CN116161697A - Method for preparing bismuth oxyfluoride microspheres, bismuth oxyfluoride microspheres and application of bismuth oxyfluoride microspheres - Google Patents
Method for preparing bismuth oxyfluoride microspheres, bismuth oxyfluoride microspheres and application of bismuth oxyfluoride microspheres Download PDFInfo
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- IPNGSXQUQIUWKO-UHFFFAOYSA-N bismuth;fluoro hypofluorite Chemical compound [Bi].FOF IPNGSXQUQIUWKO-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000004005 microsphere Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000011259 mixed solution Substances 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000004729 solvothermal method Methods 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000012798 spherical particle Substances 0.000 claims description 17
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 10
- -1 fluoride ions Chemical class 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 238000004020 luminiscence type Methods 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 47
- 239000000463 material Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 23
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 22
- 238000001035 drying Methods 0.000 description 11
- 235000013024 sodium fluoride Nutrition 0.000 description 11
- 239000011775 sodium fluoride Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 239000002135 nanosheet Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PIMIKCFPAJSEQM-UHFFFAOYSA-N bismuth;trinitrate;hydrate Chemical compound O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PIMIKCFPAJSEQM-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 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 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of inorganic material synthesis, and particularly relates to a method for preparing bismuth oxyfluoride microspheres, bismuth oxyfluoride microspheres and application thereof, wherein the method comprises the following steps: (1) Dissolving a bismuth source in ethylene glycol to obtain a transparent solution; (2) Adding a fluorine source into the transparent solution, and fully stirring to obtain a mixed solution; (3) Regulating the pH value of the mixed solution to be alkaline by using an alkaline reagent to obtain a precursor mixed solution; (4) Transferring the precursor mixed solution into a hydrothermal kettle for solvothermal reaction; (5) And cooling after the reaction is finished, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres. According to the method, the micron-sized bismuth oxyfluoride microspheres with high sphere rate and regular morphology are prepared under the conventional solvothermal condition by limiting the mole ratio and pH of a system by utilizing a conventional bismuth source, a fluorine source, a solvent and an alkaline reagent. The method has simple process, low cost and high product quality, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of inorganic material synthesis, and particularly relates to a method for preparing bismuth oxyfluoride microspheres, bismuth oxyfluoride microspheres and application thereof.
Background
Bismuth oxyfluoride (BiOF) has a tetragonal phase structure belonging to the P4/nmm space group, in which [ Bi ] 2 O 2 ]The atomic layers being sandwiched between two F atomic layers, in [001 ]]According to [ F-Bi-O-Bi-F ] in the crystal orientation]The atomic layer period is arranged. The layered structure formed by the unique atomic arrangement provides a larger space for the polarization of atoms, so that the separation of electron-hole pairs generated by illumination is facilitated, and the material has wider application in the fields of photocatalysis and luminescence.
The catalytic effect of a catalytic material is related to its structure, morphology, surface state and particle size. Among the various morphologies, spherical particles can bear more catalytic active centers due to larger specific surface area. In addition, since the nano-particle catalyst is deactivated rapidly and has a short life in the catalytic process, in order to pursue high activity and long life of the catalyst, it is necessary to prepare the material into micron-sized spherical particles.
For fluorescent materials, the morphology features, such as particle morphology regularity, size distribution, length-diameter ratio, particle size, dispersibility and the like, directly affect the luminescence performance of the fluorescent materials. It is worth mentioning that, in the fluorescent particles with spherical morphology, a dense fluorescent powder layer can be formed through close packing, so that the scattering degree of light on the surface of the device is effectively reduced, and the brightness and uniformity of light emission are improved.
The current controllable preparation method of the BiOF comprises a precipitation method, a hydrothermal method, a template method and the like, but based on the intrinsic layered structure of the BiOF, the product is often tetragonal tablet or particles formed by tetragonal tablet clusters, which greatly limits the application of the BiOF in the fields of catalysis and fluorescence. For example: the Chinese patent No. 108483495B discloses a preparation method of BiOF material, which takes bismuthate, reducing agent, fluorine source and auxiliary agent as raw materials, synchronously acts the mechanical force of high-energy ball milling on oxidation-reduction and fluorination reaction, and prepares the BiOF material by heat treatment, washing, impurity removal, solid-liquid separation and drying, wherein the prepared BiOF material is formed by stacking nano sheets of 2-500 nm. Although the Chinese patent No. 104148094B discloses a preparation method of bismuth oxyfluoride/graphene composite visible light catalyst, which uses bismuth nitrate hydrate, ethylene glycol, sodium fluoride and deionized water as raw materials, and obtains spherical bismuth oxyfluoride with the particle size of 800nm through filtering, washing, drying and heat preservation, the method can prepare the spherical bismuth oxyfluoride, but the product has serious aggregation, is actually in a cluster structure, and has poor dispersibility and morphology regularity.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing bismuth oxyfluoride microspheres, which adopts a mixed solution of ethylene glycol and water as a reaction solvent and precisely controls F in a reaction system - /Bi 3+ The BiOF microsphere with better dispersibility is prepared through solvothermal reaction according to the molar ratio and the pH value.
A method for preparing bismuth oxyfluoride microspheres, comprising the steps of:
(1) Dissolving a bismuth source in ethylene glycol to obtain a transparent solution;
(2) Adding a fluorine source into the transparent solution, and fully stirring to obtain a mixed solution;
(3) Regulating the pH value of the mixed solution to be alkaline by using an alkaline reagent to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle for hydrothermal reaction;
(5) And cooling after the reaction is finished, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres.
In some of these embodiments, the bismuth source is selected from hydrated or non-hydrated Bi (NO 3 ) 3 The fluorine source is selected from LiF, naF, KF, NH 4 F, one or more of the alkaline reagents are selected from NaOH solution. Wherein the solvent water is derived from the hydrated bismuth nitrate on the one hand and from the alkaline agent, i.e. sodium hydroxide solution, on the other hand.
In some of these embodiments, in step (1), the concentration of bismuth ions in the clear solution is from 0.01 to 0.1mmol/mL.
Specifically, in step (1), the solution may be subjected to a heat treatment, for example, to 60 ℃ in order to accelerate dissolution.
In some embodiments, in step (2), the molar ratio of fluoride ion to bismuth ion in the mixed solution is greater than or equal to 3:1.
in some preferred embodiments, in the step (2), the molar ratio of the fluoride ion to the bismuth ion in the mixed solution is (3-6): 1.
in some of these embodiments, in step (2), the stirring time is at least 30 minutes; preferably, in the step (2), the stirring time is 30-60min.
In some embodiments, in step (3), the pH of the mixture is adjusted to a pH in the range of 12-13.
BiOF intrinsic has a layered structure, and is usually synthesized by adding Bi to bismuth oxyhalide 3+ And the stoichiometric ratio of halide ions (namely, the molar ratio of fluoride ions to bismuth ions is 1:1) is used as a reference, the preparation of a reaction precursor mixed solution is carried out, the reaction precursor mixed solution is nucleated and grown in a natural state, the prepared product can be crystallized according to the intrinsic lamellar growth tendency of bismuth oxyhalide, and the {001} crystal face group is used as an exposed crystal face, so that the bismuth oxyhalide nano-sheet is finally obtained. However, in the preparation process of the inorganic material, factors influencing the growth form of the particles not only comprise the dominant growth trend of the crystal, but also comprise a plurality of external manually controllable factors such as nucleation rate, complexing agent, pH, surfactant, temperature, reaction time, solvent and the like.
Firstly, the inventor mixes bismuth source, glycol and fluorine source to control F - With Bi 3+ The molar ratio of (2) is increased to at least 3:1 and thoroughly stirring for at least 30min, since the fluorine source, i.e. the fluoride source such as NaF, is insoluble in ethylene glycol, the transparent solution is heated prior to addition of NaF to promote the reaction of NaF with Bi (NO) 3 ) 3 Is carried out by a reaction; due to Bi 3+ And F is equal to - Is stronger than Bi in coordination ability 3+ With NO 3 - Coordination ability of F - Will gradually diffuse to Bi 3+ Nearby conversion to BiF 3 Precipitating; then hydrogen is passed through alkaline reagentThe pH value of the mixed solution is regulated to be alkaline by the sodium oxide solution, so that a large amount of OH is introduced into the mixed solution - Obtaining a precursor mixed solution, and in the subsequent solvothermal reaction process, the precursor mixed solution is prepared due to OH - With Bi 3+ Is greater than F in coordination ability - With Bi 3+ The coordination ability of (2), thus OH - Will gradually replace BiF 3 Part F of (3) - Finally, a stable BiOF product is formed by hydrolysis. In the present invention, the initial fluorine ion excess is controlled to control the BiF 3 After the precipitate has formed sufficiently, excess OH is introduced - So that the product formation process is an ion exchange process, rather than a conventional "nucleation-growth" process, i.e., the product is difficult to crystallize according to an intrinsic growth tendency, and has a high concentration of OH - The growth of the product in all directions is ensured, and spherical particles are thus finally obtained.
Meanwhile, the inventors have found during the research that the formation and dispersion of bismuth oxyfluoride spherical particles is also related to the molar ratio of fluoride ions and bismuth ions in the mixed solution, the concentration of hydroxide ions in the mixed solution, i.e. the pH range of the solution, only in F - /Bi 3+ The molar ratio is greater than or equal to 3: when the pH of the mixed solution is 12-13, the product which is in the shape of micron-sized spheres and has good dispersibility can be obtained. When the pH of the mixed solution is only controlled to be 12-13, and the molar ratio of fluoride ions to bismuth ions is less than 3:1, due to F in the reaction system - And OH (OH) - The concentration of (2) is low so that the product can still grow according to the intrinsic growth trend, for example in F - /Bi 3+ The molar ratio is 1:1 and 2:1, the product is a microsphere formed by stacking lamellar structures, namely the product is still lamellar, and bismuth oxyfluoride microspheres can not be obtained. When the molar ratio of fluorine ion and bismuth ion is controlled to be 3 or more: 1, when the pH of the mixed solution is adjusted without using an alkaline agent or when the pH of the mixed solution is not adjusted, the balling rate and dispersibility of the obtained product are difficult to be ensured, for example, when the pH of the mixed solution is not adjusted or when the pH is relatively low (below 12), OH in the system - The concentration is low, bismuth oxyfluoride grows according to the nucleation of the intrinsic trend, and the product is lamellar structure or contains a small amount of spherical particles; when the pH of the mixture is too high (greater than 13), thisThe reaction proceeds in the ion exchange mode, but due to OH in the system - Too high a concentration results in limited ion diffusion, severe agglomeration between product particles and poor dispersibility.
In some embodiments, in step (4), the hydrothermal reaction is carried out at a reaction temperature of 120-220 ℃ for a reaction time of 20-28 hours; preferably, in the step (4), the reaction temperature of the hydrothermal reaction is 150-200 ℃ and the reaction time is 24-26h.
The bismuth oxyfluoride microsphere prepared by the method is micron-sized spherical particles, and the average size of the particles is smaller than 5 mu m.
The bismuth oxyfluoride microsphere is applied to the fields of photocatalysis and luminescence.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for preparing bismuth oxyfluoride microspheres, which utilizes a conventional bismuth source, a fluorine source and a solvent to prepare micron-sized bismuth oxyfluoride microspheres with high sphere rate and regular morphology under the conventional solvothermal condition by limiting the pH of a system. The method has simple process, low cost and high product quality, and is suitable for popularization and application.
(2) Compared with the traditional growth mode of 'nucleation-growth' bismuth oxyhalide, the invention develops a novel preparation method of bismuth oxyfluoride characterized by 'ion exchange', and the ion concentration of a reaction system at different stages is controlled by controlling the addition sequence and the addition amount of different raw materials, so that the growth state of a bismuth oxyfluoride product is influenced. The method overcomes the layered growth tendency of the intrinsic anisotropy of bismuth oxyfluoride, and bismuth oxyfluoride crystals can grow along all directions, so that the spherical bismuth oxyfluoride material is prepared.
(3) According to the method for preparing the bismuth oxyfluoride microsphere, disclosed by the invention, the prepared bismuth oxyfluoride microsphere does not contain flaky impurities by strictly controlling the amounts of fluoride ions and hydroxide ions in different stages of reaction systems, so that the balling rate is high and the dispersibility is good.
(4) The bismuth oxyfluoride material prepared by the invention has a microspherical structure, regular morphology and good dispersibility, and is suitable for being used as a photocatalytic material and a fluorescent material.
Drawings
For a clearer description of embodiments of the invention or of solutions in the prior art, the drawings which are used in the description of the embodiments or of the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of bismuth oxyfluoride microspheres prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of bismuth oxyfluoride microspheres prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of bismuth oxyfluoride microspheres prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of bismuth oxyfluoride microspheres prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of the product prepared in comparative example 1 of the present invention;
FIG. 6 is a scanning electron microscope image of the product prepared in comparative example 2 of the present invention;
FIG. 7 is a scanning electron microscope image of the product prepared in comparative example 3 of the present invention;
FIG. 8 is a scanning electron microscope image of the product prepared in comparative example 4 of the present invention;
FIG. 9 is a scanning electron microscope image of the product prepared in comparative example 5 of the present invention.
Detailed Description
The experimental methods of the present invention, in which specific conditions are not specified in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The various chemicals commonly used in the examples are commercially available.
Unless defined otherwise, 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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
The bismuth oxyfluoride microsphere is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 6mmol of NaF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Regulating the pH value of the mixed solution to 12 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 24 hours in a drying oven at 200 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres, wherein a scanning electron microscope diagram of the bismuth oxyfluoride microspheres is shown in figure 1.
As shown in FIG. 1, the products were mostly in the form of micron spherical particles, the average size was 5 μm or less, and the dispersibility was good.
Example 2
The bismuth oxyfluoride microsphere is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 8mmol KF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Regulating the pH value of the mixed solution to 13 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 20h in a drying oven at 150 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres, wherein a scanning electron microscope diagram of the bismuth oxyfluoride microspheres is shown in figure 2.
As shown in FIG. 2, the products were mostly in the form of micron spherical particles, with an average size of 2 μm or less, and good dispersibility.
Example 3
The bismuth oxyfluoride microsphere is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 Stirring and dissolving in 60mL of ethylene glycol to obtain a transparent solution, and heating to 60 ℃;
(2) To the clear solution 12mmol NH was added 4 F, fully stirring for 30min to obtain turbid mixed liquid;
(3) Regulating the pH value of the mixed solution to 12 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 28h in a drying oven at 220 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres, wherein a scanning electron microscope diagram of the bismuth oxyfluoride microspheres is shown in figure 3.
As shown in FIG. 3, the products were mostly in the form of micron spherical particles, the average size was 5 μm or less, and the dispersibility was good.
Example 4
The bismuth oxyfluoride microsphere is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 12mmol of NaF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Regulating the pH value of the mixed solution to 13 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 20h in a drying oven at 200 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres, wherein a scanning electron microscope diagram of the bismuth oxyfluoride microspheres is shown in figure 4.
As shown in FIG. 4, the products were mostly in the form of micron spherical particles, the average size was 3 μm or less, and the dispersibility was good.
Comparative example 1
The comparative example differs from example 1 in that the pH of the mixed solution in step (3) is different.
The bismuth oxyfluoride material is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 6mmol of NaF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Adjusting the pH value of the mixed solution to 13.6 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 24 hours in a drying oven at 200 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride material, wherein a scanning electron microscope diagram of the bismuth oxyfluoride material is shown in figure 5.
As shown in FIG. 5, it was found that the product was approximately microsphere-shaped, but the agglomeration between particles was severe and the dispersibility was poor.
Comparative example 2
The comparative example differs from example 1 in that the pH of the mixed solution in step (3) is different.
The bismuth oxyfluoride material is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 6mmol of NaF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Adjusting the pH value of the mixed solution to 11 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 24 hours in a drying oven at 200 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride material, wherein a scanning electron microscope diagram of the bismuth oxyfluoride material is shown in figure 6.
As shown in FIG. 6, it can be seen that the product is mostly flaky particles, containing a small amount of spherical particles.
Comparative example 3
This comparative example differs from example 1 in that the pH of the mixed solution was not adjusted.
The bismuth oxyfluoride material is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 6mmol of NaF into the transparent solution, fully stirring for 30min to obtain turbid mixed solution, and testing the pH value of the mixed solution to be 7;
(3) Transferring the mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 24 hours in a drying oven at 200 ℃;
(4) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride material, wherein a scanning electron microscope diagram of the bismuth oxyfluoride material is shown in figure 7.
As shown in fig. 7, it can be seen that the product was a nanosheet and bismuth oxyfluoride microspheres were not obtained.
Comparative example 4
The comparative example differs from example 1 in that the amount of fluorine source added is different, i.e., the molar ratio of fluorine ion to bismuth ion in the mixed solution is different.
The bismuth oxyfluoride material is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 2mmol of NaF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Regulating the pH value of the mixed solution to 12 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 24 hours in a drying oven at 200 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride material, wherein a scanning electron microscope diagram of the bismuth oxyfluoride material is shown in figure 8.
As shown in fig. 8, it can be seen that the spherical particles in the product are fewer and are cross-stacked from the nano-sheets, i.e. bismuth oxyfluoride still grows according to the intrinsic tendency to give a sheet material.
Comparative example 5
The comparative example differs from example 1 in that the amount of fluorine source added is different, i.e., the molar ratio of fluorine ion to bismuth ion in the mixed solution is different.
The bismuth oxyfluoride material is prepared by the following method:
(1) 2mmol Bi (NO) 3 ) 3 ·5H 2 O is stirred and dissolved in 60mL of ethylene glycol to obtain transparent solution, and the transparent solution is heated to 60 ℃;
(2) Adding 4mmol of NaF into the transparent solution, and fully stirring for 30min to obtain turbid mixed solution;
(3) Regulating the pH value of the mixed solution to 12 by adopting a 4mol/L NaOH solution to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle, and performing solvothermal reaction for 24 hours in a drying oven at 200 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally cleaning the product to obtain the bismuth oxyfluoride material, wherein a scanning electron microscope diagram of the bismuth oxyfluoride material is shown in figure 9.
As shown in fig. 9, although the spherical particles in the product are increased, the spherical particles are formed by cross stacking of nano sheets, namely, the bismuth oxyfluoride material is still in a sheet structure, and the bismuth oxyfluoride microsphere is not obtained.
According to examples 1 to 4, as can be seen from FIGS. 1 to 4, the bismuth oxyfluoride prepared by the method of the present invention is microspherical, the average size is below 5 μm, the balling rate is high, the morphology is regular, and the dispersibility is good. In comparative examples 1 and comparative examples 1 to 3, the pH of the mixed solution in comparative example 1 was too high, so that the hydroxide concentration was too high and ion diffusion was inhibited, and the prepared product was bismuth oxyfluoride microspheres, but the aggregation of the product was severe and the dispersibility was poor; the pH value of the mixed solution in the comparative example 2 is relatively low, the intrinsic growth trend of bismuth oxyfluoride cannot be effectively inhibited, the prepared product is mostly flaky particles, the balling rate is low, and the bismuth oxyfluoride microspheres are less; in comparative example 3, the pH of the mixed solution was not adjusted, the concentration of hydroxide ions in the mixed solution was low, bismuth oxyfluoride still grew according to the "nucleation-growth" eigenmode, and the product was a lamellar structure. Comparative example 1 and comparative examples 4 to 5, the molar ratio of fluorine ion to bismuth ion in comparative examples 4 to 5 was 1:1 and 2:1, the fluorine ion content is insufficient and approaches to the stoichiometric ratio in the product, so that the intrinsic growth trend of the product is shown, and therefore, the spherical particles are formed by cross stacking of nano sheets.
In conclusion, the BiOF micron-sized spherical particles are prepared by a solvothermal method, the method is simple and convenient to operate, environment-friendly, low in cost and good in product dispersibility, the application of the material in the field of photocatalysis is hopefully promoted, the fluorescence performance of the material can be effectively improved, and the method has good application value.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for preparing bismuth oxyfluoride microspheres, comprising the steps of:
(1) Dissolving a bismuth source in ethylene glycol to obtain a transparent solution;
(2) Adding a fluorine source into the transparent solution, and fully stirring to obtain a mixed solution;
(3) Regulating the pH value of the mixed solution to be alkaline by using an alkaline reagent to obtain a precursor mixed solution;
(4) Transferring the precursor mixed solution into a hydrothermal kettle for solvothermal reaction;
(5) And cooling after the reaction is finished, and centrifugally cleaning the product to obtain the bismuth oxyfluoride microspheres.
2. A method of preparing bismuth oxyfluoride microspheres according to claim 1, wherein the bismuth source is selected from hydrated or non-hydrated Bi (NO 3 ) 3 The fluorine source is selected from LiF, naF, KF, NH 4 F, one or more of the alkaline reagents are selected from NaOH solution.
3. The method for preparing bismuth oxyfluoride microspheres according to claim 1, wherein in the step (1), the concentration of bismuth ions in the transparent solution is 0.01-0.1mmol/mL.
4. The method for preparing bismuth oxyfluoride microspheres according to claim 1, wherein in the step (2), the molar ratio of fluoride ions to bismuth ions in the mixed solution is greater than or equal to 3:1.
5. the method for preparing bismuth oxyfluoride microspheres according to claim 4, wherein in the step (2), the molar ratio of fluoride ion to bismuth ion in the mixed solution is (3-6): 1.
6. the method for preparing bismuth oxyfluoride microspheres according to claim 1, wherein in step (2), the stirring time is at least 30min.
7. The method for preparing bismuth oxyfluoride microspheres according to claim 1, wherein in the step (3), the pH value of the mixed solution after pH adjustment is in the range of 12 to 13.
8. The method for preparing bismuth oxyfluoride microspheres according to claim 1, wherein in the step (4), the reaction temperature of the hydrothermal reaction is 120-220 ℃ and the reaction time is 20-28h.
9. Bismuth oxyfluoride microspheres prepared according to any one of claims 1-8, wherein the bismuth oxyfluoride microspheres are micron-sized spherical particles having an average particle size of less than 5 μm.
10. Use of the bismuth oxyfluoride microspheres according to claim 9 in the fields of photocatalysis and luminescence.
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