CN108295877B - Bismuth oxyhalide/porous titanium hydroxyapatite composite material and preparation method and application thereof - Google Patents
Bismuth oxyhalide/porous titanium hydroxyapatite composite material and preparation method and application thereof Download PDFInfo
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- CN108295877B CN108295877B CN201710781097.8A CN201710781097A CN108295877B CN 108295877 B CN108295877 B CN 108295877B CN 201710781097 A CN201710781097 A CN 201710781097A CN 108295877 B CN108295877 B CN 108295877B
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- bismuth
- composite material
- porous titanium
- titanium hydroxyapatite
- hydroxyapatite composite
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- 239000010936 titanium Substances 0.000 title claims abstract description 96
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 94
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 87
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 52
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 70
- 239000000725 suspension Substances 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229910001868 water Inorganic materials 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 22
- 239000004005 microsphere Substances 0.000 claims description 22
- -1 sodium halide Chemical class 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 18
- 150000001621 bismuth Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910001507 metal halide Inorganic materials 0.000 claims description 13
- 150000005309 metal halides Chemical class 0.000 claims description 13
- 230000001699 photocatalysis Effects 0.000 claims description 12
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 7
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001509 metal bromide Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001511 metal iodide Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 61
- 229940073609 bismuth oxychloride Drugs 0.000 description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 23
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 16
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 16
- 229910000348 titanium sulfate Inorganic materials 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000001103 potassium chloride Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LGKICYMSTAPUPY-UHFFFAOYSA-M O(Br)Br.[Bi].Cl[Bi]=O Chemical compound O(Br)Br.[Bi].Cl[Bi]=O LGKICYMSTAPUPY-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
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- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PIJVDJTXPKJZHD-UHFFFAOYSA-M bismuth;oxygen(2-);bromide Chemical compound [O-2].[Br-].[Bi+3] PIJVDJTXPKJZHD-UHFFFAOYSA-M 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
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- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- 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
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention relates to the technical field of removing harmful gases in interior decoration, and particularly discloses a bismuth oxyhalide/porous titanium hydroxyapatite composite material and a preparation method and application thereof. The chemical formula of the porous titanium hydroxyapatite in the bismuth oxyhalide/porous titanium hydroxyapatite composite material is TixCa(5‑x)(PO4)(3+2x/3)(OH), x is more than or equal to 1 and less than or equal to 5, the porous titanium hydroxyapatite has a honeycomb porous structure, and the bismuth oxyhalide is enriched on the surface and in the pore channel structure of the porous titanium hydroxyapatite. The composite material has an average pore diameter of 8-12nm and a specific surface area of 50-150cm2The energy gap is 2.50eV, the material has strong adsorption capacity on harmful gases in interior decoration, and formaldehyde and the like can be organically oxidized into CO under illumination2And H2And O, no secondary pollution.
Description
Technical Field
The invention relates to the technical field of removing harmful gases in interior decoration, in particular to a preparation method and application of a bismuth oxyhalide/porous titanium hydroxyapatite composite material.
Background
The rapid development of economy causes serious environmental pollution problems, especially indoor environment pollution, and has great negative effects on our lives. In recent years, due to the uneven quality of indoor decoration materials, indoor harmful gas pollution exceeds the national standard, and the life health of human beings is seriously threatened. According to statistics, the types of indoor harmful gases after decoration are over 400, wherein the main harmful gases comprise Volatile Organic Compounds (VOCs) such as benzene, formaldehyde, ammonia and the like, and the harmful gases mainly come from building materials, indoor decoration materials, paints, adhesives, furniture, adhesives and the like. The long-term pollution in indoor environment can cause symptoms such as headache, nausea, fatigue, dysphoria, immunity reduction and allergy, and can also cause cancer, deformity, mutation and the like.
The photocatalytic degradation technology is one of effective methods for treating persistent toxic and harmful organic pollutants in the environment, and can decompose macromolecular organic pollutants such as formaldehyde, ammonia gas, benzene and the like into non-toxic and harmless micromolecules of N2, H2O and CO at room temperature2No secondary pollution, durability, and wide application prospect in the aspect of treating air pollution and other environmental pollution, especially indoor air pollution.
Bismuth oxyhalide BiOX (X ═ Cl, Br, I) belongs to a V-VI-VII main group, is a novel semiconductor material, has a unique electronic structure, a small forbidden band degree, good optical performance and photocatalytic performance, and has a large visible light corresponding range. Particularly, BiOCl has good stability, no toxicity, unique layered structure and indirect transition mode, is beneficial to effective separation and charge transfer of electron-hole, effectively prevents electron-hole recombination, and has higher photocatalytic activity. However, the single BiOX catalyst has the problems of easy agglomeration, poor dispersibility, insufficient contact with pollutants such as formaldehyde, acetaldehyde and the like, unsatisfactory adsorption and low photocatalytic efficiency in the catalytic process.
Disclosure of Invention
Aiming at the problems that a single BiOX catalyst is easy to agglomerate in the catalysis process, poor in dispersity, incapable of fully contacting with pollutants such as formaldehyde and acetaldehyde, unsatisfactory in adsorbability and low in photocatalysis efficiency, the invention provides a bismuth oxyhalide/porous titanium hydroxyapatite composite material.
Further, the invention also provides a preparation method of the bismuth oxyhalide/porous titanium hydroxyapatite composite material.
Further, the invention also provides application of the bismuth oxyhalide/porous titanium hydroxyapatite composite material.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a bismuth oxyhalide/porous titanium hydroxyapatite composite material is characterized in that: the chemical formula of the porous titanium hydroxyapatite is TixCa(5-x)(PO4)(3+2x/3)(OH)，1≤x<5, the porous titanium hydroxyapatite has a honeycomb porous structure, the average pore diameter is 8-12nm, and the specific surface area is 50-150cm2(ii)/g; the bismuth oxyhalide is enriched on the surface and in the pore channel structure of the porous titanium hydroxyapatite.
Compared with the prior art, the porous titanium hydroxyapatite in the bismuth oxyhalide/porous titanium hydroxyapatite composite material provided by the invention has high bactericidal effect and affinity to gas, has high photocatalytic activity under illumination, has a honeycomb-shaped porous structure and a large specific surface area, and increases the adsorption of harmful pollutants such as formaldehyde, acetaldehyde and the like, so that the porous TiHA is a good carrier in photocatalysis. The bismuth oxyhalide is enriched on the surface and in the pore canal of the TiHA, so that the problems of easy agglomeration and poor dispersibility of the photocatalyst in the catalytic process can be solved, and the high adsorbability of the porous TiHA and the high photocatalytic degradation capability of the BiOX are organically combined, so that the adsorbability and the photocatalytic efficiency can be improved.
Further, the invention also provides a preparation method of the bismuth oxyhalide/porous titanium hydroxyapatite composite material. The preparation method at least comprises the following steps:
step 1, adding metal halide into a bismuth salt solution, reacting at constant temperature, and after the reaction is finished, purifying and drying to obtain bismuth oxyhalide;
step 2, mixingPorous microsphere CaCO3Dispersing the template powder and the bismuth oxyhalide obtained in the step (1) into water to obtain a suspension;
step 3, adding a titanium source into the suspension, and uniformly dispersing;
step 4, dripping a monohydrogen phosphate solution into the suspension, adjusting the pH value to 9-11 by using a pH regulator, and reacting at constant temperature;
and 5, after the reaction is finished, purifying and drying to obtain a product.
Compared with the prior art, the preparation method of the bismuth oxyhalide/porous titanium hydroxyapatite composite material provided by the invention is simple, and the porous microsphere CaCO is used3As a template, with Ti4+Substitution of Ca in apatite2+The process is easy to control.
Further, the invention also provides application of the bismuth oxyhalide/porous titanium hydroxyapatite composite material in preparation of photocatalytic environment-friendly coatings.
Compared with the prior art, the bismuth oxyhalide/porous titanium hydroxyapatite composite material has the thickness of 50-150cm2The specific surface area per gram is greatly increased, the adsorption capacity to harmful gases in interior decoration is greatly increased, and the oxidative degradation rate of the harmful gases such as formaldehyde and the like is accelerated under illumination to degrade the harmful gases into CO2And H2And O, no secondary pollution.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 and FIG. 2 are micrographs of BiOCl/porous TiHA composite material;
FIG. 3 is an XRD pattern of a BiOCl/porous TiHA composite;
FIG. 4 is a graph of the diffuse reflectance of ultraviolet-visible light for BiOCl, TiHA, BiOCl/porous TiHA composites;
FIG. 5 is a diagram of the forbidden band widths of BiOCl, TiHA and BiOCl/porous TiHA composite materials;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a bismuth oxyhalide/porous titanium hydroxyapatite composite material, wherein the chemical formula of the porous titanium hydroxyapatite is TixCa(5-x)(PO4)(3+2x/3)(OH)，1≤x<5, the porous titanium hydroxyapatite has a honeycomb porous structure, the average pore diameter is 8-12nm, and the specific surface area is 50-150cm2(ii)/g; the bismuth oxyhalide is enriched on the surface and in the pore channel structure of the porous titanium hydroxyapatite.
The bismuth oxyhalide/porous titanium hydroxyapatite composite material provided by the embodiment of the invention organically combines the high adsorbability of porous TiHA and the high photocatalytic degradation capability of BiOX, and can improve adsorbability and photocatalytic efficiency.
Further, the invention also provides a preparation method of the bismuth oxyhalide/porous titanium hydroxyapatite composite material, which at least comprises the following steps:
step 1, adding metal halide into a bismuth salt solution, reacting at constant temperature, and after the reaction is finished, purifying and drying to obtain bismuth oxyhalide;
step 2, preparing porous microspheres CaCO3Dispersing the template powder and the bismuth oxyhalide obtained in the step (1) into water to obtain a suspension;
step 3, adding a titanium source into the suspension, and uniformly dispersing;
step 4, dripping a monohydrogen phosphate solution into the suspension, adjusting the pH value to 9-11 by using a pH regulator, and reacting at constant temperature;
and 5, after the reaction is finished, purifying and drying to obtain a product.
The preparation method provided by the invention is simple.
The above preparation process is further explained below:
specifically, in the step 1, the metal halide is added into the bismuth salt solution, and the mixture is reacted at a constant temperature, and after the reaction is finished, the bismuth oxyhalide is purified and dried to obtain the bismuth oxyhalide. The metal halide is at least one of metal chloride, metal iodide and metal bromide. The bismuth salt is preferably bismuth nitrate pentahydrate or bismuth sulfate, and the preferred bismuth salt is cheap and easy to obtain, so that the production cost of the bismuth oxyhalide/porous titanium hydroxyapatite composite material can be reduced.
Further preferably, Bi is contained in the bismuth salt solution3+Has a concentration of 0.005 to 0.5 mol/L, preferably Bi3+The concentration can ensure that the bismuth salt is fully dissolved in the solution so as to ensure that the bismuth salt fully participates in the reaction.
Further preferably, the metal halide is a sodium halide or a potassium halide. The sodium halide or the potassium halide is a metal halide with excellent water solubility, so that the dissolving operation is easy to carry out, and the time cost is saved.
More preferably, the mixed solution obtained by adding a metal halide in which a halogen ion X is present to the bismuth salt solution-And Bi3+The molar ratio of (A) to (B) is 1-1.5: 1. suitable X-And Bi3+The molar ratio of the bismuth salt can ensure that the bismuth salt fully participates in the reaction and avoid waste. If the metal halide content is too high, the residual metal halide increases the difficulty of purification treatment and prolongs the production period.
Further preferably, the isothermal reaction conditions are as follows: reacting for 2.5-3.5 h at 70-90 ℃. The above reaction temperature and time are adopted, so that the reactants can be sufficiently reacted at a proper temperature and time. If the temperature is too high or the time is too long, byproducts are generated and energy is wasted; if the temperature is too low or the time is too short, the reaction will be incomplete, resulting in waste of raw materials.
Further preferably, the purification is performed by washing with deionized water or absolute ethyl alcohol until the washing solution does not contain halogen ions. Deionized water or absolute ethyl alcohol is adopted to wash the reactant, so that other impurities can be avoided being introduced; the standard of washing until no halogen ion is contained in the washing liquid can be used for detecting that the impurity residue in the solution meets the requirement.
Preferably, the drying treatment is drying at 75-85 ℃ for 10-14 h. By adopting the drying temperature and time, the product to be dried can be sufficiently dried, the generation of impurities and the increase of cost caused by overhigh temperature or overlong time are avoided, and incomplete drying caused by overlow temperature or overlong time is avoided.
In the step 2, the concentration of the bismuth oxyhalide in the suspension is 0.005-0.5 mlol/L, and the porous microspheres are CaCO3Concentration: the molar ratio of the concentration of bismuth oxyhalide is 1: 1 to 10. The preferable concentration of the bismuth oxyhalide can ensure that the bismuth oxyhalide is well dispersed in the solution, thereby being beneficial to the full reaction; preferred porous Microspherical CaCO3The molar ratio of the concentration to the concentration of the bismuth oxyhalide can be used for controlling the molar ratio of the porous titanium hydroxyapatite to the bismuth oxyhalide in the final product, thereby achieving the purpose of controlling the product quality.
In the step 3, the concentration of the dispersed titanium source is 0.001-0.1 mol/L, and the preferable concentration of the titanium source can be used for controlling Ti4+Substituted Ca2+And thus the product quality.
In the step 4, the concentration of the monohydrogen phosphate solution is 0.01-0.1 mol/L, and the preferable concentration of the monohydrogen phosphate solution can ensure that the monohydrogen phosphate solution is fully dissolved in the solution, so that the reaction is fully carried out, and the porous titanium hydroxyapatite is further obtained.
Further preferably, the dropping speed is 1-3 m L/min, and the preferable speed is adopted, so that the working efficiency can be ensured, and the phenomenon that the dropping is too fast to generate byproducts is avoided.
Further preferably, the pH regulator is ammonia water or sodium hydroxide. Ammonia and sodium hydroxide are sensitive pH regulators, and the pH value of the solution can be easily and accurately regulated to the required range in the invention.
Preferably, the constant temperature reaction is carried out for 1-3 hours at the temperature of 60-80 ℃. The reaction temperature and the reaction time are adopted, so that reactants can fully react, byproducts can be generated and energy is wasted when the temperature is too high or the time is too long, and the reaction is incomplete when the temperature is too low or the time is too short, so that raw materials are wasted.
In the step 5, the purification is carried out by washing with deionized water or absolute ethyl alcohol until the pH value of the washing solution is 6.5-7.5, and then washing for 2-4 times. The invention adopts deionized water or absolute ethyl alcohol to wash the reactant, thereby avoiding introducing other impurities. The standard of washing until the pH value of the washing liquid is 6.5-7.5 can be used for detecting that the impurity residue in the solution meets the requirement, and the soluble impurities can be fully washed away after washing for 2-4 times.
More preferably, the drying treatment is drying at 75-85 ℃ for 10-14 h. The preferable drying temperature and time can ensure that the product to be dried is fully dried, impurities can be generated and the cost is increased when the temperature is too high or the time is too long, the drying is incomplete when the temperature is too low or the time is too short, and the moisture content does not meet the requirement.
Further, the invention also provides application of the bismuth oxyhalide/porous titanium hydroxyapatite composite material in preparation of photocatalytic environment-friendly coatings.
In order to better illustrate the embodiments of the present invention, the following examples are further illustrative.
Example 1
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.01mol of potassium chloride into 200ml of 0.05 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using absolute ethyl alcohol until the washing liquid does not contain chloride ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.01mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.005 mol/L into the suspension under the stirring condition;
step 5Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 9 with NaOH, and reacting in a constant-temperature water bath at 60 ℃ under normal pressure for 3 h;
and 6, after the reaction is finished, washing the product obtained in the step 5 with absolute ethyl alcohol until the pH value of the washing liquid is 6.5, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 2
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.012mol of potassium chloride into 200ml of 0.05 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in 70 ℃ water bath for 3 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using absolute ethyl alcohol until the washing liquid does not contain chloride ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.01mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.005 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 3m L/min, adjusting the pH value to 11 with NaOH after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 70 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with absolute ethyl alcohol until the pH value of the washing liquid is 7, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 3
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.015mol of potassium chloride into 200ml of bismuth sulfate solution with the concentration of 0.025 mol/L, and reacting for 3 hours in a water bath at the temperature of 80 ℃;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using deionized water until the washing liquid does not contain chloride ions, and drying the product in an oven at 80 ℃ for 14 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.01mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.005 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 1m L/min, adjusting the pH value to 10 with NaOH, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 1 h;
and 6, after the reaction is finished, washing the product obtained in the step 5 with absolute ethyl alcohol until the pH value of the washing liquid is 7.5, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 4
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.0012mol of sodium chloride into 200ml of 0.0025 mol/L mol of bismuth sulfate solution, and reacting in a water bath at 90 ℃ for 2.5 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using deionized water until the washing liquid does not contain chloride ions, and drying the product in an oven at 85 ℃ for 12 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.001mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.01 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 9 with ammonia water after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with absolute ethyl alcohol until the pH value of the washing liquid is 7, washing with deionized water for 3 times, and finally drying the product in an oven at 85 ℃ for 14 hours to obtain the bismuthyl chloride/porous titanium hydroxyapatite composite material.
Example 5
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.0036mol of potassium chloride into 200ml of bismuth nitrate solution with the concentration of 0.015 mol/L, and reacting in a water bath at the temperature of 80 ℃ for 3.5 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using deionized water until the washing liquid does not contain chloride ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.001mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.01 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 3m L/min, adjusting the pH value to 11 with ammonia water after dropwise adding, and reacting in a constant-temperature water bath at the temperature of 60 ℃ under normal pressure for 3 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with absolute ethyl alcohol until the pH value of the washing liquid is 7, washing with absolute ethyl alcohol for 3 times, and finally drying the product in a 75-DEG C oven for 10 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 6
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.006mol of sodium chloride into 200ml of 0.0125 mol/L-concentration bismuth sulfate solution, and reacting in a water bath at 80 ℃ for 3.5 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using absolute ethyl alcohol until the washing liquid does not contain chloride ions, and drying the product in an oven at 75 ℃ for 10 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.001mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.01 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 1m L/min, adjusting the pH value to 10 with ammonia water after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 70 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 6.8, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 75 ℃ for 12 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 7
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.012mol of sodium chloride into 200ml of bismuth nitrate solution with the concentration of 0.05 mol/L, and reacting in a water bath at 90 ℃ for 2.5 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using deionized water until the washing liquid does not contain chloride ions, and drying the product in an oven at 80 ℃ for 14 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.001mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.01 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.03 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 9 with ammonia water after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 7.2, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 14 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 8
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.02mol of potassium chloride into 200ml of 0.1 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 70 ℃ for 3.5 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using absolute ethyl alcohol until the washing liquid does not contain chloride ions, and drying the product in an oven at 85 ℃ for 10 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.01mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.05 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.01 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 3m L/min, adjusting the pH value to 10 with NaOH, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 3 h;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 7.4, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 10 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 9
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.06mol of sodium chloride into 200ml of 0.15 mol/L-concentration bismuth sulfate solution, and reacting in a water bath at 80 ℃ for 2.5 h;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using deionized water until the washing liquid does not contain chloride ions, and drying the product in an oven at 80 ℃ for 14 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.01mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.05 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.1 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 1m L/min, adjusting the pH value to 11 with NaOH after dropwise adding, and reacting in a constant-temperature water bath at the temperature of 60 ℃ under normal pressure for 1 h;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 6.7, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 75 ℃ for 12 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 10
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.1mol of potassium chloride into 200ml of 0.25 mol/L-concentration bismuth sulfate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using absolute ethyl alcohol until the washing liquid does not contain chloride ions, and drying the product in an oven at 75 ℃ for 12 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.01mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.05 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.05 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 9 with ammonia water after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 70 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 6.9, washing with absolute ethyl alcohol for 3 times, and finally drying the product in a 75 ℃ oven for 14 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 11
The embodiment of the invention provides a bismuth oxychloride/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.02mol of potassium chloride into 200m of a L concentration 0.1 mol/L pentahydrate bismuth nitrate solution, and reacting in a water bath at 80 ℃ for 3.5 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by using absolute ethyl alcohol until the washing liquid does not contain chloride ions, and drying the product in an oven at 85 ℃ for 10 hours to obtain bismuth oxychloride;
step 3, dissolving the bismuthyl chloride prepared in the step 2 in 200ml of deionized water, and adding 0.1mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.1 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.01 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 9 with NaOH, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 h;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 7.1, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 85 ℃ for 10 hours to obtain the bismuth oxychloride/porous titanium hydroxyapatite composite material.
Example 12
The embodiment of the invention provides a bismuthyl bromide/porous titanium hydroxyapatite composite material, and a preparation method thereof comprises the following steps:
step 1, adding 0.005mol of potassium bromide into 200ml of 0.025 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by deionized water until the washing liquid does not contain bromide ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxybromide;
step 3, dissolving the bismuthyl bromide prepared in the step 2 in 200ml of deionized water, and adding 0.005mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.001 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.01 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 3m L/min, adjusting the pH value to 11 with NaOH after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 3 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 7.3, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxybromide/porous titanium hydroxyapatite composite material.
Example 13
The embodiment of the invention provides a bismuth oxyiodide/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.006mol of sodium iodide into 200ml of 0.025 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by deionized water until the washing liquid does not contain iodide ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxyiodide;
step 3, dissolving the bismuth oxyiodide prepared in the step 2 in 200ml of deionized water, and adding 0.005mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.001 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.1 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 1m L/min, adjusting the pH value to 11 with NaOH after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 7.5, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxyiodide/porous titanium hydroxyapatite composite material.
Example 14
The embodiment of the invention provides a bismuth oxychloride-bismuth oxybromide/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.003mol of potassium chloride and 0.003mol of potassium bromide into 200ml of 0.025 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by deionized water until the washing liquid does not contain chlorine and bromine ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxychloride-bismuth oxybromide;
step 3, dissolving the bismuthyl chloride-bismuthyl bromide prepared in the step 2 into 200ml of deionized water, and adding 0.005mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.1 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.1 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 11 with NaOH after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 7.1, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxychloride-bismuth oxybromide/porous titanium hydroxyapatite composite material.
Example 15
The embodiment of the invention provides a bismuth oxychloride-bismuth oxyiodide/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.003mol of sodium chloride and 0.003mol of sodium iodide into 200ml of 0.025 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by deionized water until the washing liquid does not contain chlorine and iodine ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxychloride-bismuth oxyiodide;
step 3, dissolving the bismuthyl chloride-bismuthyl iodide prepared in the step 2 into 200ml of deionized water, and adding 0.005mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.1 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.1 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 10 with NaOH, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 h;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 6.8, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxychloride-bismuth oxyiodide/porous titanium hydroxyapatite composite material.
Example 16
The embodiment of the invention provides a bismuthyl chloride-bismuthyl bromide-bismuthyl iodide/porous titanium hydroxyapatite composite material, and the preparation method comprises the following steps:
step 1, adding 0.002mol of sodium chloride, 0.002mol of sodium iodide and 0.002mol of sodium bromide into 200ml of 0.025 mol/L-concentration bismuth nitrate pentahydrate solution, and reacting in a water bath at 80 ℃ for 3 hours;
step 2, after the reaction is finished, washing the product obtained in the step 1 by deionized water until the washing liquid does not contain chlorine, iodine and bromine ions, and drying the product in an oven at 80 ℃ for 12 hours to obtain bismuth oxychloride-bismuth oxybromide-bismuth oxyiodide;
step 3, dissolving the bismuthyl chloride-bismuthyl bromide-bismuthyl iodide prepared in the step 2 into 200ml of deionized water, and adding 0.005mol of porous microsphere CaCO3Preparing a template into suspension;
step 4, slowly adding 200ml of titanium sulfate solution with the concentration of 0.1 mol/L into the suspension under the stirring condition;
step 5, adding Na with the concentration of 0.1 mol/L2HPO4Dropwise adding the solution into the suspension at a speed of 2m L/min, adjusting the pH value to 11 with NaOH after dropwise adding, and reacting in a constant-temperature water bath at normal pressure and 80 ℃ for 2 hours;
and 6, after the reaction is finished, washing the product obtained in the step 5 with deionized water until the pH value of the washing liquid is 6.9, washing with absolute ethyl alcohol for 3 times, and finally drying the product in an oven at 80 ℃ for 12 hours to obtain the bismuth oxychloride-bismuth oxybromide-bismuth oxyiodide/porous titanium hydroxyapatite composite material.
Example 17
In order to better illustrate the characteristics of the bismuth oxychloride/porous titanium hydroxyapatite composite material provided by the embodiment of the invention, XRD detection, ultraviolet-visible light diffuse reflection detection and forbidden bandwidth test are performed on the bismuth oxychloride/porous titanium hydroxyapatite composite material prepared in the embodiment 1, and the results are shown in fig. 1 to 5.
As can be seen from fig. 1 and 2, the bismuth oxychloride/porous titanium hydroxyapatite composite material is of a honeycomb-shaped porous structure, so that the specific surface area of a sample is increased, the adsorption capacity of the sample on harmful gases can be enhanced, and the photocatalytic efficiency is improved.
As can be seen from FIG. 3, the characteristic diffraction peaks of the sample obtained in example 1 are substantially matched with the standard card of tetragonal BiOCl (JCPDSNO.82-0485) and the standard card of HAP (JCPDS 9-432), no other impurity peaks exist, and the peak values of the characteristic peaks are sharper, which indicates that the sample has better crystallinity;
as can be seen from fig. 4, the bismuth oxychloride/porous titanium hydroxyapatite composite material and TiHA have stronger absorption in the ultraviolet region, which is higher than the absorption strength of BiOCl; the absorption intensity of the composite material between 350nm and 400nm is obviously better than that of BiOCl and TiHA, which are caused by the interaction between BiOCl and TiHA. FIG. 2 shows that the absorption of the material to light is improved to some extent after BiOCl and TiHA are compounded.
As can be seen from fig. 5, the energy gap widths of BiOCl and TiHA are 2.68eV and 2.82eV, respectively, while the energy gap width of the BiOCl/porous TiHA composite material is 2.50eV, which has a smaller energy gap width than that of BiOCl and TiHA, so that electrons can easily transit between energy levels, and more photogenerated electrons and holes can be generated, which is beneficial to improving the catalytic efficiency.
The BET specific surface area table test was carried out on the samples obtained in examples 4, 5, 6 and 7, and the results are shown in Table 1.
TABLE 1
As can be seen from the test data in Table 1, the bismuth oxychloride/porous titanium hydroxyapatite composite sample prepared in the example has a larger specific surface area than BiOCl, and the specific surface area of the bismuth oxychloride/porous titanium hydroxyapatite prepared in embodiment 6 is 136.47cm2G, while the specific surface area of a single BiOCl is only 11.92cm2The specific surface area of the bismuth oxychloride/porous titanium hydroxyapatite composite material is improved by compounding BiOCl and TiHA, the contact area of the bismuth oxychloride/porous titanium hydroxyapatite composite material and pollutant gas is increased beneficially, the gas is adsorbed on the surface of solid particles, and the catalytic efficiency is improved.
10g of the bismuth oxychloride/porous titanium hydroxyapatite composite material prepared in the embodiments 1-7 of the invention is fully ground, added into 100g of acrylic acid aqueous emulsion, and stirred for 72 hours at the speed of 900r/min of 700-. And adding assistants such as a leveling agent, a dispersing agent, a defoaming agent and the like, and fully stirring to ensure that the water-soluble interior wall coating reaches the standard (JC/T423-91). Uniformly coating the paint on a glass plate, naturally drying, and adding 2mg/m of the paint3In a closed transparent glass box for acetaldehyde gas, under the irradiation of a simulated fluorescent lamp, the removal rate of acetaldehyde after 24 hours is measured; the prepared bismuth oxychloride/porous titanium hydroxyapatiteThe composite material was directly added to a 0.01 mol/L acetaldehyde solution, and the removal efficiency of acetaldehyde after 120min was measured under irradiation of a 300W xenon lamp, and the results are shown in Table 2.
TABLE 2
According to test results, the degradation rate of the bismuth oxychloride/porous titanium hydroxyapatite photocatalyst on acetaldehyde solution is 67-74%, and the degradation effect on acetaldehyde gas is above 84% and can reach 88.4% at most. The results show that the samples obtained by the invention can degrade acetaldehyde in gas and can degrade acetaldehyde in solution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A bismuth oxyhalide/porous titanium hydroxyapatite composite material is characterized in that: the chemical formula of the porous titanium hydroxyapatite is TixCa(5-x)(PO4)(3+2x/3)(OH), x is more than or equal to 1 and less than 5, the porous titanium hydroxyapatite has a honeycomb porous structure, the average pore diameter is 8-12nm, and the specific surface area is 50-150cm2(ii)/g; the bismuth oxyhalide is enriched on the surface and in the pore channel structure of the porous titanium hydroxyapatite.
2. The method for preparing bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 1, characterized in that: the preparation method at least comprises the following steps:
step 1, adding metal halide into a bismuth salt solution, reacting at constant temperature, and after the reaction is finished, purifying and drying to obtain bismuth oxyhalide;
step 2, preparing porous microspheres CaCO3Dispersing the template powder and the bismuth oxyhalide obtained in the step (1) into water to obtain a suspension;
step 3, adding a titanium source into the suspension, and uniformly dispersing;
step 4, dripping a monohydrogen phosphate solution into the suspension, adjusting the pH value to 9-11 by using a pH regulator, and reacting at constant temperature;
and 5, after the reaction is finished, purifying and drying to obtain a product.
3. The method for preparing a bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, characterized in that: the metal halide in the step 1 is at least one of metal chloride, metal iodide and metal bromide; and/or
The bismuth salt in the step 1 is bismuth nitrate pentahydrate or bismuth sulfate.
4. The method for preparing a bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, characterized in that: the metal halide in the step 1 is sodium halide or potassium halide.
5. The method for preparing a bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, characterized in that: bi in the bismuth salt solution in the step 13+Has a concentration of 0.005 to 0.5 mol/L, and/or
In the step 1, metal halide is added into the mixed solution obtained from the bismuth salt solution, and halogen ions X-And Bi3+The molar ratio of (A) to (B) is 1-1.5: 1; and/or
The concentration of the bismuth oxyhalide in the suspension in the step 2 is 0.005-0.5 mol/L, and the porous microspheres are CaCO3Concentration: the molar ratio of the concentration of bismuth oxyhalide is 1: 1-10; and/or
The concentration of the dispersed titanium source in the step 3 is 0.001-0.1 mol/L, and/or
The concentration of the monohydrogen phosphate solution in the step 4 is 0.01-0.1 mol/L.
6. The method for preparing a bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, characterized in that: the constant-temperature reaction in the step 1 is carried out for 2.5-3.5 h at 70-90 ℃; and/or
The constant temperature reaction in the step 4 is carried out for 1-3 h at the temperature of 60-80 ℃.
7. The method for preparing a bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, characterized in that: the drying treatment in the step 1 is drying at the temperature of 75-85 ℃ for 10-14 h; and/or
And the drying treatment in the step 5 is drying at the temperature of 75-85 ℃ for 10-14 h.
8. The method for preparing a bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, characterized in that: the purification in the step 1 is to wash the solution by deionized water or absolute ethyl alcohol until the washing solution does not contain halogen ions; and/or
And the purification in the step 5 is to wash the mixture by using deionized water or absolute ethyl alcohol until the pH value of the washing liquid is 6.5-7.5, and then wash the mixture for 2-4 times.
9. The method for preparing bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 2, wherein the dropping rate in the step 4 is 1-3 m L/min, and/or
And the pH regulator in the step 4 is ammonia water or sodium hydroxide.
10. The bismuth oxyhalide/porous titanium hydroxyapatite composite material according to claim 1 or the bismuth oxyhalide/porous titanium hydroxyapatite composite material obtained by the method according to any one of claims 2 to 9 is applied as a photocatalyst in the field of photocatalytic environment-friendly coatings.
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