CN117380245A - N-bismuth subcarbonate composite graphite-phase carbon nitride material and preparation method and application thereof - Google Patents
N-bismuth subcarbonate composite graphite-phase carbon nitride material and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 50
- 229940036358 bismuth subcarbonate Drugs 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 20
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 6
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- VZZHAYFWMLLWGG-UHFFFAOYSA-K triazanium;bismuth;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].[NH4+].[NH4+].[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZZHAYFWMLLWGG-UHFFFAOYSA-K 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
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- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 3
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- 239000002351 wastewater Substances 0.000 abstract description 2
- GACUIHAEKGVEIC-UHFFFAOYSA-L [Bi+2]=O.C([O-])([O-])=O Chemical compound [Bi+2]=O.C([O-])([O-])=O GACUIHAEKGVEIC-UHFFFAOYSA-L 0.000 description 19
- 239000011941 photocatalyst Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000010718 Oxidation Activity Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
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- -1 carbon nitrides Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
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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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02F2305/10—Photocatalysts
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Abstract
The invention provides an N-bismuth subcarbonate composite graphite-phase carbon nitride material, a preparation method and application thereof, and belongs to the technical field of photocatalytic materials for degrading wastewater pollutants. The invention synthesizes the N-bismuth subcarbonate by a hydrothermal method, and then utilizes an electrostatic adsorption method to condense and reflux the N-bismuth subcarbonate and graphite-phase carbon nitride to synthesize the N-bismuth subcarbonate composite graphite-phase carbon nitride material. According to the invention, the N-doped bismuth subcarbonate and the graphite-phase carbon nitride are effectively compounded, and the interaction between the N-doped bismuth subcarbonate and the graphite-phase carbon nitride is utilized to compound the N-doped bismuth subcarbonate and the graphite-phase carbon nitride and form an S-type heterojunction structure, so that the light absorption range can be widened, the light absorption intensity is enhanced, the separation and transfer of photogenerated carriers are promoted, and the performance of photocatalytic degradation of environmental water body organic dye, antibiotics and phenolic pollutants is further improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials for degrading wastewater pollutants, and particularly relates to an N-doped bismuth subcarbonate composite graphite-phase carbon nitride material, and a preparation method and application thereof.
Background
The increasing environmental pollution and the increasing demand for clean energy are serious global problems. To solve the above problems, many strategies and solutions have been adopted. Among them, the photocatalytic technology has great potential in solving the current energy crisis and environmental deterioration. Bismuth oxide carbonate is a very promising photocatalyst among various semiconductor photocatalytic materials because of its attractive morphology and excellent photochemical stability. However, the photocatalytic performance of bismuth oxide carbonate is limited for two reasons: (1) The wide bandgap of bismuth oxide carbonate results in poor visible light capturing capability; (2) The electron-hole pairs generated by photocatalysis have a rapid recombination rate in bismuth oxide carbonate, and limit the photocatalytic activity of the bismuth oxide carbonate. Therefore, improving the photocatalytic efficiency of monomeric bismuth subcarbonates remains a serious problem.
An effective method for improving the photocatalytic performance of a single semiconductor is to compound the two semiconductors to construct a heterojunction by utilizing the synergistic effect between the two promising semiconductors, and the separation and transfer of photo-generated electron-hole pairs can be effectively promoted by utilizing the tightly contacted interface between the semiconductors, well-matched energy band and crystal face coupling, so that the surface photochemical reaction is accelerated. Compared with the traditional heterojunction, the novel S-type heterojunction photocatalyst is widely focused due to the advantages of the energy band structure of the novel S-type heterojunction photocatalyst. The construction of S-type heterojunction has become one of the effective methods for improving the photocatalytic performance of monomers.
Based on the above, the invention provides a method for improving the defects of limited visible light response and fewer active sites of a photocatalyst by constructing an S-type heterojunction in monomer bismuth oxide carbonate.
Disclosure of Invention
In order to solve the technical problems, the invention provides an N-doped bismuth subcarbonate composite graphite-phase carbon nitride material, and a preparation method and application thereof. According to the invention, the N-doped bismuth oxide carbonate with uniform morphology is synthesized by a hydrothermal method, and the N-doped bismuth oxide carbonate composite graphite phase carbon nitride material is synthesized by an electrostatic adsorption method in a condensation reflux mode, so that the N-doped bismuth oxide carbonate and the graphite phase carbon nitride are effectively compounded to form an effective and environment-friendly S-shaped heterojunction of the N-doped bismuth oxide carbonate and the monomer photocatalyst, the defects of limited visible light response and fewer active sites of the monomer photocatalyst are overcome, more photo-generated carriers are generated, and the performance of photocatalytic degradation of environmental water organic dyes, antibiotics and phenolic pollutants is further improved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows:
the preparation method of the N-bismuth subcarbonate composite graphite-phase carbon nitride material comprises the steps of synthesizing the N-bismuth subcarbonate by a hydrothermal method, condensing and refluxing the N-bismuth subcarbonate and graphite-phase carbon nitride by an electrostatic adsorption method, and synthesizing the N-bismuth subcarbonate composite graphite-phase carbon nitride material.
Further, the hydrothermal synthesis of the N-doped bismuth oxide carbonate specifically comprises the following steps:
and (3) adding bismuth ammonium citrate and urea into deionized water, stirring, adding polyvinylpyrrolidone, continuously stirring, performing hydrothermal treatment, centrifuging, washing and drying to obtain the N-bismuth subcarbonate.
Still further, the dosage ratio of bismuth ammonium citrate, urea and polyvinylpyrrolidone is 2 mmol:10 mmol:600 mg.
Further, the temperature of the hydrothermal treatment is 60 ℃ and the time is 12 hours.
Further, the process of synthesizing the N-bismuth subcarbonate and graphite-phase carbon nitride material by condensing and refluxing the N-bismuth subcarbonate and the graphite-phase carbon nitride by using an electrostatic adsorption method specifically comprises the following steps:
and dispersing graphite-phase carbon nitride with a methanol aqueous solution to obtain a suspension, adding the N-bismuth subcarbonate into the suspension, stirring to obtain a mixture, condensing and refluxing the mixture, and washing and drying to obtain the N-bismuth subcarbonate composite graphite-phase carbon nitride material.
Still further, the concentration of the graphite phase carbon nitride in the suspension is 3 to 15wt%, and as a preferred concentration is 10wt%.
Still further, the suspension was used in an amount ratio of 150mL to 1g to the bismuth N-heterocarbonate.
Further, the temperature of the condensed reflux is 75 ℃ and the time is 4 hours.
More specifically, the preparation method of the N-bismuth subcarbonate composite graphite-phase carbon nitride material provided by the invention comprises the following steps:
step S1: preparation of bismuth N-heterocarbonate
Putting 2mmol of bismuth ammonium citrate and 10mmol of urea into deionized water, stirring at a high speed for 40min by using a stirrer with the rotating speed of 7000-8000rpm, adding 600mg of polyvinylpyrrolidone into the solution, continuously stirring at a high speed for 50min, sealing the solution into a 100mL high-pressure reaction kettle after stirring, performing hydrothermal treatment at 60 ℃ for 12h, centrifuging, washing with water and ethanol for 5min at 7000rpm for three times, and drying for 12h to obtain N-bismuth subcarbonate (p-BOC);
step S2: preparation of graphite phase carbon nitride
10g of urea was placed in a 50mL crucible and heated to 550℃in a muffle furnace at a heating rate of 10℃per minute, the temperature was maintained for 4 hours, and after cooling the muffle furnace, the mixture was taken out and ground to obtain graphite-phase carbon nitride (g-C) 3 N 4 )；
Step S3: preparation of N-doped bismuth oxide carbonate composite graphite phase carbon nitride material
Mixing deionized water and a methanol solution according to a volume ratio of 1:1 to obtain a methanol aqueous solution, adding graphite-phase carbon nitride into the methanol aqueous solution, carrying out ultrasonic treatment for 30min to obtain a completely dispersed suspension, introducing 1g p-BOC into 150mL of the suspension, magnetically stirring for 24h to obtain a mixture, finally evaporating, condensing and refluxing the mixture for 4h at 75 ℃ under continuous stirring, taking out water and ethanol, washing for 5min under 7000rpm, respectively three times, and then drying in a vacuum drying oven at 60 ℃ for 12h to obtain the N-bismuth subcarbonate composite graphite-phase carbon nitride material (CN/p-BOC).
The graphite phase carbon nitride is used as a novel organic photocatalyst, and is more concerned due to the inherent physical and chemical properties, the electronic structure and the surface properties of the graphite phase carbon nitride also make the graphite phase carbon nitride become a photocatalyst with potential application for degrading pollutants and generating renewable energy sources, and the two-dimensional structure of the graphite phase carbon nitride can provide a good contact plane with other semiconductors, so that nanojunctions are easier to form. In addition, the layered structure can promote the transfer of photo-generated charges at a tight interface, and is expected to improve the photocatalytic performance compared with a single photocatalyst.
VB and CB for graphite-phase carbon nitrides are about 1.40 and-1.21 eV, respectively, and VB and CB for bismuth N-heterocarbonate are 1.48 and-0.78 eV, respectively. Therefore, the band gaps of the graphite-phase carbon nitride and the N-doped bismuth oxide carbonate material can be matched in a crossing way, the directional migration of carriers can be realized by forming the composite photocatalyst, and the separation of photo-generated electron-hole pairs is promoted, so that the photocatalytic activity is enhanced. The two semiconductors form a composite photocatalyst, so that directional migration of carriers is promoted, and rapid separation of photo-generated electron-hole pairs is realized, thereby enhancing photocatalytic activity.
The second technical scheme of the invention is as follows:
the SEM image of the N-doped bismuth subcarbonate composite graphite-phase carbon nitride material prepared by the preparation method is peony-shaped.
The third technical scheme of the invention:
the application of the N-bismuth subcarbonate composite graphite-phase carbon nitride material in photocatalytic degradation of organic dye, antibiotics or phenolic pollutants.
Compared with the prior art, the invention has the following advantages and technical effects:
1. according to the invention, the N-doped bismuth oxide carbonate with uniform morphology is synthesized by a hydrothermal method, and the N-doped bismuth oxide carbonate and graphite-phase carbon nitride are synthesized into the composite material by an electrostatic adsorption method through a condensation reflux method, so that an effective and environment-friendly S-type heterojunction of the N-doped bismuth oxide carbonate composite graphite-phase carbon nitride is formed, the defects of limited visible light response and fewer active sites of a monomer photocatalyst are overcome, charge separation is accelerated, more photo-generated carriers are generated, the spectral response range of the monomer photocatalyst is improved, and therefore, the efficient visible light catalytic oxidation activity is realized, and the performances of photocatalytic degradation of environmental water organic dyes, antibiotics and phenolic pollutants are further improved.
2. According to the invention, when the N-doped bismuth oxide carbonate composite graphite-phase carbon nitride material is prepared, the ratio of graphite-phase carbon nitride to N-doped bismuth oxide carbonate is controlled, so that the composite material with a proper energy band structure and optimal photocatalytic activity is obtained, and the photocatalytic performance of the monomer is effectively improved.
3. According to the invention, the interaction between the N-doped bismuth subcarbonate and the graphite-phase carbon nitride is utilized to compound the N-doped bismuth subcarbonate and the graphite-phase carbon nitride and form an S-type heterojunction structure, so that the light absorption range can be widened, the light absorption intensity can be enhanced, and the separation and transfer of photo-generated carriers can be promoted, thereby improving the photocatalytic degradation performance of the composite material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a schematic diagram of the synthetic flow for preparing N-bismuth subcarbonate composite graphite-phase carbon nitride material (CN/p-BOC) in example 1 of the present invention;
FIG. 2 is a SEM image of p-BOC, CN and 10wt% CN/p-BOC prepared according to example 1 of the invention, where a is p-BOC, b is CN, c, d are 10wt% CN/p-BOC at different magnifications;
FIG. 3 is a TEM image of p-BOC, CN and 10wt% CN/p-BOC prepared in example 1 of the invention, where a is p-BOC, b is CN, c, d are 10wt% CN/p-BOC at different magnifications;
FIG. 4 shows the photocatalytic degradation performance of the bismuth subcarbonate N complex graphite phase carbon nitride material prepared according to the present invention for dye RhB (a), antibiotics TC (b) and CIP (c) under visible light, and the kinetics curves (d) of the degradation of RhB for all samples.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the examples of the present invention are all commercially available.
The technical scheme of the invention is further described by the following examples.
Example 1
Step S1: preparation of bismuth N-heterocarbonate
Putting 2mmol of bismuth ammonium citrate and 10mmol of urea into deionized water, stirring at a high speed for 40min by using a stirrer with the rotating speed of 7000-8000rpm, adding 600mg of polyvinylpyrrolidone into the solution, continuously stirring at a high speed for 50min, sealing the solution into a 100mL high-pressure reaction kettle after stirring, performing hydrothermal treatment at 60 ℃ for 12h, centrifuging, washing with water and ethanol for 5min at 7000rpm for three times, and drying for 12h to obtain N-bismuth subcarbonate (p-BOC);
step S2: preparation of graphite phase carbon nitride
10g of urea was placed in a 50mL crucible and heated to 550℃in a muffle furnace at a heating rate of 10℃per minute, the temperature was maintained for 4 hours, and after cooling the muffle furnace, the mixture was taken out and ground to obtain graphite-phase carbon nitride (g-C) 3 N 4 Abbreviated CN);
step S3: preparation of N-doped bismuth oxide carbonate composite graphite phase carbon nitride material
Mixing deionized water and a methanol solution according to a volume ratio of 1:1 to obtain 150mL of a methanol aqueous solution, adding graphite-phase carbon nitride into the methanol aqueous solution, performing ultrasonic treatment for 30min to obtain a completely dispersed suspension, introducing 1g p-BOC into 150mL of the suspension, magnetically stirring for 24h to obtain a mixture, finally evaporating, condensing and refluxing the mixture for 4h at 75 ℃ under continuous stirring, taking out water and ethanol, washing for 5min under 7000rpm, respectively three times, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain the N-bismuth subcarbonate composite graphite-phase carbon nitride material (10 wt%CN/p-BOC).
The synthetic flow diagram of the preparation of the N-bismuth subcarbonate composite graphite-phase carbon nitride material (CN/p-BOC) in the embodiment 1 of the invention is shown in figure 1.
Example 2
The only difference from example 1 is that the concentration of graphite phase carbon nitride in the suspension is 3wt% giving 3wt% CN/p-BOC.
Example 3
The only difference from example 1 is that the concentration of graphite phase carbon nitride in the suspension is 5wt% giving 5wt% CN/p-BOC.
Example 4
The only difference from example 1 was that the concentration of graphite phase carbon nitride in the suspension was 15wt% giving 15wt% CN/p-BOC.
1. Topography analysis
In order to verify the morphology and crystal phase characteristics of the N-bismuth subcarbonate composite graphite-phase carbon nitride material prepared by the invention, the samples obtained in the example 1 were photographed by using a thermal field emission scanning electron microscope (model: JSM-7001F) and a transmission electron microscope (model: JEOL JSM-2010), and the results are shown in FIG. 2 and FIG. 3, wherein FIG. 2 shows SEM images, a shows p-BOC prepared in the example 1, b shows CN prepared in the example 1, c and d show 10wt% of CN/p-BOC prepared in the example 1 under different magnifications, FIG. 3 shows TEM images, a shows p-BOC prepared in the example 1, b shows CN prepared in the example 1, c and d show 10wt% of CN/p-BOC prepared in the example 1.
As can be seen from FIG. 2, the pure p-BOC is 3D peony sphere with a diameter of about 1.3 μm, while CN shows a typical lamellar structure, indicating that it comprises one or more layers of stacked graphite-like structures, whereas 10wt% of the CN/p-BOC prepared in example 1 has morphology that 3D p-BOC is wrapped by a layer of CN with a two-dimensional structure, further indicating that CN is wrapped on p-BOC, and the interface between CN and p-BOC is tight. The 10wt% CN/p-BOC prepared in example 1 is shown in inset d in FIG. 3 with a lattice spacing of 0.273nm, corresponding to the (110) plane of the p-BOC. The result can obtain that CN and p-BOC are tightly connected, so that a heterostructure is easier to form, and the transfer of photogenerated carriers is facilitated, so that the photocatalytic activity is enhanced.
2. Performance testing
The visible light catalytic oxidation activity of the material prepared by the embodiment of the invention is evaluated by taking 10mg/L of dye RhB (rhodamine), antibiotic TC and antibiotic CIP as target pollutants for photocatalytic degradation.
1. Visible light catalytic oxidation activity to RhB
50mg of the samples (p-BOC prepared in example 1, 10wt% CN/p-BOC prepared in example 1, 3wt% CN/p-BOC prepared in example 2, 5wt% CN/p-BOC prepared in example 3 and 15wt% CN/p-BOC prepared in example 4) were each taken and placed in a photocatalytic reactor, 100mL of RhB (lambda >400 nm) was photodegraded under a 250W xenon lamp, and a blank (RhB) without catalyst sample was set.
A flowing cooling water system was used to maintain the temperature at 30 ℃ to avoid thermocatalysis. Before the xenon lamp irradiates, the solution is magnetically stirred for 30min, so that the photocatalyst reaches adsorption-desorption equilibrium on the surface of the material. After the lamp was turned on, 3mL of the solution was taken at 15min intervals, centrifuged and the particles were removed by filtration through 0.2 μm polyethersulfone for subsequent analysis. The concentration change of the target contaminant is measured with an ultraviolet-visible spectrophotometer at maximum absorption wavelengths 554, 358 and 276 nm.
The measurement result of the visible light catalytic oxidation activity of RhB is shown as a in FIG. 4.
2. Visible light catalytic oxidation activity on TC
50mg of the samples (p-BOC and 10wt% CN/p-BOC prepared in example 1) were each taken and placed in a photocatalytic reactor, 100mL of TC (lambda >400 nm) was photodegradation under a 250W xenon lamp, and a blank (TC) without catalyst sample was set.
A flowing cooling water system was used to maintain the temperature at 30 ℃ to avoid thermocatalysis. Before the xenon lamp irradiates, the solution is magnetically stirred for 30min, so that the photocatalyst reaches adsorption-desorption equilibrium on the surface of the material. After the lamp was turned on, 3mL of the solution was taken at 15min intervals, centrifuged and the particles were removed by filtration through 0.2 μm polyethersulfone for subsequent analysis. The concentration change of the target contaminant is measured with an ultraviolet-visible spectrophotometer at maximum absorption wavelengths 554, 358 and 276 nm.
The results of the visible light catalytic oxidation activity measurements of TC for p-BOC and 10wt% CN/p-BOC prepared in example 1 are shown in FIG. 4 b.
3. Visible light catalytic oxidation Activity against CIP
50mg of samples (p-BOC and 10wt% CN/p-BOC prepared in example 1) were each taken and placed in a photocatalytic reactor, 100mL of CIP (lambda >400 nm) was photodegradation under a 250W xenon lamp, and a blank (CIP) without catalyst sample was set.
A flowing cooling water system was used to maintain the temperature at 30 ℃ to avoid thermocatalysis. Before the xenon lamp irradiates, the solution is magnetically stirred for 30min, so that the photocatalyst reaches adsorption-desorption equilibrium on the surface of the material. After the lamp was turned on, 3mL of the solution was taken at 15min intervals, centrifuged and the particles were removed by filtration through 0.2 μm polyethersulfone for subsequent analysis. The concentration change of the target contaminant is measured with an ultraviolet-visible spectrophotometer at maximum absorption wavelengths 554, 358 and 276 nm.
The results of the visible light catalytic oxidation activity measurements of the p-BOC prepared in example 1 and 10wt% CN/p-BOC on CIP are shown in FIG. 4, c.
4. Kinetic profile of degradation of RhB
The kinetic curve results for the degradation of RhB for the samples (p-BOC prepared in example 1, 10wt% CN/p-BOC prepared in example 1, 3wt% CN/p-BOC prepared in example 2, 5wt% CN/p-BOC prepared in example 3 and 15wt% CN/p-BOC prepared in example 4) and the Blank (Blank) are shown in FIG. 4, d.
As can be seen from FIG. 4, 10wt% CN/p-BOC prepared in example 1 degraded various contaminants with optimal performance.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the N-doped bismuth subcarbonate composite graphite-phase carbon nitride material is characterized by synthesizing the N-doped bismuth subcarbonate by a hydrothermal method, and condensing and refluxing the N-doped bismuth subcarbonate and the graphite-phase carbon nitride by an electrostatic adsorption method.
2. The preparation method of the N-bismuth subcarbonate composite graphite-phase carbon nitride material according to claim 1, which is characterized by comprising the following steps of:
and (3) adding bismuth ammonium citrate and urea into deionized water, stirring, adding polyvinylpyrrolidone, continuously stirring, performing hydrothermal treatment, centrifuging, washing and drying to obtain the N-bismuth subcarbonate.
3. The method for preparing the bismuth subcarbonate-N composite graphite-phase carbon nitride material according to claim 2, wherein the dosage ratio of bismuth ammonium citrate, urea and polyvinylpyrrolidone is 2 mmol/10 mmol/600 mg.
4. The method for preparing the N-bismuth subcarbonate composite graphite-phase carbon nitride material according to claim 2, wherein the hydrothermal treatment is performed at a temperature of 60 ℃ for 12 hours.
5. The preparation method of the N-bismuth subcarbonate composite graphite-phase carbon nitride material according to claim 1, wherein the process of synthesizing the N-bismuth subcarbonate composite graphite-phase carbon nitride material by condensing and refluxing the N-bismuth subcarbonate and the graphite-phase carbon nitride by using an electrostatic adsorption method specifically comprises the following steps:
and dispersing graphite-phase carbon nitride with a methanol aqueous solution to obtain a suspension, adding the N-bismuth subcarbonate into the suspension, stirring to obtain a mixture, condensing and refluxing the mixture, and washing and drying to obtain the N-bismuth subcarbonate composite graphite-phase carbon nitride material.
6. The method for producing an N-bismuth subcarbonate composite graphite-phase carbon nitride material according to claim 5, wherein the concentration of the graphite-phase carbon nitride in the suspension is 3 to 15wt%.
7. The method for preparing a bismuth subcarbonate composite graphite phase carbon nitride material according to claim 5, wherein the dosage ratio of the suspension to the bismuth subcarbonate is 150 mL/1 g.
8. The method for preparing the N-bismuth subcarbonate composite graphite-phase carbon nitride material according to claim 5, wherein the condensation reflux temperature is 75 ℃ and the time is 4 hours.
9. An N-bismuth subcarbonate composite graphite-phase carbon nitride material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the bismuth subcarbonate composite graphite-phase carbon nitride material of claim 9 for photocatalytic degradation of organic dyes, antibiotics or phenolic contaminants.
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| PCT/CN2023/129058 WO2024088432A1 (en) | 2023-10-25 | 2023-11-01 | N-doped bismuth oxycarbonate composite graphite-phase carbon nitride material, and preparation method therefor and use thereof |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09183620A (en) * | 1995-12-27 | 1997-07-15 | Dowa Mining Co Ltd | Bismuth oxycarbonate powder and its production |
| CN104549406A (en) * | 2014-12-19 | 2015-04-29 | 华南理工大学 | Composite visible light catalyst of g-C3N4/bismuth-based oxide and preparation method and application of composite visible light catalyst |
| CN105268462A (en) * | 2015-07-03 | 2016-01-27 | 西南石油大学 | Preparation method of nitrogen doped bismuth-containing oxides at low temperature |
| CN106166497A (en) * | 2016-06-27 | 2016-11-30 | 湘潭大学 | A kind of green catalyst and the method processing organic wastewater |
| CN107029770A (en) * | 2017-04-27 | 2017-08-11 | 中南大学 | A kind of preparation method of metastable phase bismuth oxide and its application in photocatalysis degradation organic contaminant |
| CN108927196A (en) * | 2018-07-07 | 2018-12-04 | 启东祥瑞建设有限公司 | A kind of g-C3N4/Bi2O2CO3The preparation method of nanosheet composite material |
| CN111054413A (en) * | 2020-03-05 | 2020-04-24 | 南京师范大学 | Ternary composite multi-effect photocatalyst and preparation method thereof |
| CN111659447A (en) * | 2020-07-07 | 2020-09-15 | 天津大学 | Photocatalyst for treating dye in high-salinity wastewater and preparation method thereof |
| CN114956170A (en) * | 2022-05-18 | 2022-08-30 | 海南师范大学 | Preparation method and application of peony-shaped bismuthyl carbonate with morphology normalization |
| CN115121276A (en) * | 2022-06-23 | 2022-09-30 | 湖南农业大学 | Composite photocatalyst, preparation method thereof and treatment method of wastewater containing antibiotics |
| CN116651489A (en) * | 2023-06-01 | 2023-08-29 | 四川轻化工大学 | Magnetic modified three-dimensional flower-shaped N-Bi 2 O 2 CO 3 / g-C 3 N 4 Preparation method and application of photocatalytic material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708551B (en) * | 2013-12-26 | 2015-12-30 | 湛江师范学院 | The preparation method of a kind of ethylene glycol-water mixed solvent thermal synthesis bismuth oxycarbonate flower-like microsphere |
| CN107684926B (en) * | 2017-10-31 | 2020-04-07 | 滨州学院 | Photocatalyst for treating dye in high-salinity wastewater and preparation method thereof |
| CN110721718A (en) * | 2019-10-14 | 2020-01-24 | 南昌航空大学 | Preparation method of graphite-phase carbon nitride-doped bismuth molybdate binary photocatalyst with good performance |
| CN111450819B (en) * | 2020-04-27 | 2020-12-04 | 成都信息工程大学 | Biochar modified bismuth vanadate catalyst, preparation method and application thereof |
| CN112121866A (en) * | 2020-10-09 | 2020-12-25 | 广州大学 | Photocatalyst and preparation method thereof |
-
2023
- 2023-10-25 CN CN202311386982.8A patent/CN117380245A/en active Pending
- 2023-11-01 WO PCT/CN2023/129058 patent/WO2024088432A1/en unknown
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09183620A (en) * | 1995-12-27 | 1997-07-15 | Dowa Mining Co Ltd | Bismuth oxycarbonate powder and its production |
| CN104549406A (en) * | 2014-12-19 | 2015-04-29 | 华南理工大学 | Composite visible light catalyst of g-C3N4/bismuth-based oxide and preparation method and application of composite visible light catalyst |
| CN105268462A (en) * | 2015-07-03 | 2016-01-27 | 西南石油大学 | Preparation method of nitrogen doped bismuth-containing oxides at low temperature |
| CN106166497A (en) * | 2016-06-27 | 2016-11-30 | 湘潭大学 | A kind of green catalyst and the method processing organic wastewater |
| CN107029770A (en) * | 2017-04-27 | 2017-08-11 | 中南大学 | A kind of preparation method of metastable phase bismuth oxide and its application in photocatalysis degradation organic contaminant |
| CN108927196A (en) * | 2018-07-07 | 2018-12-04 | 启东祥瑞建设有限公司 | A kind of g-C3N4/Bi2O2CO3The preparation method of nanosheet composite material |
| CN111054413A (en) * | 2020-03-05 | 2020-04-24 | 南京师范大学 | Ternary composite multi-effect photocatalyst and preparation method thereof |
| CN111659447A (en) * | 2020-07-07 | 2020-09-15 | 天津大学 | Photocatalyst for treating dye in high-salinity wastewater and preparation method thereof |
| CN114956170A (en) * | 2022-05-18 | 2022-08-30 | 海南师范大学 | Preparation method and application of peony-shaped bismuthyl carbonate with morphology normalization |
| CN115121276A (en) * | 2022-06-23 | 2022-09-30 | 湖南农业大学 | Composite photocatalyst, preparation method thereof and treatment method of wastewater containing antibiotics |
| CN116651489A (en) * | 2023-06-01 | 2023-08-29 | 四川轻化工大学 | Magnetic modified three-dimensional flower-shaped N-Bi 2 O 2 CO 3 / g-C 3 N 4 Preparation method and application of photocatalytic material |
Non-Patent Citations (4)
| Title |
|---|
| HUIPING ZHAO ET.AL: "g-C3N4 surface-decorated Bi2O2CO3 for improved photocatalytic performance: Theoretical calculation and photodegradation of antibiotics in actual water matrix", 《CHEMICAL ENGINEERING JOURNAL》, vol. 366, 13 February 2019 (2019-02-13), pages 468 * |
| LIEXIAO LI ET.AL: "Comparative investigation on synthesis, morphological tailoring and photocatalytic activities of Bi2O2CO3 nanostructures", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》, vol. 644, 23 March 2022 (2022-03-23), pages 128758 * |
| NA TIAN ET.AL: "A g-C3N4/Bi2O2CO3 composite with high visible-light-driven photocatalytic activity for rhodamine B degradation", 《APPLIED SURFACE SCIENCE》, vol. 322, 23 October 2014 (2014-10-23), pages 249 * |
| 王鹏远;郭昌胜;高建峰;徐建;: "石墨相氮化碳(g-C_3N_4)与Bi系复合光催化材料的制备及在环境中的应用", 化学进展, no. 2, 24 March 2017 (2017-03-24), pages 241 - 251 * |
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