CN112090438B - BiOCl/g-C3N4/CeO2Synthesis method of three-phase photocatalytic material - Google Patents
BiOCl/g-C3N4/CeO2Synthesis method of three-phase photocatalytic material Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
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- 238000001354 calcination Methods 0.000 claims description 8
- 239000002060 nanoflake Substances 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
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- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 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 abstract description 4
- 229940043267 rhodamine b Drugs 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
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- 239000002105 nanoparticle Substances 0.000 abstract description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B01J35/39—
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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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses BiOCl/g-C3N4/CeO2Method for synthesizing three-phase photocatalytic material, which is layered g-C3N4Layered BiOCl nano-sheet and CeO2The nano-particles are used as a structural reference substance to construct a three-phase composite system, and BiOCl/g-C with higher photocatalytic efficiency under visible light is synthesized3N4/CeO2A three-phase photocatalytic material. The three phases in the ternary heterojunction are divided into definite parts, double charge transfer can be realized, the separation of photo-generated charge carriers is accelerated, and the oxidation capacity is enhanced, so that the overall photocatalytic activity is improved, the material has high capacity of degrading organic pollutants under the irradiation of visible light, and the degradation rate of the material to rhodamine B is close to 100%. The catalytic material is easy to synthesize, low in raw material cost, capable of being produced in batches, and suitable for industrial popularization and application, and is a clean and efficient organic pollutant treatment material with low energy consumption.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to BiOCl/g-C3N4/CeO2A method for synthesizing a three-phase photocatalytic material.
Background
In recent years, dye wastewater pollution has become one of the most serious problems in environmental pollution, and photocatalysis is considered as one of the most promising and most effective and safe methods for solving such problems. As a novel photocatalytic material, BiOCl has a unique layered structure of tetragonal magnesite (P)bFCl type) structure consisting of a positively charged [ Bi ]2O2]2+Layer and two layers of negatively charged Cl-The ions are alternately stacked and arranged. This creates an internal electrostatic field that promotes electron-hole separation and enhances photocatalytic activity. Besides the above, it also has the advantages of good chemical stability, non-toxicity and abundant reserves. The valence band of BiOCl is mainly composed of O2p and Cl3p states, while the conduction band is mainly formed by the Bi6p state, which indicates that electrons in BiOCl should have higher mobility to facilitate the transfer and separation of photo-generated electron-hole pairs. Therefore, BiOCl shows good photocatalytic performance on degradation of organic pollutants such as RhB, acetophenone and the like in wastewater. However, there are some inherent disadvantages to the BiOCl catalyst, such as its wide band gap that makes it only absorb a small fraction of natural light, and the high recombination rate of photogenerated electron-hole pairs is one of the factors that limits its application in photocatalysis.
A very effective way to improve the photocatalytic efficiency and hence the photocatalytic stability by increasing the separation and transfer of the photogenerated electron-hole pairs is to build a heterojunction between two semiconductors. Currently, researchers have constructed heterojunctions between BiOCl and many materials to improve its photocatalytic performance. For example: wang et al prepared a novel vacancy-rich (2D/2D) BiOCl/g-C by simple solvothermal3N4The introduction of oxygen vacancies, a heterogeneous nanoplatelet for degradation of non-dye organic contaminants, brings a new level of defects, leading to increased light absorption. The final experiment shows that the synergistic effect between the 2D/2D heterojunction and the oxygen vacancy greatly promotes the visible light absorption and the photon-generated carrier separation efficiency, and the service life is prolonged. However, designing a simple and efficient method of synthesizing novel BiOCl-based photocatalytic materials with a broad spectral response range and high photocatalytic efficiency remains a great challenge.
Cerium oxide (CeO)2) As an important rare earth material, the rare earth material has the advantages of high chemical stability, environmental friendliness, narrow band gap and the like, so that the rare earth material is widely researched in the field of photocatalysis. These unique advantages make it an improved BiOX (X = Cl,Br, I) to improve their visible light activity. In addition, due to small size effects and higher quantum confinement, more opportunities may be provided to connect with other atoms in the heterostructure system, resulting in a more intimate contact interface between the two components. In addition, a shorter average diffusion time from volume to surface may also reduce charge carrier recombination.
Based on the above considerations, ultra-thin (2D) BiOCl nanosheets can be prepared solvothermally and CeO can be synthesized by simple co-precipitation2BiOCl, again based on g-C3N4The BiOCl/g-C with a heterostructure is prepared by solvent thermal evaporation3N4/CeO2A photocatalytic composite material.
Through the literature search of the prior art, the BiOCl/g-C is surrounded3N4The preparation of the photocatalytic system has some patent reports, such as Chinese patent application No. 201811496661.2, which is named as 'a BiOCl/graphite-like phase carbon nitride composite photocatalyst with an exposed (010) crystal face and a preparation method and application thereof', and the patent adopts a BiOCl/g-C prepared by a light composite method3N4The composite material has higher photocatalytic activity and good application prospect; chinese patent application No. 201611060038.3 entitled BiOCl/g-C3N4/Bi2O3The composite powder, the preparation method and the application thereof greatly improve pure phase BiOCl and g-C3N4And Bi2O3The photocatalytic effect of the powder. Therefore, two or three energy band matched narrow band gap semiconductors are compounded, and the transfer of photogenerated carriers between the two or three compounded semiconductors can improve the quantum yield, thereby becoming a popular research and having good application prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide BiOCl/g-C3N4/CeO2A method for synthesizing a three-phase photocatalytic material. Making CeO2the/BiOCl composite material has the g-C3N4Is the substrate, and is ultimately supported thereon. Wherein the ternary heterojunction can form double charge transfer and accelerateThe separation of photo-generated charge carriers is realized, the oxidation capability is enhanced, the integral photocatalytic activity is improved, and the recombination of photo-generated electron hole pairs is reduced to the greatest extent, so that organic pollutants can be effectively degraded under the irradiation of visible light.
In order to achieve the purpose, the invention provides the following technical scheme:
BiOCl/g-C3N4/CeO2The synthesis method of the three-phase photocatalytic material comprises the following steps:
(1) preparation of ultrathin BiOCl nanosheet
Slowly pouring a certain amount of NaCl solution into Bi (NO)3)3·5H2Adding a surface active agent PVP into an O ethanol solution, fully stirring, transferring the mixed solution into a stainless steel high-pressure kettle lined with polytetrafluoroethylene for heating, collecting white precipitates, centrifugally washing the white precipitates for a plurality of times by using deionized water and ethanol, drying the white precipitates in an oven, and grinding the white precipitates to obtain the nano-silver-doped nano-silver oxide powder;
(2) preparation of CeO2/BiOCl composite material
Pouring the prepared BiOCl into deionized water for ultrasonic treatment, and then adding a certain amount of Ce (NO)3)3·6H2Mixing and stirring O, slowly dropwise adding a certain amount of ammonia water and stirring, finally centrifugally washing the mixture for a plurality of times by using deionized water and ethanol, drying the washed mixture in an oven, grinding and collecting the dried mixture;
(3) preparation of g-C3N4Nano-flakes
Putting any one of urea, melamine, thiourea or dicyandiamide as a raw material into an alumina crucible, sealing a cover, transferring into a muffle furnace for calcining, and grinding after calcining to obtain g-C3N4A nanoflake;
(4) preparation of BiOCl/g-C3N4/CeO2Three-phase photocatalytic material
Firstly, g-C is weighed3N4Adding ethanol, ultrasonic treating to obtain emulsion, and adding CeO2The BiOCl is continuously subjected to ultrasonic treatment and stirred, is taken out for centrifugal washing, is put into an oven for drying, and is finally ground and collected to obtain the BiOCl/g-C3N4/CeO2A three-phase photocatalytic material.
Further, the molar ratio of the bismuth nitrate to the sodium chloride in the step (1) is 1: 2-4, and the reaction time is 30min after fully stirring.
Further, in the step (1), the reaction temperature in the reaction kettle is 120-160 ℃, the reaction time is 12-24 hours, and the drying temperature is 60 ℃.
Further, in the step (2), CeO with the molar ratio of 1: 0.25-4 is prepared by a simple precipitation method2a/BiOCl composite material.
Further, in the step (2), the ultrasonic time is 30min, the stirring reaction time is 2-4 h, and the drying temperature is 60 ℃.
Further, the reaction conditions for calcining in the muffle furnace in the step (3) are as follows: heating to 450-550 ℃ at a speed of 2-5 ℃/min under an air atmosphere, and preserving heat for 2-4 h.
Further, g to C in the step (4)3N4The mass fraction of the ultrasonic wave is 5-20%, the continuous ultrasonic time is 2 hours, and the stirring reaction is carried out for 2-4 hours.
Further, in the step (4), the drying temperature is 80 ℃ and the drying time is 16-24 hours.
Has the advantages that: the invention provides BiOCl/g-C3N4/CeO2Method for synthesizing three-phase photocatalytic material, which is layered g-C3N4Layered BiOCl nano-sheet and CeO2The nano-particles are used as a structural reference substance to construct a three-phase composite system, and BiOCl/g-C with higher photocatalytic efficiency under visible light is synthesized3N4/CeO2A three-phase photocatalytic material. The three phases in the ternary heterojunction are divided into definite parts, double-charge transfer can be realized, the separation of photo-generated charge carriers is accelerated, and the oxidation capability is enhanced, so that the overall photocatalytic activity is improved, and the capacity of degrading organic pollutants under the irradiation of visible light is high. Optimum BiOCl/g-C3N4/CeO2After the three-phase photocatalytic material is irradiated by visible light for 1 hour, the degradation rate of 20 mg/L rhodamine B is close to 100 percent. The catalytic material is easy to synthesize, has low raw material cost, and can be used for batch productionThe organic pollutant treating material is suitable for industrial popularization and application, is clean and efficient, and has low energy consumption.
Drawings
FIG. 1 shows BiOCl/g-C3N4/CeO2An XRD pattern of the photocatalytic material, wherein CBC-21 represents a molar ratio of Ce to Bi of 2: 1 CeO2the/BiOCl composite material, CN represents g-C3N45CNCBC represents the mass of CN in BiOCl/g-C3N4/CeO25wt% of the photocatalytic material, 10CNCBC represents the mass of CN in BiOCl/g-C3N4/CeO210wt% of the photocatalytic material, 15CNCBC represents the mass of CN in BiOCl/g-C3N4/CeO215wt% of the photocatalytic material, 20CNCBC represents the mass of CN accounting for BiOCl/g-C3N4/CeO220wt% of photocatalytic material;
FIG. 2 shows BiOCl/g-C3N4/CeO2SEM images of photocatalytic materials;
FIG. 3 shows BiOCl/g-C3N4/CeO2TEM images of photocatalytic materials;
FIG. 4 is a graph of visible light degradation rhodamine B curves for different samples;
FIG. 5 (a) is BiOCl/g-C3N4/CeO24-time cyclic degradation RhB dye curve diagram of the photocatalytic material; (b) is BiOCl/g-C3N4/CeO2XRD patterns of the photocatalytic material before and after a circulating photocatalytic experiment;
FIG. 6 shows BiOCl/g-C3N4/CeO2A photocatalytic principle diagram of the photocatalytic material.
Detailed Description
The present invention will be described in more detail and fully with reference to the following examples, which are not intended to limit the scope of the invention.
Example 1
(1) 3.395 g of Bi (NO) were weighed out3)3·5H2O pour it into 40 mL of ethanol and record as solution A. 0.409 g of NaCl was poured into 20mL of deionized water and recorded as solution B. Then stirring for 30min respectively to slowly dissolve the solution BSolution A was poured slowly, noted as solution C, while 0.4g PVP was poured into solution C and stirring was continued for 2 h. The solution was then transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heated at 120 ℃ for 12 h, then cooled to room temperature, the white precipitate was collected and washed several times with deionized water and ethanol centrifugation, dried overnight in an oven at 60 ℃, ground and collected for use.
(2) Preparation of CeO with a molar ratio of 1:0.5 by a simple precipitation method2the/BiOCl composite material is prepared by pouring 1 mmol of BiOCl into 50mL of deionized water, performing ultrasonic treatment for 30min, and adding 1 mmol of Ce (NO)3)3·6H2O, mixing and stirring, then slowly dropwise adding a plurality of drops of ammonia water to the mixture until a large amount of precipitates appear, stirring for 2 hours, then centrifugally washing the mixture for a plurality of times by using deionized water and ethanol, drying the mixture in an oven at 60 ℃ overnight, and then grinding and collecting the dried mixture.
(3) 10g of urea and 3g of thiourea were accurately weighed, ground from bulk into fine powder with a mortar, placed in a 100mL alumina crucible, heated to 550 ℃ at 2 ℃/min in the air atmosphere, calcined, and kept warm for 4 hours. Naturally cooling to room temperature, grinding into powder and collecting for later use.
(4) Weighing 0.02g g-C3N4Adding 50mL of ethanol, performing ultrasonic treatment to form emulsion, and adding 0.38g of prepared CeO2Continuing to perform ultrasonic treatment on the/BiOCl composite material for 2 hours, stirring for 2 hours, taking out the composite material, centrifugally washing, putting the composite material into an oven, heating for 18 hours at 80 ℃, grinding and collecting to obtain BiOCl/g-C3N4/CeO2A three-phase photocatalytic material.
Example 2
(1) First, 3.395 g of Bi (NO) were weighed3)3·5H2O pour it into 40 mL of ethanol and record as solution A. 1.636 g of NaCl was poured into 20mL of deionized water and designated solution B. After stirring for 30min, solution B was slowly poured into solution A, noted as solution C, while 0.5g PVP was poured into solution C and stirring was continued for 2 h. Then the solution is poured into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heated at 150 ℃ for 18h, then cooled to room temperature, white precipitate is collected and centrifugally washed with deionized water and ethanol for a plurality of times, after drying in an oven at 60 ℃ overnight,grinding and collecting for later use.
(2) Preparation of CeO in a molar ratio of 1:1 by a simple precipitation method2the/BiOCl composite material is prepared by pouring 1 mmol of BiOCl into 50mL of deionized water, performing ultrasonic treatment for 30min, and adding 2 mmol of Ce (NO)3)3·6H2O, mixing and stirring, then slowly dropwise adding a plurality of drops of ammonia water to the mixture until a large amount of precipitates are generated, stirring for 4 hours, centrifugally washing the mixture for a plurality of times by using deionized water and ethanol, drying the mixture in an oven at 60 ℃ overnight, and then grinding and collecting the dried mixture.
(3) Taking 10g of melamine as a raw material, placing the melamine in an alumina crucible, sealing the alumina crucible, transferring the melamine into a muffle furnace, heating the melamine to 500 ℃ at a speed of 4 ℃/min in an air atmosphere, preserving the heat for 3 hours, and grinding the melamine after calcination to obtain light yellow g-C3N4And (4) nano flakes.
(4) Weighing 0.02g g-C3N4Adding 50mL of ethanol, performing ultrasonic treatment to form emulsion, and adding 0.18g of prepared CeO2Continuing to perform ultrasonic treatment on the/BiOCl composite material for 2 hours, stirring for 4 hours, taking out the composite material, centrifugally washing, putting the composite material into an oven, heating for 16 hours at 80 ℃, grinding and collecting to obtain BiOCl/g-C3N4/CeO2A three-phase photocatalytic material.
Example 3:
(1) 3.395 g of Bi (NO) were weighed out3)3·5H2O pour it into 40 mL of ethanol and record as solution A. 1.636 g of NaCl was poured into 20mL of deionized water and designated solution B. After stirring for 30min, solution B was slowly poured into solution A, noted as solution C, while 0.4g PVP was poured into solution C and stirring was continued for 2 h. The solution was then poured into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, heated at 160 ℃ for 24h, then cooled to room temperature, the white precipitate was collected and washed several times with deionized water and ethanol centrifugation, dried overnight in an oven at 60 ℃, and then ground for collection.
(2) Preparation of CeO in a molar ratio of 1:2 by a simple precipitation method2the/BiOCl composite material is prepared by pouring 2 mmol of BiOCl into 50mL of deionized water, performing ultrasonic treatment for 30min, and adding 1 mmol of Ce (NO)3)3·6H2O mixing and stirring, and then slowly dripping a plurality of drops into the mixtureAmmonia until a large amount of precipitate appeared, after stirring for 3h, it was washed several times by centrifugation with deionized water and ethanol, and after drying overnight in an oven at 60 ℃, collected by grinding.
(3) Taking 10g of thiourea as a raw material, placing the thiourea in an alumina crucible, sealing the alumina crucible, transferring the thiourea into a muffle furnace, heating the thiourea to 450 ℃ at the speed of 3.5 ℃/min under the air atmosphere, preserving the temperature for 2 hours, and grinding the thiourea after calcination to obtain light yellow g-C3N4And (4) nano flakes.
(4) Weighing 0.02g g-C3N4Adding 50mL of ethanol, performing ultrasonic treatment to form emulsion, and adding 0.08g of prepared CeO2Continuing to perform ultrasonic treatment on the/BiOCl composite material for 2 hours, stirring for 3 hours, taking out the composite material, centrifugally washing, putting the composite material into an oven, heating for 20 hours at 80 ℃, grinding and collecting to obtain BiOCl/g-C3N4/CeO2A three-phase photocatalytic material.
FIGS. 2 and 3 are BiOCl/g-C prepared in example 13N4/CeO2Scanning and transmission spectra of the photocatalytic material, from which CeO can be clearly seen2the/BiOCl composite material is fixed at g-C3N4Above, it has a layer-to-layer stacking structure as a whole, and is not directed to BiOCl and g-C3N4Has a large change in overall morphology of CeO2Fine particles are uniformly distributed in BiOCl and g-C3N4Above, this indicates that CeO2BiOCl and g-C3N4Successful coupling, g-C3N4/BiOCl/CeO2The ternary photocatalytic material is successfully synthesized.
On the basis of example 1, by adjusting g-C3N4Nano-flake and CeO2Preparation of composite material containing different g-C by mixing proportion of/BiOCl3N4BiOCl/g-C3N4/CeO with mass fraction (5 wt%, 10wt%, 15wt%, 20 wt%)2A three-phase photocatalytic material. FIG. 1 shows four BiOCl/g-C preparations based on example 13N4/CeO2Photocatalytic Material g-C3N4Nano-flake, CeO2XRD pattern of/BiOCl composite material, from which four triphase g-C prepared3N4/BiOCl/CeO2No g-C was observed in any of the composite materials3N4Due to low crystallinity and small amounts of g-C3N4. In addition, no other diffraction peaks were detected, indicating high purity of the heterojunction.
Four BiOCl/g-C samples prepared on the basis of example 13N4/CeO2Photocatalytic material and BiOCl/CeO2The composite materials are respectively added into rhodamine B solution with the concentration of 20 mg/L, sampling is carried out every 1h under simulated visible light irradiation of a xenon lamp, the concentration change of the composite materials is analyzed by utilizing an ultraviolet-visible spectrophotometer and combining a standard curve, and the degradation rate of the composite materials is up to 99 percent after illumination for 50 min (figure 4).
The results of the cycling experiments for example 1 shown in FIG. 5 show that there is no significant difference before and after cycling, which indicates 5wt% g-C3N4/BiOCl/CeO2The compound has excellent recoverability and repeatability, and has great potential in practical application.
The photocatalytic mechanism diagram (FIG. 6) shows that when visible light is irradiated on the composite photocatalytic material, BiOCl cannot be excited due to its wide band gap of 3.53 eV, but CeO2、g-C3N4Including RhB, can be excited and produce photo-induced electron-hole pairs. BiOCl, g-C3N4And CeO2The energy levels of the semiconductors are well matched due to g-C3N4Potential ratio of conduction band of BiOCl (0.07 eV) and CeO2More negative (-0.50 eV), so that photogenerated electrons easily migrate to BiOCl and CeO2On the guide belt. On the other hand, the photoinduced holes are transferred from VB to g-C of BiOCl3N4VB, the charge is transferred directly from the interface, shortening the transport distance and thus accelerating the transport of photogenerated holes on the BiOCl, and the oxygen vacancies on the surface of the BiOCl act as active electron traps to capture electrons and promote the separation of photogenerated electron-hole pairs, which will be adsorbed on the O on the surface of the material2Reduced to superoxide radical, and these superoxide radicals can in turn activate H2O2And hydroxyl radicals (. OH) are generated. CeO (CeO)2The light excited hole in the valence band is excited by the energy level ratio g-C of the valence band3N4Has a greater influence on the valence band energy level of (1) to g-C3N4The valence band of (3). Therefore, double charge transfer can be formed in the ternary heterojunction, the separation of photo-generated charge carriers is accelerated, the oxidation capability is enhanced, the overall photocatalytic activity is improved, and the recombination of photo-generated electron hole pairs is reduced to the maximum extent, so that the RhB can be effectively degraded under the irradiation of visible light.
Claims (8)
1. BiOCl/g-C3N4/CeO2The synthesis method of the three-phase photocatalytic material is characterized by comprising the following steps of:
(1) preparation of ultrathin BiOCl nanosheet
Slowly pouring NaCl solution into Bi (NO)3)3·5H2Adding a surface active agent PVP into an O ethanol solution, fully stirring, transferring the mixed solution into a stainless steel high-pressure kettle lined with polytetrafluoroethylene for heating, collecting white precipitates, centrifugally washing the white precipitates for a plurality of times by using deionized water and ethanol, drying the white precipitates in an oven, and grinding the white precipitates to obtain the nano-silver-doped nano-silver oxide powder;
(2) preparation of CeO2/BiOCl composite material
The prepared BiOCl is poured into deionized water for ultrasonic treatment, and then Ce (NO) is added3)3·6H2Mixing and stirring O, slowly dropwise adding ammonia water and stirring, finally centrifugally washing the mixture for a plurality of times by using deionized water and ethanol, drying the washed mixture in an oven, grinding and collecting the dried mixture;
(3) preparation of g-C3N4Nano-flakes
Putting any one of urea, melamine, thiourea or dicyandiamide as a raw material into an alumina crucible, sealing a cover, transferring into a muffle furnace for calcining, and grinding after calcining to obtain g-C3N4A nanoflake;
(4) preparation of BiOCl/g-C3N4/CeO2Three-phase photocatalytic material
Firstly, g-C is weighed3N4Adding ethanol, ultrasonic treating to obtain emulsion, and adding CeO2The BiOCl continues to carry out ultrasonic treatment and stirring, after being taken out and centrifugally washed,drying in a drying oven, and grinding and collecting to obtain BiOCl/g-C3N4/CeO2A three-phase photocatalytic material.
2. The synthesis method according to claim 1, wherein the molar ratio of bismuth nitrate to sodium chloride in the step (1) is 1: 2-4, and the reaction time is 30min under full stirring.
3. The synthesis method according to claim 1, wherein the reaction temperature in the autoclave in the step (1) is 120-160 ℃, the reaction time is 12-24 h, and the drying temperature is 60 ℃.
4. The synthesis method of claim 1, wherein the CeO with the molar ratio of 1: 0.25-4 is prepared by using a precipitation method in the step (2)2a/BiOCl composite material.
5. The synthesis method according to claim 1, wherein the ultrasonic time in the step (2) is 30min, the stirring reaction time is 2-4 h, and the drying temperature is 60 ℃.
6. The synthesis method according to claim 1, wherein the calcination in the muffle furnace in the step (3) is carried out under the following reaction conditions: heating to 450-550 ℃ at a speed of 2-5 ℃/min under an air atmosphere, and preserving heat for 2-4 h.
7. The method of claim 1, wherein step (4) comprises g-C3N4The mass fraction of the mixture in ethanol is 5-20%, the continuous ultrasonic treatment time is 2 hours, and the stirring reaction is carried out for 2-4 hours.
8. The synthesis method according to claim 1, wherein the drying temperature in the step (4) is 80 ℃ and the time is 16-24 h.
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