4%.
The degradation efficiency of the {001} bismuth oxychloride photocatalyst (BOC-001) on CIP in a photocatalytic reaction for 60min is 9.4%.
The degradation efficiency of the {001} bismuth oxychloride photocatalyst (10 NBOC-001) on CIP in the photocatalytic reaction for 60min is 63.4%.
From this, the degradation efficiency is sequentially from high to low: the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots (10 NBOC-010) > the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots (14 NBOC-010) > the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots (6 NBOC-010) > {001} bismuth oxychloride photocatalyst (10 NBOC-001) > {010} bismuth oxychloride photocatalyst (BOC-010) > {001} bismuth oxychloride photocatalyst (BOC-001).
FIG. 6b shows degradation coefficients for BOC-010, BOC-001, 6NBOC-010, 10NBOC-010, 14NBOC-010 and 10NBOC-001 treatments.
The mass percentage of the nitrogen-doped carbon quantum dots in the {010} bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots is 0.02%, the degradation efficiency of the {010} bismuth oxychloride nanosheets is highest when the mass percentage of the nitrogen-doped carbon quantum dots is 99.98%, and in addition, the degradation efficiency of the material can be obviously affected by the excessively high or excessively low mass percentage of the nitrogen-doped carbon quantum dots.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The bismuth oxychloride photocatalyst anchored by the nitrogen-doped carbon quantum dots is characterized by comprising bismuth oxychloride and the nitrogen-doped carbon quantum dots, wherein the crystal face of the bismuth oxychloride is mainly exposed {010}, the nitrogen-doped carbon quantum dots are anchored on the {010} crystal face of the bismuth oxychloride, and the mass percentage of the nitrogen-doped carbon quantum dots is 0.01-0.08%.
2. The nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst of claim 1, wherein the nitrogen-doped carbon quantum dot has a diameter < 10nm.
3. The nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst of claim 1, wherein the bismuth oxychloride is an ultrathin irregular nanosheet structure.
4. The preparation method of the nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst is characterized by comprising the following steps of:
s1, adding bismuth nitrate pentahydrate and a nitrogen-doped carbon quantum dot solution into a mixed solvent of glycerol and water, and ultrasonically stirring until a uniform mixed solution is formed;
s2, dropwise adding a saturated sodium chloride solution into the mixed solution obtained in the step S1, and uniformly stirring by ultrasonic waves;
s3, dropwise adding an alkaline solution into the mixed solution obtained in the step S2 to adjust the pH to 5-7;
s4, carrying out hydrothermal reaction on the mixed solution obtained in the step S3, and cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain the {010} bismuth oxychloride anchored by the nitrogen-doped carbon quantum dots.
5. The method according to claim 4, wherein the molar ratio of bismuth nitrate pentahydrate to the nitrogen-doped carbon quantum dot solution in the step S1 is 1: 0.002-0.008; in the step S1, the volume ratio of the glycerol to the water is 1:0.5-1.
6. The method according to claim 4, wherein the alkaline solution in the step S3 is any one of sodium hydroxide solution and potassium hydroxide solution.
7. The preparation method according to claim 4, wherein the hydrothermal reaction temperature in the step S4 is 120-180 ℃ and the reaction time is 5-10 h.
8. Use of the nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst according to any one of claims 1 to 3 or the nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst prepared by the preparation method according to any one of claims 4 to 7 in the catalytic degradation of antibiotics in wastewater.
9. The use according to claim 8, wherein the photocatalytic degradation of antibiotics in wastewater comprises the steps of: mixing the nitrogen-doped carbon quantum dot anchored bismuth oxychloride photocatalyst with wastewater containing antibiotic pollutants, stirring, and carrying out photocatalytic reaction under the illumination condition to finish the degradation of the antibiotic pollutants;
the addition amount of the photocatalyst in each liter of wastewater containing antibiotics is 0.2 g-1.0 g.
10. The use according to claim 9, wherein the antibiotic contaminant is ciprofloxacin, the initial concentration of ciprofloxacin contaminant being from 5mg/L to 20mg/L; the illumination condition lambda is more than or equal to 420nm; the time of the photocatalytic reaction is more than or equal to 60min.
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