CN112547100B - Silver/bismuth oxyhalide composite photocatalyst and preparation method and application thereof - Google Patents
Silver/bismuth oxyhalide composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN112547100B CN112547100B CN202011543717.2A CN202011543717A CN112547100B CN 112547100 B CN112547100 B CN 112547100B CN 202011543717 A CN202011543717 A CN 202011543717A CN 112547100 B CN112547100 B CN 112547100B
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 89
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 60
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 239000004332 silver Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006722 reduction reaction Methods 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910052691 Erbium Inorganic materials 0.000 claims description 187
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 143
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 97
- 238000011068 loading method Methods 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910016295 BiOF Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 23
- -1 rare earth ions Chemical class 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 18
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 22
- 238000006731 degradation reaction Methods 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- 238000001878 scanning electron micrograph Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 18
- 229940012189 methyl orange Drugs 0.000 description 18
- 238000001027 hydrothermal synthesis Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 14
- 239000003814 drug Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229940043267 rhodamine b Drugs 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000004098 Tetracycline Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229960002180 tetracycline Drugs 0.000 description 7
- 229930101283 tetracycline Natural products 0.000 description 7
- 235000019364 tetracycline Nutrition 0.000 description 7
- 150000003522 tetracyclines Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 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 6
- 238000011049 filling Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000004729 solvothermal method Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229940073609 bismuth oxychloride Drugs 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a silver/bismuth oxyhalide composite photocatalyst as well as a preparation method and application thereof, belonging to the technical field of semiconductor photocatalytic materials. Firstly, Bi is addedmOpXq:nRe、Ag(NO3)3Mixing with water to obtain a mixed solution; and then carrying out reduction reaction on the mixed solution under a near-infrared light source to obtain the silver/bismuth oxyhalide composite photocatalyst. According to the method, the rare earth ions are used for absorbing near infrared light to generate electrons, so that Ag nano particles are reduced, a reducing agent is not used in the method, and the influence of the reducing agent on the activity of a catalyst is avoided; bismuth oxyhalide substrate Bi for use in the present inventionmOpXqnRe is not limited to Bi having a non-polyhedral structure or a polyhedral structuremOpXqnRe can also be used for synthesizing the silver/bismuth oxyhalide composite photocatalyst by using the method, so that the method greatly expands the raw material range of the bismuth oxyhalide substrate.
Description
Technical Field
The invention relates to the technical field of semiconductor photocatalytic materials, in particular to a silver/bismuth oxyhalide composite photocatalyst as well as a preparation method and application thereof.
Background
In recent years, semiconductor materials have attracted attention because of their unique optical and physicochemical properties, and have a wide application prospect in the fields of photocatalysis and energy.
Bismuth oxyhalide is a new semiconductor material, belonging to V-VI-VII ternary compound semiconductor, and is made up by using [ Bi2O2]2+The layered structure formed by alternately arranging the layer and the double-layer halogen atoms has a unique electronic structure, large specific surface area and excellent optical and physicochemical properties, and is considered as a new generation of most effective and environment-friendly photocatalytic materials. Bismuth oxyhalides, however, have limited solar energy utilization and produce photogenerated electricityThe compound probability of the photon and the cavity is still high in the process of transferring, and the photocatalytic efficiency is greatly reduced. In recent years, modification of photocatalytic materials by noble metals has attracted much attention. The electron trap effect and the Local Surface Plasmon Resonance (LSPR) effect of Ag can effectively increase the absorption of visible light and promote electron-hole separation. However, the prior art scheme requires the use of a reducing agent, such as sodium borohydride (NaBH), when Ag is supported on the surface of bismuth oxyhalide4) Potassium borohydride (KBH)4) Sodium citrate, these reducing agents generate free radicals which adversely affect the catalytic activity of the catalyst.
Disclosure of Invention
In view of the above, the present invention aims to provide a silver/bismuth oxyhalide composite photocatalyst, and a preparation method and an application thereof. The method provided by the invention does not use a reducing agent, and the obtained catalyst has high catalytic activity; and the bismuth oxyhalide substrate used is not limited to non-polyhedral structures of bismuth oxyhalide.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
a method for preparing a silver/bismuth oxyhalide composite photocatalyst by near-infrared light comprises the following steps:
(1) the chemical composition is BimOpXqnRe rare earth ion doped bismuth oxyhalide, Ag (NO)3)3Mixing with water to obtain a mixed solution; the BimOpXqnRe, wherein m is 1, 2, 3, 4, 5, 7, 12 or 24, n is 0.1-40%, p is 1, 3, 4, 5, 7, 11, 16 or 31, q is 1, 2, 3, 5 or 10, Re is one or more of rare earth ions, and X is halogen;
(2) and carrying out reduction reaction on the mixed solution under a near-infrared light source to obtain the silver/bismuth oxyhalide composite photocatalyst.
Preferably, said BimOpXqnRe has a polyhedral structure.
Preferably, said BimOpXqIs BiOF, BiOCl, BiOBr, BiOI, Bi3O4Cl、Bi12O5Cl16、Bi24O10Cl31、Bi3O4Br or Bi12O5Br16。
Preferably, said BimOpXqnRe and Ag (NO)3)3The mass ratio of (A) to (B) is 1: 0.001-0.3.
Preferably, the wavelength of the near-infrared light source is 750-2500 nm.
Preferably, the temperature of the reduction reaction is 20-30 ℃ and the time is 1-15 h.
The invention provides a silver/bismuth oxyhalide composite photocatalyst obtained by the method, which comprises rare earth ion-doped bismuth oxyhalide and Ag loaded on the surface of the rare earth ion-doped bismuth oxyhalide.
Preferably, the loading amount of the Ag is 0.1-30%.
The invention provides application of the silver/bismuth oxyhalide composite photocatalyst in photocatalytic degradation of organic pollutants.
Preferably, the organic contaminants comprise organic dyes and/or organic pharmaceuticals.
The invention provides a method for preparing a silver/bismuth oxyhalide composite photocatalyst by near-infrared lightmOpXq:nRe、Ag(NO3)3Mixing with water to obtain a mixed solution; and then carrying out reduction reaction on the mixed solution under a near-infrared light source to obtain the silver/bismuth oxyhalide composite photocatalyst. According to the method, electrons are generated by absorption of the rare earth ions to near infrared light, so that Ag nano particles are reduced, free reducing agents cannot be generated, and the influence of the reducing agents on the activity of the catalyst is avoided; bismuth oxyhalide substrate Bi for use in the present inventionmOpXqnRe is not limited to Bi having a non-polyhedral structure or a polyhedral structuremOpXqnRe can also be used for synthesizing the silver/bismuth oxyhalide composite photocatalyst by using the method, so that the method greatly expands the raw material range of the bismuth oxyhalide substrate. Meanwhile, the method provided by the invention is simple to operate, low in cost and easy to realize industrial mass production.
The invention provides a silver/bismuth oxyhalide composite photocatalyst prepared based on the method. The catalyst has high catalytic activity when being used for photocatalytic degradation of organic wastewater. The results of the examples show that the degradation rate of methyl orange can reach 96% when the silver/bismuth oxyhalide composite photocatalyst provided by the invention is used for photocatalytic degradation of methyl orange, and the degradation rate of rhodamine can reach 97% when rhodamine is photocatalytic degradation.
Drawings
FIG. 1 is an X-ray diffraction pattern of BiOCl: 10% Er and Ag/BiOCl: 10% Er samples;
FIG. 2 is a graph of the UV-vis absorption spectra of BiOCl: 10% Er and Ag/BiOCl: 10% Er samples;
FIG. 3 is a scanning electron microscope spectrum of BiOCl 10% Er and Ag/BiOCl 10% Er samples;
FIG. 4 is a graph of the catalytic degradation of methyl orange by BiOCl: 10% Er and Ag/BiOCl: 10% Er samples under ultraviolet-visible-near infrared light;
FIG. 5 is an X-ray diffraction pattern of a sample of BiOBr: 5% Yb, 5% Er and Ag/BiOBr: 5% Yb, 5% Er;
FIG. 6 is a UV-vis absorption spectrum of BiOBr: 5% Yb, 5% Er and Ag/BiOBr: 5% Yb, 5% Er samples;
FIG. 7 is a Scanning Electron Microscope (SEM) spectrum of BiOBr: 5% Yb, 5% Er and Ag/BiOBr: 5% Yb, 5% Er samples;
FIG. 8 is a catalytic degradation spectrum of a BiOBr of 5% Yb, 5% Er and Ag/BiOBr of 5% Yb, 5% Er sample on rhodamine B under ultraviolet-visible-near infrared light;
FIG. 9 shows Bi7F11O55% Er and Ag/Bi7F11O5An X-ray diffraction spectrum of a 5 percent Er sample;
FIG. 10 shows Bi7F11 O 55% Er and Ag/Bi7F11O55% Er sample UV-vis absorption spectrogram;
FIG. 11 shows Bi7F11O55% Er and Ag/Bi7F11O5Scanning electron microscope atlas of 5% Er sample;
FIG. 12 shows Bi7F11O55% Er and Ag/Bi7F11O55% Er sample in ultravioletSee-catalytic degradation pattern of methyl orange under near infrared light.
FIG. 13 is an X-ray diffraction pattern of polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er samples;
FIG. 14 is a plot of UV-vis absorption spectra for polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er samples;
FIG. 15 shows scanning electron micrographs of polyhedral BiOCl 4% Er and Ag/polyhedral BiOCl 4% Er;
FIG. 16 is a graph of the catalytic degradation profile of polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er samples for methyl orange under UV-visible-near infrared light;
FIG. 17 is an X-ray diffraction pattern of polyhedral BiOCl: 10% Yb, 2% Er and Ag/polyhedral BiOCl: 10% Yb, 2% Er samples;
FIG. 18 is a graph of UV-vis absorption spectra for polyhedral BiOCl: 10% Yb, 2% Er and Ag/polyhedral BiOCl: 10% Yb, 2% Er samples;
FIG. 19 is a scanning electron microscope micrograph of polyhedral BiOCl: 10% Yb, 2% Er and Ag/polyhedral BiOCl: 10% Yb, 2% Er samples;
FIG. 20 is a graph showing the catalytic degradation of rhodamine B by a polyhedral BiOCl sample of 10% Yb, 2% Er and an Ag/polyhedral BiOCl sample of 10% Yb, 2% Er under ultraviolet-visible-near infrared light;
FIG. 21 is an X-ray diffraction pattern of BiOCl: 5% Yb, 3% Er and Ag/BiOCl: 5% Yb, 3% Er samples;
FIG. 22 is a graph of the UV-vis absorption spectra of BiOCl: 5% Yb, 3% Er and Ag/BiOCl: 5% Yb, 3% Er samples;
FIG. 23 is a scanning electron microscope spectrum of BiOCl: 5% Yb, 3% Er and Ag/BiOCl: 5% Yb, 3% Er samples;
FIG. 24 is a graph of the catalytic degradation profile of a BiOCl 5% Yb, 3% Er and Ag/BiOCl 5% Yb, 3% Er sample for tetracycline under UV-visible-near infrared light.
Detailed Description
The invention provides a method for preparing a silver/bismuth oxyhalide composite photocatalyst by near-infrared light, which comprises the following steps:
(1) the chemical composition is BimOpXqnRe rare earth ion doped bismuth oxyhalide, Ag (NO)3)3Mixing with water to obtain a mixed solution; the BimOpXqnRe, wherein m is 1, 2, 3, 4, 5, 7, 12 or 24, n is 0.1-40%, p is 1, 3, 4, 5, 7, 11, 16 or 31, q is 1, 2, 3, 5 or 10, Re is one or more of rare earth ions, and X is halogen;
(2) and carrying out reduction reaction on the mixed solution under a near-infrared light source to obtain the silver/bismuth oxyhalide composite photocatalyst.
The invention makes the chemical composition of BimOpXqnRe rare earth ion doped bismuth oxyhalide, Ag (NO)3)3And mixing with water to obtain a mixed solution. In the invention, Re is preferably one or more of Tb, Ce, Nd, Dy, Sm, Pr, Lu, Eu, Tm, Yb, Gd, Ho and Er, and X is preferably F, Cl, Br or I. In the present invention, the rare earth ion has a valence of + 3. In the present invention, the BimOpXqPreferably BiOF, BiOCl, BiOBr, BiOI, Bi3O4Cl、Bi12O5Cl16、Bi24O10Cl31、Bi7F11O5、Bi3O4Br or Bi12O5Br16。
As a specific example of the present invention, the BimOpXqnRe comprises BiOCl 10% Er, BiOBr 5% Yb 5% Er and Bi7F11 O 55% Er, 4% BiOCl, 10% Yb 2% BiOCl or 5% Yb 3% BiOCl.
In the present invention, the BimOpXqnRe has a polyhedral structure or a non-polyhedral structure.
In the present invention, the BimOpXqnRe is preferably BimOpXqnRe powder, the BimOpXqThe nRe powder preferably has a nano-scale particle size, and a thickness of 20 to 3000nm, more preferably 100 to 1000nm, and even more preferably 200 to 500 nm. In the present invention, when said BimOpXqWhen nRe has a polyhedral structure, the BimOpXqThe preferred thickness of the nRe powder is 500-3000nm, more preferably 1000 to 2000 nm.
The invention is directed to the BimOpXqThe source of nRe is not particularly limited, and Bi commercially available in the art is usedmOpXqEither nRe or self-prepared. When preparing the Bi by itselfmOpXqWhen nRe is present, the Bi ismOpXqPreferably, nRe is prepared by a hydrothermal method, a solvothermal method or a solid-phase sintering method.
In the present invention, the hydrothermal process preferably comprises the steps of:
(1) mixing a bismuth source, an oxygen-containing rare earth ion raw material, a halogen ion raw material and water, adjusting the pH value to 1-8, and carrying out hydrothermal reaction to obtain a hydrothermal reaction solution;
(2) carrying out solid-liquid separation on the hydrothermal reaction solution, and sequentially washing, drying and carrying out heat treatment on the obtained solid to obtain BimOpXq:nRe。
In the present invention, the bismuth source is preferably Bi (NO)3)3.5H2O、Bi2O3Or BiCl3The oxygen-containing rare earth ion raw material is nitrate of rare earth or halide of rare earth, and the halogen ion raw material is NaCl, NaBr, NaI, NaF, KCl, KBr, KI or NH4Cl、NH4Br or NH4F. The invention has no special requirement on the dosage of the water, and the raw materials can be dissolved. The invention does not require any particular mixing means, as is known to those skilled in the art, such as stirring. In the invention, the pH value regulator used for regulating the pH value is preferably one or more of NaOH, KOH and ammonia water.
The hydrothermal reaction is preferably carried out in a hydrothermal kettle with a polytetrafluoroethylene lining, and the filling degree of the hydrothermal kettle is preferably 0.5-0.8. In the invention, the temperature of the hydrothermal reaction is preferably 140-180 ℃, and more preferably 150-160 ℃; the time of the hydrothermal reaction is preferably 3-250 h. In the invention, when the temperature of the hydrothermal reaction is 3-72 h (not including 72h), Bi is obtainedmOpXqThe nRe powder is of a non-polyhedral structure, and when the temperature of the hydrothermal reaction is 72-250 h, the Bi is obtainedmOpXqThe nRe powder has a multi-face structure. In the invention, the Bi with a non-polyhedral structure prepared by the hydrothermal methodmOpXqThe nRe thickness is preferably 20 to 200nm, more preferably 50 to 100nm, and Bi with a polyhedral structure is prepared by a hydrothermal methodmOpXqThe preferred thickness of nRe is 500 to 3000nm, and the more preferred thickness is 1000 to 2000 nm.
The present invention has no special requirements on the solid-liquid separation mode, and the solid-liquid separation mode known to those skilled in the art can be used, such as filtration. In the present invention, the washing manner is preferably three times of each washing with deionized water and absolute ethyl alcohol. In the invention, the drying temperature is preferably 50-90 ℃, more preferably 60 ℃, the drying time is not specially required, and the obtained solid is dried to constant weight. In the invention, the temperature of the heat treatment is preferably 300-500 ℃, more preferably 300-450 ℃, and the time is preferably 0.5-3 h, more preferably 1-2 h. According to the invention, the crystallinity of the sample can be improved through the heat treatment.
In the present invention, the solvothermal method preferably comprises the steps of:
(a) mixing a bismuth source, an oxygen-containing rare earth ion raw material, a halogen ion raw material and an alcohol solvent, adjusting the pH value to 1-8, and carrying out hydrothermal reaction to obtain a hydrothermal reaction solution;
(b) carrying out solid-liquid separation on the hydrothermal reaction solution, and sequentially washing, drying and carrying out heat treatment on the obtained solid to obtain BimOpXq:nRe。
In the present invention, the alcoholic solvent is preferably mannitol, isopropanol, ethylene glycol or ethanol. In the present invention, the solvothermal method and the hydrothermal method are different only in the solvent, and the rest of the operations are the same, and are not described herein again. In the invention, when the temperature of the solvothermal reaction is 3-72 h (not including 72h), the Bi obtained ismOpXqThe nRe powder is of a non-polyhedral structure, and when the solvent is heated and reactedWhen the temperature is 72-250 h, the BimOpXq: nRe powder is of a multi-face structure. In the invention, the thickness of the BimOpXq: nRe of the non-polyhedral structure prepared by the solvothermal method is preferably 20-300 nm, more preferably 50-200 nm, and the thickness of the BimOpXq: nRe of the polyhedral structure prepared by the solvothermal method is preferably 500-3000 nm, more preferably 1000-2000 nm.
In the present invention, the solid-phase sintering method preferably includes the steps of:
mixing a bismuth source, an oxygen-containing rare earth ion raw material and a halogen ion raw material, and sequentially grinding and solid-phase sintering to obtain BimOpXqnRe. In the invention, the grinding mode is preferably that the required raw materials are weighed in an agate mortar, absolute ethyl alcohol is adopted as a grinding aid to be fully mixed, the mixture is transferred to an alumina crucible, and the particle size of the mixed material after grinding is preferably micron-sized. In the invention, the temperature of the solid-phase sintering is preferably 300-500 ℃, and the time is preferably 0.5-3 h. In the present invention, Bi obtained by the solid-phase sintering methodmOpXqThe nRe thickness is preferably 100 to 500nm, more preferably 200 to 400 nm.
The invention is directed to the BimOpXq:nRe、Ag(NO3)3The manner of mixing with water is not particularly limited, and mixing means known to those skilled in the art, such as stirring, may be used. In the invention, Bi is preferably firstly selectedmOpXqMixing nRe with water to obtain BimOpXqThe aqueous solution of nRe, and then the BimOpXqMixing the nRe aqueous solution with water. In the present invention, the BimOpXqnRe and Ag (NO)3)3The mass ratio of (A) to (B) is preferably 1:0.001 to 0.3, more preferably 1:0.05 to 0.2, and still more preferably 1:0.1 to 0.15. In the present invention, the BimOpXqThe mass ratio of nRe to water is preferably 4-8 mg: 1mL, more preferably 5-6 mg: 1 mL.
And after the mixed solution is obtained, carrying out reduction reaction on the mixed solution under a near-infrared light source to obtain the silver/bismuth oxyhalide composite photocatalyst. In the invention, the wavelength of the near-infrared light source is preferably 750-2500 nm, and more preferably 1000-2000 nm; in the invention, the power of the device for providing the near-infrared light source is preferably 0.001-100W, and more preferably 0.1-10W. In the invention, the reduction temperature is preferably room temperature, and the time is preferably 1-15 h, and more preferably 5-10 h.
After the reduction reaction, the present invention also preferably includes post-treating the obtained reduction reaction solution, and the post-treating preferably includes the steps of:
and sequentially carrying out solid-liquid separation, washing and drying on the reduction reaction liquid.
The present invention has no special requirement on the solid-liquid separation mode, and the solid-liquid separation mode known to those skilled in the art can be used, such as filtration. In the invention, the washing is preferably carried out 3-6 times by using deionized water and absolute ethyl alcohol respectively. In the invention, the drying temperature is preferably 50-90 ℃, more preferably 60-80 ℃, and the time is preferably 8-12 h.
The invention provides a silver/bismuth oxyhalide composite photocatalyst prepared by the preparation method, which comprises rare earth ion-doped bismuth oxyhalide and Ag loaded on the surface of the rare earth ion-doped bismuth oxyhalide, wherein the loading capacity of the Ag is preferably 0.1-30%, more preferably 1-20%, and further preferably 2-15%. In the invention, the chemical formula of the silver/bismuth oxyhalide composite photocatalyst is Ag/BimOpXqnRe, wherein m is 1, 2, 3, 4, 5, 7, 12 or 24, n is 0.001-0.4, p is 1, 3, 4, 5, 7, 11, 16 or 31, q is 1, 2, 3, 5 or 10, Re is one or more of Tb, Ce, Nd, Dy, Sm, Pr, Lu, Eu, Tm, Yb, Gd, Ho and Er, and X is F, Cl, Br or I. As a specific embodiment of the invention, the silver/bismuth oxyhalide composite photocatalyst comprises Ag/BiOCl of 10% Er, Ag/BiOBr of 5% Yb 5% Er and Ag/Bi7F11O55% Er, 4% Er, 10% Yb 2% Er or 5% Yb 3% Er.
In the inventionIn (b) the above BimOpXqThe mass ratio of nRe to Ag is preferably 1: 0.001-0.3, more preferably 1: 0.01-0.2, and still more preferably 1: 0.02-0.15.
The invention provides application of the silver/bismuth oxyhalide composite photocatalyst in photocatalytic degradation of organic pollutants. In the present invention, the organic contaminants include organic dyes and/or organic pharmaceuticals; the organic dye is preferably one or more of methyl orange, rhodamine B, methylene blue and methyl blue; the organic medicine is preferably one or more of bisphenol A, tetracycline and phenol.
The silver/bismuth oxyhalide composite photocatalyst provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) According to the Bi ion: er ions: molar ratio of Cl ion 0.9: 0.1: 1, with Bi (NO)3)3·5H2O、Er2(NO3)3NaCl is taken as a raw material, and the medicine is weighed, dissolved in deionized water and stirred uniformly; adjusting the pH value to 6 by using 1mol/L NaOH solution, stirring for 0.5 hour, transferring into a hydrothermal kettle with a polytetrafluoroethylene lining, wherein the filling degree is 0.8, heating to 140 ℃, and carrying out hydrothermal reaction for 12 hours; after the reaction is finished and the temperature is reduced to room temperature, taking out the reaction kettle, standing to remove supernatant, washing the precipitate with deionized water and absolute ethyl alcohol respectively for three times in sequence, drying at 60 ℃, and then carrying out heat treatment at 450 ℃ for 2.5 hours to obtain BiOCl 10% Er powder;
(2) dissolving 300mgBiOCl 10% Er powder in 60mL water, stirring at room temperature for 30min to obtain BiOCl 10% Er water solution, adding 0.0190g Ag (NO)3)3Adding into BiOCl 10% Er water solution to obtain mixed solution, placing the mixed solution under a simulated fluorescent xenon lamp light source (lambda) with power of 350W>750nm) light for 5h to obtain a reduction reaction liquid, filtering the reduction reaction liquid, washing the precipitate for 3 times respectively by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the silver/bismuth oxyhalide composite photocatalyst Ag/BiOCl of 10% Er, wherein the Ag load is4wt％。
The X-ray diffraction patterns of the obtained BiOCl 10% Er and Ag/BiOCl 10% Er are shown in figure 1. As can be seen from FIG. 1, the crystal form of Ag/BiOCl: 10% Er still maintains tetragonal BiOCl crystals, compared with the Ag-unloaded nanoparticles.
The UV-vis absorption spectra of the resulting BiOCl: 10% Er and Ag/BiOCl: 10% Er are shown in FIG. 2. As can be seen from FIG. 2, the Ag/BiOCl 10% Er increased the absorption of visible and near infrared light compared to BiOCl 10% Er.
The scanning electron micrographs of BiOCl: 10% Er and Ag/BiOCl: 10% Er obtained are shown in FIG. 3, (a) is the scanning electron micrograph of BiOCl: 10% Er, and (b) is the scanning electron micrograph of Ag/BiOCl: 10% Er. As can be seen from FIG. 3, the samples are all in a nano-sheet shape, the surface of BiOCl 10% Er is smooth, and Ag particles loaded by Ag/BiOCl 10% Er are mainly arranged on the side surface of the BiOCl 10% Er nano-sheet.
The catalytic degradation conditions of the obtained BiOCl 10% Er and Ag/BiOCl 10% Er on methyl orange under ultraviolet-visible-near infrared light are shown in figure 4, wherein the volume of the methyl orange solution is 50mL, the initial concentration of the methyl orange is 10mg/L, the dosage of the catalyst is 50mg, and the catalytic degradation is carried out at room temperature. As can be seen from fig. 4, methyl orange (Blank) did not degrade without the catalyst after 60 minutes of light; in the presence of the catalyst, the degradation of BiOCl and 10% Er of methyl orange is 72%, and the degradation of Ag/BiOCl and 10% Er is 96%. This shows that the catalytic performance of Ag/BiOCl 10% Er is obviously improved after Ag is loaded.
Example 2
(1) According to the Bi ion: yb ion: er ions: molar ratio of Br ion 0.9: 0.05: 0.05: 1, with Bi (NO)3)3·5H2O、Yb2(NO3)3、Er2(NO3)3Weighing medicine by taking NaBr as raw materials, dissolving the medicine in 0.1mol/L mannitol, stirring for 0.5 hour, transferring the medicine into a hydrothermal kettle with a polytetrafluoroethylene lining, keeping the filling degree at 0.8, heating to 160 ℃, and keeping the temperature for 18 hours; cooling to room temperature after the reaction, taking out the reaction kettle, standing to remove supernatant, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and cooling to 60 deg.CDrying, and then carrying out heat treatment for 2 hours at the temperature of 450 ℃ to obtain BiOBr powder of 5% Yb and 5% Er powder;
(2) dissolving 400mg of BiOBr 5% Yb and 5% Er powder in 80mL of water, stirring for 30min at room temperature to obtain a BiOBr 5% Yb and 5% Er aqueous solution, adding 0.0190g of Ag (NO3)3 into the BiOBr 5% Yb and 5% Er aqueous solution to obtain a mixed solution, placing the mixed solution in a 980nm laser with the power of 2W for illumination for 9h to obtain a reduction reaction solution, filtering the reduction reaction solution, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 60 ℃ to obtain the silver/bismuth oxyhalide composite photocatalyst Ag/BiOBr 5% Yb and 5% Er, wherein the Ag load is 3 wt%.
The X-ray diffraction patterns of the obtained BiOBr of 5% Yb, 5% Er and Ag/BiOBr of 5% Yb and 5% Er are shown in figure 5. It can be seen from fig. 5 that the crystal form of Ag/BiOBr: 5% Yb, 5% Er still remains tetragonal BiOBr crystals compared to the unsupported Ag nanoparticles.
The UV-vis absorption spectra of the resulting BiOBr of 5% Yb, 5% Er and Ag/BiOBr of 5% Yb, 5% Er are shown in FIG. 6. As can be seen in FIG. 6, the Ag/BiOBr: 5% Yb, 5% Er sample increased the absorption of visible and near infrared light compared to the BiOBr: 5% Yb, 5% Er samples.
The scanning electron micrographs of BiOBr 5% Yb and Er 5% and Ag/BiOBr 5% Yb and Er 5% are shown in FIG. 7, (a) is the scanning electron micrograph of BiOBr 5% Yb and Er 5%, and (b) is the scanning electron micrograph of Ag/BiOBr 5% Yb and Er 5%. As can be seen from FIG. 7, the samples are all nano-flake, the BiOBr is 5% Yb, the surface of the Er is smooth, and Ag/BiOBr is 5% Yb, 5% Er-loaded Ag particles are mainly on the side surface of the sample.
The catalytic degradation of the obtained BiOBr, namely 5% Yb, 5% Er and Ag/BiOBr, namely 5% Yb and 5% Er to rhodamine B under ultraviolet-visible-near infrared light is shown in a figure 8, wherein the volume of rhodamine B solution is 50mL, the initial concentration of rhodamine B is 10mg/L, the dosage of a catalyst is 50mg, and the catalytic degradation is carried out at room temperature. As can be seen from FIG. 8, after 50 minutes of light exposure, rhodamine B (blank) did not degrade without the catalyst; under the condition of a catalyst, BiOBr is 5% of Yb, 5% of Er degrades rhodamine B by 75%, Ag/BiOBr is 5% of Yb, and 5% of Er degrades by 97%. After Ag is loaded, the Ag/BiOBr is 5% Yb, and the catalytic performance of 5% Er is obviously improved.
Example 3
(1) According to the Bi ion: er ions: molar ratio of F ion 0.95: 0.05: 3 with Bi (NO)3)3·5H2O、Er2(NO3)3、NH4F is taken as a raw material, medicine is weighed, dissolved in ethylene glycol, stirred uniformly, the pH value is adjusted to 1 by 0.2mol/LNaOH solution, stirred for 0.5 hour, then transferred into a hydrothermal kettle with a polytetrafluoroethylene lining, the filling degree is 0.8, then the temperature is raised to 140 ℃, and the temperature is kept for 18 hours; after the reaction is finished and the temperature is reduced to room temperature, the reaction kettle is taken out, the supernatant is removed by standing, the precipitate is respectively washed by deionized water and absolute ethyl alcohol for three times in sequence, dried at 60 ℃, and then thermally treated for 2 hours at 450 ℃ to obtain Bi7F11O55% of Er powder;
(2) taking 400mgBi7F11O5Dissolving 5% Er powder in 80mL water, stirring at room temperature for 30min to obtain Bi7F11O55% Er in water, 0.0380gAg (NO)3)3Is added to Bi7F11O5Obtaining a mixed solution in a 5% Er aqueous solution, placing the mixed solution under a 808nm laser with the power of 5W for illumination for 7h to obtain a reduction reaction solution, filtering the reduction reaction solution, respectively cleaning precipitates for 3 times by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the silver/bismuth oxyhalide composite photocatalyst Ag/Bi7F11O55 percent of Er, wherein the Ag loading is 6 weight percent.
The obtained Bi7F11O55% Er and Ag/Bi7F11O5An X-ray diffraction pattern of 5% Er is shown in FIG. 9. As can be seen from FIG. 9, Ag/Bi compares to the unsupported Ag nanoparticles7F11O5Bi with 5 percent of Er still maintaining tetragonal phase7F11O5And (4) crystals.
The obtained Bi7F11O55% Er and Ag/Bi7F11O55% Er the UV-vis absorption spectrum is shown in FIG. 10, and it can be seen from FIG. 10 that Ag/Bi7F11O55% Er sample and Bi7F11O55% Er increases the absorption of visible and near infrared light.
The obtained Bi7F11O55% Er and Ag/Bi7F11O5FIG. 11 shows a scanning electron micrograph of 5% Er, in which (a) in FIG. 11 shows Bi7F11O55% Er as a scanning electron micrograph, and (b) Ag/Bi7F11O5Scanning electron micrograph of 5% Er. As can be seen from FIG. 11, the samples are all in the form of nanosheets, Bi7F11O55% Er with smooth surface and Ag/Bi7F11O55% Er loaded Ag particles were predominantly on the sample side.
The obtained Bi7F11O55% Er and Ag/Bi7F11O5The catalytic degradation of methyl orange by 5 percent Er under ultraviolet-visible-near infrared light is shown in figure 12, wherein the volume of a methyl orange solution is 50mL, the initial concentration of the methyl orange is 10mg/L, the dosage of a catalyst is 50mg, the catalytic degradation is carried out at room temperature, and as can be seen from figure 12, after 50 minutes of illumination, the methyl orange (Blank) is not degraded under the condition of no catalyst; in the presence of a catalyst, Bi7F11O55% Er degrades methyl orange by 61%, Ag/Bi7F11O55% Er degrades by 75%. After loading Ag, Ag/Bi7F11O5The catalytic performance of 5 percent Er is obviously improved.
Example 4
(1) According to the Bi ion: er ions: molar ratio of Cl ion 0.96: 0.04: 1, with Bi (NO)3)3·5H2O、Er2(NO3)3Weighing the medicines by taking KCl as raw materials, dissolving the medicines in deionized water, stirring for 1 hour, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, wherein the filling degree is 0.7, heating to 160 ℃, and preserving heat for 200 hours; cooling to room temperature after the reaction, taking out the reaction kettle, standing to remove supernatant, washing the precipitate with deionized water and anhydrous ethanol for 3 times, drying at 70 deg.C, and processing at 450 deg.CPerforming heat treatment for 1.5 hours to obtain an octadecyl body of BiOCl: 4% Er;
(2) dissolving 300mg of polyhedral BiOCl and 4% Er powder in 60mL of water, stirring at room temperature for 40min to obtain BiOCl and 4% Er aqueous solution, and adding 0.0190g Ag (NO)3)3Adding into BiOCl 4% Er water solution to obtain mixed solution, and placing the mixed solution in a simulated fluorescent xenon lamp light source (lambda) with power of 500W>780nm) for 5 hours to obtain a reduction reaction solution, filtering the reduction reaction solution, washing the precipitate for 4 times by using deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain the silver/bismuth oxyhalide composite photocatalyst Ag/polyhedral BiOCl: 4% Er, wherein the Ag loading is 4 wt%.
The X-ray diffraction patterns of the obtained polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er are shown in FIG. 13. As can be seen from FIG. 13, the crystal form of Ag/polyhedral BiOCl: 4% Er still maintained tetragonal BiOCl crystals compared to the unsupported Ag nanoparticles.
The UV-vis absorption spectra of the resulting polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er are shown in FIG. 14. it can be seen from FIG. 14 that the Ag/polyhedral BiOCl: 4% Er samples have increased absorption of visible and near infrared light compared to the polyhedral BiOCl: 4% Er.
The scanning electron micrographs of the resulting polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er are shown in FIG. 15, in which (a) is the scanning electron micrograph of BiOCl: 4% Er and (b) is the scanning electron micrograph of Ag/polyhedral BiOCl: 4% Er. As can be seen from FIG. 15, the polyhedral BiOCl: 4% Er had smooth surfaces, and Ag particles were loaded on each surface of the BiOCl: 4% Er by near-infrared light.
The catalytic degradation of methyl orange by the obtained polyhedral BiOCl: 4% Er and Ag/polyhedral BiOCl: 4% Er under ultraviolet-visible-near infrared light is shown in figure 16, wherein the volume of a methyl orange solution is 50mL, the initial concentration of the methyl orange is 10mg/L, the dosage of the catalyst is 50mg, the catalytic degradation is carried out at room temperature, and as can be seen from figure 16, the methyl orange (Blank) is not degraded under the condition of no catalyst after being illuminated for 50 minutes; in the presence of the catalyst, the polyhedral BiOCl (bismuth oxychloride) 4 percent Er degrades methyl orange by 71 percent, and the Ag/polyhedral BiOCl (bismuth oxychloride) 4 percent Er degrades by 85 percent. After Ag is loaded, the catalytic performance of Ag/polyhedral BiOCl: 4% Er is obviously improved.
Example 5
(1) According to the Bi ion: yb ion: er ions: molar ratio of Cl ion 0.88: 0.1: 0.02: 1, with Bi (NO)3)3·5H2O、Yb2(NO3)3、Er2(NO3)3Weighing the medicines by taking KCl as raw materials, dissolving the medicines in deionized water, stirring for 1 hour, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining, wherein the filling degree is 0.7, heating to 160 ℃, and preserving heat for 180 hours; after the temperature is reduced to room temperature after the reaction is finished, taking out the reaction kettle, standing to remove supernatant, washing the precipitate for 3 times by using deionized water and absolute ethyl alcohol in sequence, drying at 70 ℃, and then carrying out heat treatment for 1.5 hours at 450 ℃ to obtain polyhedral BiOCl (bismuth oxychloride) powder of 10 percent Yb and 2 percent Er powder;
(2) dissolving 400mg of polyhedral BiOCl of 10% Yb and 2% Er powder in 80mL of water, stirring at room temperature for 40min to obtain a BiOCl of 10% Yb and 2% Er aqueous solution, and adding 0.0317g of Ag (NO)3)3Adding the silver/bismuth oxyhalide composite photocatalyst Ag/polyhedral BiOCl 10% Yb and 2% Er into a BiOCl 10% Er aqueous solution to obtain a mixed solution, placing the mixed solution under a 808-W laser (3W) to irradiate for 8 hours to obtain a reduction reaction solution, filtering the reduction reaction solution, washing precipitates for 4 times respectively by using deionized water and absolute ethyl alcohol, and drying at 70 ℃ to obtain the silver/bismuth oxyhalide composite photocatalyst Ag/polyhedral BiOCl 10% Yb and 2% Er, wherein the Ag loading capacity is 5 wt%.
The X-ray diffraction patterns of the obtained polyhedral BiOCl of 10% Yb and 2% Er and Ag/polyhedral BiOCl of 10% Yb and 2% Er are shown in FIG. 17. It can be seen from fig. 17 that the crystal form of Ag/polyhedral BiOCl: 10% Yb, 2% Er still maintains tetragonal BiOCl crystals compared to the unsupported Ag nanoparticles.
The UV-vis absorption spectra of the resulting polyhedral BiOCl of 10% Yb, 2% Er and Ag/polyhedral BiOCl of 10% Yb, 2% Er are shown in FIG. 18. it can be seen from FIG. 18 that the Ag/polyhedral BiOCl of 10% Yb, 2% Er samples increased the absorption of visible and near infrared light compared to the polyhedral BiOCl of 10% Yb, 2% Er.
The scanning electron micrographs of the obtained polyhedral BiOCl of 10% Yb and 2% Er and Ag/polyhedral BiOCl of 10% Yb and 2% Er are shown in FIG. 19, in which (a) is the scanning electron micrograph of the polyhedral BiOCl of 10% Yb and 2% Er and (b) is the scanning electron micrograph of the Ag/polyhedral BiOCl of 10% Yb and 2% Er. As can be seen from FIG. 19, the polyhedral BiOCl is 10% Yb, 2% Er and the Ag/polyhedral BiOCl is 10% Yb, the 2% Er is polyhedral, the polyhedral BiOCl is 10% Yb, the surface of the 2% Er is smooth, and Ag particles are loaded on each surface of the BiOCl, the 10% Yb and the 2% Er through near infrared light.
The catalytic degradation of the obtained polyhedral BiOCl (bismuth oxychloride) of 10% Yb, 2% Er and Ag/polyhedral BiOCl of 10% Yb and 2% Er under ultraviolet-visible-near infrared light is shown in a figure 20, wherein the volume of a rhodamine B solution is 50mL, the initial concentration of the rhodamine B is 10mg/L, the dosage of a catalyst is 50mg, and the catalytic degradation is carried out at room temperature. As can be seen from FIG. 20, after 50 minutes of light exposure, rhodamine B (blank) did not degrade without the catalyst; under the condition of a catalyst, 10% of Yb is used for polyhedral BiOCl, 70% of rhodamine B is degraded by 2% of Er, 10% of Yb is used for Ag/BiOCl, and 82% of Er is degraded by 2% of Er. After Ag is loaded, the catalytic performance of the Ag/polyhedral BiOCl is obviously improved by 10% Yb and 2% Er.
Example 6
(1) According to the Bi ion: yb ion: er ions: molar ratio of Cl ion 0.92: 0.05: 0.03: 1, with Bi2O3、Yb2O3、Er2O3、NH4Weighing the medicine by taking Cl as a raw material, fully grinding and uniformly mixing all samples, and sintering for 3 hours at 500 ℃ to obtain BiOCl powder of 5% Yb and 3% Er powder;
(2) dissolving 400mg of BiOCl 5% Yb and 3% Er powder in 80mL of water, stirring at room temperature for 30min to obtain a BiOCl 5% Yb and 3% Er aqueous solution, and adding 0.0190g of Ag (NO)3)3Adding the silver/bismuth oxyhalide composite photocatalyst into a BiOCl 5% Yb and 3% Er aqueous solution to obtain a mixed solution, placing the mixed solution under a 980 laser (3W) to irradiate for 8h to obtain a reduction reaction solution, filtering the reduction reaction solution, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain the silver/bismuth oxyhalide composite photocatalyst Ag/BiOCl 5% Yb and 3% Er, wherein the Ag loading amount is 3 wt%.
The X-ray diffraction patterns of the obtained BiOCl of 5% Yb and 3% Er and Ag/BiOCl of 5% Yb and 3% Er are shown in FIG. 21. It can be seen from fig. 21 that the crystal form of Ag/BiOCl: 5% Yb, 3% Er still maintains tetragonal BiOCl crystals compared to the unsupported Ag nanoparticles.
The UV-vis absorption spectra of the resulting BiOCl of 5% Yb, 3% Er and Ag/BiOCl of 5% Yb, 3% Er are shown in FIG. 22. it can be seen from FIG. 22 that the Ag/BiOCl of 5% Yb, 3% Er samples increased the absorption of visible and near infrared light compared to BiOCl of 5% Yb, 3% Er.
The scanning electron micrographs of BiOCl of 5% Yb and 3% Er and Ag/BiOCl of 5% Yb and 3% Er are shown in FIG. 23, (a) is the scanning electron micrograph of BiOCl of 5% Yb and 3% Er, and (b) is the scanning electron micrograph of Ag/BiOCl of 5% Yb and 3% Er. As can be seen from FIG. 23, the surface of BiOCl of 5% Yb and the surface of 3% Er were smooth, and Ag particles were supported on the side surfaces of BiOCl of 5% Yb and 3% Er by near infrared light.
The catalytic degradation of the obtained BiOCl of 5% Yb, 3% Er and Ag/BiOCl of 5% Yb and 3% Er to tetracycline under ultraviolet-visible-near infrared light is shown in figure 24, wherein the volume of the tetracycline solution is 50mL, the initial concentration of the tetracycline is 10mg/L, the dosage of the catalyst is 50mg, and the catalytic degradation is carried out at room temperature. As can be seen in FIG. 24, after 50 minutes of light exposure, tetracycline (Blank) was not degraded without the catalyst; in the presence of a catalyst, 5% of Yb in BiOCl, 59% of tetracycline degraded by 3% of Er, 5% of Yb in Ag/BiOCl and 71% of Err degraded by 3%. After Ag is loaded, the catalytic performance of Ag/BiOCl is obviously improved by 5% Yb and 3% Er.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for preparing a silver/bismuth oxyhalide composite photocatalyst by near-infrared light comprises the following steps:
(1) the chemical composition is BimOpXqnRe rare earth ion doped bismuth oxyhalide, Ag (NO)3)3Mixing with water to obtain a mixed solution; the BimOpXqnRe with m =1, 2, 3, 4, 5, 7, 12 or 24, n =0.1% to 40%, p =1, 3, 4, 5, 7, 11, 16 or 31, q =1, 2, 3, 5 or 10, Re is a rare earth ion Er, Yb, Tm and NdOne or more, X is halogen; the BimOpXqnRe has a polyhedral structure or a non-polyhedral structure;
(2) carrying out reduction reaction on the mixed solution under a near-infrared light source to obtain a silver/bismuth oxyhalide composite photocatalyst; the wavelength of the near-infrared light source is 750-2500 nm.
2. The method of claim 1, wherein said Bi ismOpXqnRe has a polyhedral structure.
3. The method of claim 1, wherein said Bi ismOpXqIs BiOF, BiOCl, BiOBr, BiOI, Bi3O4Cl、Bi12O5Cl16、Bi24O10Cl31、Bi3O4Br or Bi12O5Br16。
4. The method of claim 1, wherein said Bi is presentmOpXqnRe and Ag (NO)3)3The mass ratio of (A) to (B) is 1: 0.001-0.3.
5. The method according to claim 1, wherein the temperature of the reduction reaction is 20-30 ℃ and the time is 1-15 h.
6. The silver/bismuth oxyhalide composite photocatalyst obtained by the method of any one of claims 1 to 5, which comprises rare earth ion-doped bismuth oxyhalide and Ag loaded on the surface of the rare earth ion-doped bismuth oxyhalide.
7. The silver/bismuth oxyhalide composite photocatalyst according to claim 6, wherein the loading amount of Ag is 0.1-30%.
8. Use of the silver/bismuth oxyhalide composite photocatalyst according to claim 6 or 7 for photocatalytic degradation of organic pollutants.
9. Use according to claim 8, wherein the organic contaminant is an organic dye and/or an organic pharmaceutical.
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