CN113479934B - BiOCl nano-sheet and preparation method and application thereof - Google Patents
BiOCl nano-sheet and preparation method and application thereof 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 70
- 239000002135 nanosheet Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011521 glass Substances 0.000 claims abstract description 65
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 41
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000012634 fragment Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 18
- 238000004140 cleaning Methods 0.000 abstract description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 64
- 239000000463 material Substances 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000002064 nanoplatelet Substances 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 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 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- 238000012512 characterization method Methods 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229940026110 carbon dioxide / nitrogen Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- DHNCFAWJNPJGHS-UHFFFAOYSA-J [C+4].[O-]C([O-])=O.[O-]C([O-])=O Chemical class [C+4].[O-]C([O-])=O.[O-]C([O-])=O DHNCFAWJNPJGHS-UHFFFAOYSA-J 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 238000010309 melting process Methods 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- 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
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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 relates to a BiOCl nano-sheet and a preparation method and application thereof. The preparation method of the BiOCl nano-sheet comprises the following steps: adding bismuth-rich glass powder into HCl solution, fully reacting at 10-100 ℃, and then cleaning and drying to obtain the BiOCl nano-sheet.
Description
Technical Field
The invention relates to a BiOCl nano-sheet, a preparation method and application thereof, in particular to a method for synthesizing a BiOCl photocatalytic material by adopting bismuth-rich glass powder, belonging to the fields of nano-material synthesis and photo (electro) catalysis.
Background
With the rapid development of industrial technology, environmental pollution problems are more and more prominent, and the life of human beings is seriously influenced and threatened. The photocatalysis technology is a green advanced oxidation technology, and has wide research and application in the field of environmental pollution. Development of efficient, stable and low-cost photocatalysts has been a research hotspot in the field of photocatalyst research.
Bismuth oxychloride (BiOCl) is a novel photocatalyst developed in recent years, is low in cost and easy to obtain, is environment-friendly, and is a potential photocatalyst material. In addition, the BiOCl has the characteristics of special two-dimensional lamellar structure, easy modulation of crystal faces, strong hole oxidation capability and the like. Under the irradiation of visible light, electrons in the BiOCl are subjected to transition, so that water molecules, hydroxyl, dissolved oxygen and the like around the BiOCl catalyst are converted into active substances such as superoxide radicals, hydroxyl radicals and the like, and the degradation of pollutants is further promoted. Therefore, biOCl shows better application prospect in the field of photoelectrocatalytic oxidation.
Although various methods have been developed to prepare the BiOCl nanoplatelets, in order to control the thickness of the BiOCl nanomaterial, or to control the pH of the reaction system, or to add a surfactant which is difficult to clean, and to react at high temperature, there are problems such as high manufacturing cost, complex reaction process, difficulty in expanding production, and the like. Therefore, development of a tablet BiOCl preparation method with low energy consumption, low cost, simple reaction process and high efficiency is urgently needed.
Disclosure of Invention
In order to solve the technical problems of high manufacturing cost, complex reaction process, difficult expansion production and the like in the existing BiOCl preparation process. The invention provides bismuth-rich glass powder for synthesizing a BiOCl photocatalytic material and a preparation method thereof. Adding bismuth-rich glass powder serving as a raw material into hydrochloric acid solution with a certain concentration, and fully reacting the glass powder with hydrochloric acid at a certain temperature; and diluting the reacted solution to be neutral, and drying in a drying oven to obtain the BiOCl nano-sheet. The advantages of this solution fall into two aspects: first, relative to Bi 2 O 3 In order to synthesize the raw material of BiOCl, the glass network structure is looser than the crystal structure, and is easy to be corroded by HCl so as to react with the HCl to produce BiOCl, so that the reaction condition is mild; second, relative to Bi (NO) 3 ) 3 And BiCl 3 The water-soluble raw material, glass itself has [ BiO ] 4 ]And [ BiO ] 6 ]The network structure can be used for forming BiOCl crystals, and the BiOCl can be synthesized through a dissolution-recrystallization mechanism under the condition of high temperature and high pressure, so that the reaction condition is mild; thirdly, due to the looseness of the glass network structure, the structural defect of the glass in a high-temperature state can be reserved in the high-temperature melting-cold extraction process of the bismuth-enriched glass, wherein the oxygen defect has a great promotion effect on the catalytic performance of the photocatalytic material.
On one hand, the invention provides a preparation method of BiOCl nano-sheets, which comprises the steps of adding bismuth-rich glass powder into HCl solution, fully reacting at 10-100 ℃, and then cleaning and drying to obtain the BiOCl nano-sheets.
The method has the advantages of simple operation, low reaction temperature, low production cost, short production period, easy large-scale industrialized production and the like.
Preferably, the bismuth-rich glass powder comprises the following main components: bi source, glass network body including B 2 O 3 、SiO 2 At least one of (2); preferably, at least one of alkali metal oxide, alkaline earth oxide, transition metal oxide, rare earth metal oxide is also included.
Preferably, the particle size of the bismuth-rich glass powder is 0.5-50 μm.
Preferably, the bismuth-rich glass frit comprises the following main components: bi (Bi) 2 O 3 ：30～90mol％；B 2 O 3 ：5～50mol％；SiO 2 :0 to 30mol%; znO:0 to 40mol%; AO, a= Mg, ca, ba, sr: 0 to 30mol%; r is R 2 O, r=at least one of Li, na, K: 0 to 40mol%; al (Al) 2 O 3 :0 to 5mol%; rare earth oxide: 0 to 3mol%; preferably, bi 2 O 3 Comprising alpha-Bi 2 O 3 beta-Bi 2 O 3 gamma-Bi 2 O 3 At least one of bismuth nitrate and bismuth chloride.
Preferably, the preparation method of the bismuth-rich glass powder comprises the following steps:
(1) Respectively weighing the raw materials corresponding to the components, adding distilled water, performing planetary ball milling for one time, and uniformly mixing to obtain a mixture;
(2) Melting the obtained mixture to obtain uniform glass liquid, and then quenching to obtain glass fragments;
(3) Performing secondary planetary ball milling on the obtained glass fragments to obtain bismuth-rich glass powder;
preferably, the rotating speed of the primary planetary ball milling is 200-400 rpm, and the time is 0.5-3 hours;
preferably, the rotating speed of the secondary planetary ball milling is 300-600 revolutions per minute, and the time is 1-3 hours.
Preferably, the melting temperature is 700 to 1200 ℃ and the time is 0.5 to 3 hours.
Preferably, the solubility of the HCl solution is 4-38 wt%.
Preferably, the mass ratio of the bismuth-enriched glass powder to the HCl in the hydrochloric acid solution is 1: (0.5-5).
Preferably, the time for the sufficient reaction is 0.5 to 12 hours.
Preferably, the conditions for sufficient reaction further include magnetic stirring, ultrasonic treatment, or reaction vibration;
the rotating speed of the magnetic stirring is 200-1500 rpm;
the frequency of the ultrasonic treatment is 20-50 KHz;
the power of the reaction vibration is 100-2000W.
Preferably, the invention provides a BiOCl nano-sheet prepared according to a fir tree method, wherein the dimension of the BiOCl nano-sheet is 100-500 nm, and the thickness of the BiOCl nano-sheet is 10-20 nm.
In still another aspect, the invention provides an application of the BiOCl nano-sheet in the field of photocatalysis or photocatalysis, which is used for photocatalytic degradation of industrial dye, degradation of heavy metal ions, sterilization, photocatalytic hydrogen/oxygen production or carbon dioxide/nitrogen reduction.
The beneficial effects are that:
compared with the prior art which uses bismuth sources such as bismuth nitrate, bismuth chloride and the like, the invention has the advantages that:
a. the glass network structure is loose than the crystal structure, and is very easy to be matched with H + The reaction condition for preparing the BiOCl photocatalytic material by taking the bismuth-rich glass as a bismuth source is milder, and high-temperature and high-pressure conditions are not needed;
the invention provides a BiOCl nano-sheet containing oxygen vacancies, which is synthesized by taking bismuth-rich glass powder as bismuth source for the first time. The bismuth-rich glass powder can introduce defects existing in the high-temperature melting process into the prepared BiOCl nano-sheet, can improve the specific surface area of the powder and enhance the adsorption performance, and meanwhile, the existence of oxygen vacancies can play a role in regulating and controlling the energy band structure, so that the BiOCl nano-sheet exposes more reaction sites and can generate a large amount of active oxygen substances;
c. according to the invention, the bismuth-based glass composition and the glass network structure can be regulated, so that the regulation and control of glass defects can be realized, and the oxygen vacancy content of the BiOCl nanosheets can be regulated and controlled;
d. in the invention, the prepared BiOCl nano-sheet has the advantages of low energy consumption, simple and efficient preparation method, various powder shapes and no agglomeration phenomenon, and is beneficial to industrialized mass production;
e. in the invention, the prepared BiOCl nano-sheet has good photo (electro) catalytic effect and shows excellent degradation effect when industrial dye is degraded by photocatalysis.
Drawings
FIG. 1 is an X-ray diffraction pattern of BiOCl nanoplatelets prepared in examples 1-3, from which it is seen that all peaks in the XRD pattern of the prepared samples are indexed into the tetragonal phase of BiOCl, the peaks are strong and clear without other characteristic peaks, thus proving that the prepared BiOCl samples are pure phases;
FIG. 2 is an SEM image of bismuth glass powder, which shows the microstructure of bismuth glass powder having a lamellar structure of 4-20 μm after high temperature melting, by scanning electron microscopy analysis;
FIGS. 3a and 3b are scanning electron microscope images (scale is 1 μm) of BiOCl nanoplatelets prepared in examples 1-3, 5-8 and comparative examples 1-2, from which it is known that in examples 1-3 and 7-8, the obtained BiOCl photocatalytic material exhibits a lamellar structure, wherein example 8 has a relatively thin vermiform lamellar structure, and that in comparative examples 1-2, the microscopic morphology is observed, the lamellar structure of the BiOCl material is not sufficiently complete, and that some particulate catalytic material is present. Therefore, the bismuth content in the glass is too low or the reaction temperature is too low, which is unfavorable for the formation of the flake BiOCl;
FIG. 4 (a) shows the oxygen vacancy characterization of electron spin resonance (EPR) of bismuth-rich glass and BiOCl nanoplatelets prepared according to the present invention under dark conditions, wherein the oxygen vacancy peaks (g=2.003) are shown to be stronger as the alkali or alkaline earth oxide increases in the glass component, due to the increase of the component, the less stable the network structure of the glass, and the oxygen defects generated, compared with three different glasses under dark conditionsThe more this suggests that an unstable network structure would result in more defect generation; FIG. 4 (b) is an oxygen vacancy characterization of the prepared BiOCl photocatalytic material under dark conditions where BiOCl photocatalysis is still capable of generating oxygen vacancy signals, indicating that this is introduced by oxygen defects through the bismuth glass itself; FIG. 5 is an electron spin resonance (EPR) characterization of the BiOCl nanoplatelets prepared in examples 1-3 for reactive oxygen species during photocatalysis, the generation of reactive groups being due to O in air and water 2 And H 2 The O molecules and photo-generated electrons generated when the photo-catalytic material is irradiated are generated by reaction, and the prepared sample has stronger electron/hole separation efficiency and electron transmission rate under the irradiation condition;
FIGS. 6a and 6B are characteristics of the BiOCl nanoplatelets prepared in examples 1-3, 5, 8 and comparative examples 1-2 for degradation of rhodamine B under xenon irradiation, and it is understood from the figures that the time for complete degradation of rhodamine in examples 1-3, 5 and 8 under xenon irradiation is 60 minutes, 40 minutes, 35 minutes, 30 minutes and 25 minutes, respectively, while in comparative examples 1-2, the prepared samples failed to completely degrade rhodamine B in 180 minutes.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
The invention solves the problems of high manufacturing cost, complex reaction process, difficult expansion production and the like of the existing process for preparing the BiOCl nano-sheet material. The preparation method of the BiOCl nano-sheet has the advantages of simple and efficient preparation process, low cost, easy industrial production and the like. In the invention, the obtained BiOCl nanometer has the advantages of high active site, high catalytic efficiency and the like.
The following illustrates the preparation of the BiOCl nanoplatelets.
Bismuth-rich glass is prepared by a high-temperature melting-quick quenching method. Then the bismuth-rich glass is processed into bismuth-rich glass powder with the grain diameter of 0.5-50 microns.
Adding a proper amount of bismuth-rich glass powder into H with a certain concentrationIn Cl solution (mixed solution is obtained), bismuth-rich glass powder and HCl are fully reacted under certain conditions (reaction process: biO in glass 4 ]+/[BiO 6 ]+HCl→BiOCl+H 2 O) to obtain a suspension containing BiOCl nanoplatelets. Wherein the reaction temperature is 10 to 100 ℃, preferably 10 to 60 ℃, more preferably 10 to 50 ℃. The time required for the sufficient reaction may be 0.5 to 12 hours, preferably 0.5 to 6 hours, more preferably 0.5 to 3 hours.
In an alternative embodiment, the mixed solution is magnetically stirred, sonicated, or placed in a reaction vibrating bed to further promote the reaction while the mixed solution is sufficiently reacted.
In alternative embodiments, the hydrochloric acid solution may have a solubility of 4wt% to 38wt%. The mass ratio of the bismuth glass powder to the hydrochloric acid can be 1: (0.5-5).
And (3) washing the suspension containing the BiOCl nano-sheets to be neutral through deionized water, and drying in a drying oven to obtain the BiOCl nano-sheets. Wherein, the drying process can be: preserving heat for 1-12 hours at 70-150 ℃.
In the invention, the bismuth-rich glass powder mainly comprises the following components: bi source, glass network body including B 2 O 3 、SiO 2 The other materials also comprise at least one of alkali metal oxide, alkaline earth oxide, transition metal oxide and rare earth metal oxide. The following exemplifies the preparation method of the bismuth-rich glass frit.
The raw materials corresponding to the components are respectively weighed, a little distilled water is added, and planetary ball milling is carried out for 0.5 to 3 hours at the rotating speed of 200 to 400 revolutions per minute for uniformly mixing the raw materials, so as to obtain a mixture. Wherein, the raw materials generally directly correspond to oxides in the components or the oxides correspond to carbon carbonates and the like. Wherein the B source may be H 3 BO 3 . The Bi source may be Bi 2 O 3 Preferably comprises alpha-Bi 2 O 3 beta-Bi 2 O 3 gamma-Bi 2 O 3 At least one of bismuth nitrate and bismuth chloride.
And (3) quenching the molten uniform glass liquid of the mixture to obtain glass fragments. Wherein the melting temperature can be 700-1200 ℃, and the heat preservation time can be 0.5-3 hours.
And carrying out secondary planetary ball milling on the glass fragments for 1-3 hours at the rotating speed of 300-600 rpm to obtain the bismuth-enriched glass powder.
In the invention, the dimension of the BiOCl nano-sheet can be 100-500 nm, the thickness can be 10-20 nm, and the BiOCl nano-sheet can be used as a photo (electro) catalyst and has excellent catalytic activity. For example, the method can be applied to the field of photocatalysis such as photocatalytic degradation of industrial dye, degradation of heavy metal ions, sterilization, photocatalytic hydrogen/oxygen production, carbon dioxide/nitrogen/chlorine reduction and the like.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1:
1) 370.05 g of Bi 2 O 3 72.93 g H 3 BO 3 47.72 g ZnO, 9.3 g Sb 2 O 3 (1.62 mol%) glass raw materials were as follows: ball: deionized water = 1:3:2 is ball milled for 1 hour in a planetary way at 400r/min, and is dried for 6 hours in a constant temperature drying oven at 150 ℃ after being uniformly mixed;
2) Placing the dried raw materials into a corundum crucible, and preserving heat for 1h at a temperature rising rate of 5 ℃/min to 1000 ℃, wherein an alumina stirring paddle is adopted during the heat preservation, and the stirring rate is 10r/min;
3) Pouring the uniform glass liquid into deionized water to quench into glass fragments;
4) An alumina ball milling tank is adopted, and glass fragments are obtained according to the following steps: ball: absolute alcohol = 1:3:2 is ball-milled for 0.5 hour in a planetary way at 400r/min, and is dried for 6 hours in a constant temperature drying oven at 110 ℃ after discharging;
5) Adding 5g of bismuth-rich glass powder with the particle size of 15-25 mu m into 100ml of hydrochloric acid solution with the concentration of 4wt%, magnetically stirring (the rotating speed is 1000 rpm) for 2 hours at the temperature of 20 ℃ to enable the bismuth-rich glass powder to fully react with hydrochloric acid to prepare suspension;
6) Diluting the suspension with deionized water to neutrality, and drying in a drying oven at 100deg.C for 2 hr to obtain BiOCl nanosheets;
7) And (3) placing 10mg of the BiOCl nano-sheet prepared in the step (6) into 100mL of 10mg/L rhodamine B solution, stirring for 1h under a dark condition, starting a 300W xenon lamp to irradiate after the adsorption reaches equilibrium, and detecting the concentration of rhodamine B in the solution by an ultraviolet-visible light spectrophotometer every 5 minutes.
Example 2:
the preparation process of the BiOCl nanoplatelets in this example 2 is described with reference to example 1, except that: in step 1), 366.74 g Bi is added 2 O 3 72.34 g H 3 BO 3 31.87 g ZnO, 29.05 g SrCO 3 5g of Sb 2 O 3 According to the powder materials: ball: deionized water = 1:3:2 are ball milled for 1 hour in a planetary way at 400r/min, and are dried for 6 hours in a constant temperature drying oven at 150 ℃ after being uniformly mixed.
Example 3:
the preparation process of the BiOCl nanoplatelets in this example 3 is described with reference to example 1, except that: in step 1), 357.08 g Bi is added 2 O 3 70.38 g H 3 BO 3 14.61 g ZnO, 28.38 g SrCO 3 20.56 g of Na 2 CO 3 8.98 g of Sb 2 O 3 According to the powder materials: ball: deionized water = 1:3:2 are ball milled for 1 hour in a planetary way at 400r/min, and are dried for 6 hours in a constant temperature drying oven at 150 ℃ after being uniformly mixed.
Example 4:
the preparation process of the BiOCl nanoplatelets in this example 4 is described with reference to example 1, except that: in step 1), 398.11 g Bi is added 2 O 3 62.61 g H 3 BO 3 13.00 g ZnO, 18.29 g Na 2 CO 3 7.99 g of Sb 2 O 3 According to the powder materials: ball: deionized water = 1:3:2 in a ratio of 400And (3) carrying out planetary ball milling for 1 hour at r/min, uniformly mixing, and drying in a constant-temperature drying oven at 150 ℃ for 6 hours.
Example 5:
the preparation process of the BiOCl nanoplatelets in this example 5 is described with reference to example 1, except that: in step 1), 1) 451.83 g Bi is added 2 O 3 16.41 g H 3 BO 3 10.51 g ZnO, 14.79 g Na 2 CO 3 6.46 g of Sb 2 O 3 According to the powder materials: ball: deionized water = 1:3:2 are ball milled for 1 hour in a planetary way at 400r/min, and are dried for 6 hours in a constant temperature drying oven at 150 ℃ after being uniformly mixed.
Example 6:
the preparation process of the BiOCl nanoplatelets in this example 6 is described with reference to example 1, except that: in step 1), 480.95 g Bi is added 2 O 3 13.68 g H 3 BO 3 5.38 g of Sb 2 O 3 According to the powder materials: ball: deionized water = 1:3:2 are ball milled for 1 hour in a planetary way at 400r/min, and are dried for 6 hours in a constant temperature drying oven at 150 ℃ after being uniformly mixed.
Example 7:
the BiOCl nano-preparation process in this example 7 is described with reference to example 3, with the difference that: in step 5), the reaction conditions were 6wt% hydrochloric acid solution/20 ℃ C./2 h.
Example 8:
the BiOCl nano-preparation process in this example 8 is described with reference to example 3, with the difference that: in step 5), the reaction conditions were 4wt% hydrochloric acid solution/60 ℃ C./8 h.
Comparative example 1:
the preparation process of the BiOCl nanoplatelets in this comparative example 1 is described with reference to example 1, except that: in step 1), 268.16 g Bi was reacted 2 O 3 101.83 g H 3 BO 3 32.05 g SiO 2 43.89 g ZnO, 32.05 g SrCO 3 12.99 g of Sb 2 O 3 According to the powder materials: ball: deionized water = 1:3:2 are ball milled for 1 hour in a planetary way at 400r/min, and are dried for 6 hours in a constant temperature drying oven at 150 ℃ after being uniformly mixed.
Comparative example 2:
the BiOCl nano-preparation process in this comparative example 2 is described with reference to example 3, with the difference that: in step 5), the reaction conditions were 4wt% hydrochloric acid solution/0 ℃ C./2 h.
Table 1 shows the composition ratio (mol%) and the reaction conditions of each of the examples and comparative examples:
Claims (8)
1. the preparation method of the BiOCl nano-sheet is characterized in that bismuth-rich glass powder is added into HCl solution, fully reacted at 10-100 ℃, and then washed and dried to obtain the BiOCl nano-sheet;
the bismuth-rich glass powder comprises the following main components: bi (Bi) 2 O 3 ：30～90mol％；B 2 O 3 ：5～50mol％；SiO 2 :0 to 30mol%; znO:0 to 40mol%; AO, a= Mg, ca, ba, sr: 0 to 30mol%; r is R 2 O, r=at least one of Li, na, K: 0 to 40mol%; al (Al) 2 O 3 :0 to 5mol%; rare earth metal oxide: 0 to 3mol%;
the preparation method of the bismuth-rich glass powder comprises the following steps:
(1) Respectively weighing the raw materials corresponding to the components, adding distilled water, performing planetary ball milling for one time, and uniformly mixing to obtain a mixture;
(2) Melting the obtained mixture to obtain uniform glass liquid, and then quenching to obtain glass fragments;
(3) And performing secondary planetary ball milling on the obtained glass fragments to obtain bismuth-rich glass powder.
2. The method according to claim 1, wherein,
the particle size of the bismuth-rich glass powder is 0.5-50 mu m.
3. The method according to claim 1, wherein Bi 2 O 3 Comprising alpha-Bi 2 O 3 beta-Bi 2 O 3 gamma-Bi 2 O 3 At least one of bismuth nitrate and bismuth chloride.
4. The preparation method according to claim 1, wherein the rotational speed of the primary planetary ball mill is 200-400 rpm for 0.5-3 hours;
the rotating speed of the secondary planetary ball milling is 300-600 rpm, and the time is 1-3 hours.
5. The method according to claim 1, wherein the melting temperature is 700 to 1200 ℃ and the time is 0.5 to 3 hours.
6. The preparation method according to claim 1, wherein the solubility of the HCl solution is 4wt% to 38wt%.
7. The preparation method according to claim 1, wherein the mass ratio of HCl in the bismuth-rich glass powder and the hydrochloric acid solution is 1: (0.5-5).
8. The method according to any one of claims 1 to 7, wherein the time for the sufficient reaction is 0.5 to 12 hours;
the conditions for sufficient reaction also include magnetic stirring, ultrasonic treatment, or reaction vibration;
the rotating speed of the magnetic stirring is 200-1500 rpm;
the frequency of the ultrasonic treatment is 20-50 KHz;
the power of the reaction vibration is 100-2000W.
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