CN111036246A - Composite photocatalytic material and preparation method and application thereof - Google Patents
Composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- CN111036246A CN111036246A CN201911422453.2A CN201911422453A CN111036246A CN 111036246 A CN111036246 A CN 111036246A CN 201911422453 A CN201911422453 A CN 201911422453A CN 111036246 A CN111036246 A CN 111036246A
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- titanium dioxide
- copper
- photocatalytic material
- hydroxyapatite
- silver
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 70
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 42
- 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 claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical group C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 5
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 4
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 4
- 229960000623 carbamazepine Drugs 0.000 description 4
- 229960001680 ibuprofen Drugs 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 229940079593 drug Drugs 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 239000003433 contraceptive agent Substances 0.000 description 1
- 230000002254 contraceptive effect Effects 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
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- 239000002114 nanocomposite Substances 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—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
- 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
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
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- 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
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- 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
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Abstract
The invention relates to a composite photocatalytic material, which comprises sheet hydroxyapatite and titanium dioxide coated on the hydroxyapatite, wherein the length of the hydroxyapatite is 0.5-3 mu m, the particle size of the titanium dioxide is 10-30 nm, and copper and silver are deposited on the surface of the titanium dioxide.
Description
Technical Field
The invention relates to a composite photocatalytic material, in particular to a composite photocatalytic material which is formed by coating nano titanium dioxide on the surface of hydroxyapatite and simultaneously depositing silver and copper on the surface of the nano titanium dioxide, and belongs to the technical field of photocatalytic materials.
Background
With the rapid development of economy, the pollution of atmosphere, soil and water has become more serious, and in order to solve the above environmental problems, researchers have focused on the environmental-friendly photocatalytic technical field, and the photocatalytic material refers to a semiconductor catalyst material required for photochemical reaction under the action of light, and can be used as a photocatalytic material in the world, including various oxide sulfide semiconductors such as Titanium Dioxide, zinc oxide, tin oxide, zirconium Dioxide, cadmium sulfide, etc., wherein Titanium Dioxide (Titanium Dioxide) is a most red nano photocatalytic material in the world due to its strong oxidizing ability, stable chemical properties and no toxicity.
TiO2The crystal form, the grain size, the grain diameter, the surface state and other factors have great influence on the photocatalytic performance. The nano-particle with large surface area has good catalytic activity and selectivity due to the surface effect and the volume effect. Nano TiO 22The conduction band energy level and the valence band energy level of the quantum size effect become discrete energy levels due to the quantum size effect, the energy gap is widened, the conduction band potential becomes more negative, and the valence band potential becomes more positive, which means that the quantum size effect has stronger oxidation and reduction capabilities; and because the particle size of the nano particles is small, a photon-generated carrier is easier to migrate to the surface from the inside of the particles than coarse particles, the recombination probability of electrons and holes is obviously reduced, and the photocatalysis performance is also improved.
However, titanium dioxide has a wide band gap (anatase is 3.2eV), so that titanium dioxide only responds to ultraviolet light, the spectrum utilization range is narrow, and in addition, the electron hole is easy to rapidly recombine, so that the carrier efficiency is low, and the problems of low photon efficiency, low catalytic efficiency to be improved, difficult immobilization and difficult recovery of the catalyst and the like exist when the titanium dioxide is applied to the field of photocatalysis, so that the application of titanium dioxide in practice is limited.
In order to solve the problems of titanium dioxide, researchers modify titanium dioxide by different methods, such as ion doping, semiconductor compounding, noble metal loading, morphology crystal face regulation and the like, and mainly aim at widening the light absorption range, improving the quantum efficiency and promoting the occurrence of surface reaction. Through the deposition of the noble metal, photo-generated electrons can be effectively captured, so that the catalytic activity of the semiconductor is improved, and the deposition of the noble metal on the surface of the semiconductor usually has two functions: firstly, the method is beneficial to the effective separation of photo-generated electron-hole pairs; and secondly, the photocatalytic activity is improved by reducing the overpotential of the reduction reaction, but the noble metal is rare and expensive, so that the further practical application of the noble metal is hindered.
Hydroxyapatite has strong adsorption effect on organic pollutants, is non-toxic and harmless, and in recent years, the research on hydroxyapatite/titanium dioxide composite materials is continuously carried out, Taoda and the like wrap hydroxyapatite on the surface of titanium dioxide, so that the functions of titanium dioxide such as sterilization, deodorization and the like are improved. Then, the titanium dioxide/hydroxyapatite hollow composite microspheres are synthesized, and the titanium dioxide/hydroxyapatite composite microspheres show different adsorption properties and ultraviolet light catalysis properties. However, the above methods all require a subsequent heat treatment to obtain titanium dioxide in a crystalline state, which is disadvantageous for obtaining a nanocomposite.
Disclosure of Invention
The invention provides a composite photocatalytic material and a preparation method and application thereof, aiming at the defects of nano titanium dioxide as a photocatalytic material.
The technical scheme for solving the technical problems is as follows:
the composite photocatalytic material comprises flake hydroxyapatite and titanium dioxide coated on the hydroxyapatite, wherein the length of the hydroxyapatite is 0.5-3 mu m, the particle size of the titanium dioxide is 10-30 nm, and copper and silver are deposited on the surface of the titanium dioxide.
Further, the molar ratio of the titanium dioxide to the hydroxyapatite is 1: (0.5 to 5), preferably 1: (2-3).
Further, the molar ratio of the copper to the silver is (3-5): 1.
Further, the molar ratio of the total amount of copper and silver to titanium dioxide is 1: (2-4).
The preparation method of the composite photocatalytic material comprises the following steps:
1) uniformly stirring and mixing the nano titanium dioxide, a solvent and a dispersant to obtain a suspension A; dissolving copper salt, silver salt and glucose in water to prepare a mixed salt solution B for later use;
2) respectively preparing a calcium salt solution and a solution of a phosphorus-containing substance, mixing the calcium salt solution and the solution of the phosphorus-containing substance, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, uniformly mixing, carrying out hydrothermal reaction at 130-160 ℃ for 3-8 h, cooling, standing, and carrying out centrifugal separation and drying to obtain titanium dioxide-coated flaky hydroxyapatite;
4) and 3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding sodium hydroxide, potassium hydroxide or ammonia water solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding when the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum to obtain the titanium dioxide.
Further, in the step 1), the solvent is absolute ethyl alcohol, the dispersing agent is sodium dodecyl sulfate or polyvinylpyrrolidone, and preferably, the adding amount of the dispersing agent is 0.5-3% of the mass of the nano titanium dioxide.
Further, in the step 1), the copper salt is copper nitrate, copper sulfate or copper chloride, and the silver salt is silver nitrate.
Further, the calcium salt is calcium nitrate tetrahydrate or calcium chloride, and the phosphorus-containing substance is ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
Further, the molar ratio of glucose to copper salt is 1: 1.
Further, the particle size of the nano titanium dioxide is 10-30 nm.
The principle of the composite photocatalytic material is as follows:
1) the hydroxyapatite is taken as a carrier, and the nano titanium dioxide is uniformly loaded on the surface of the hydroxyapatite in the hydrothermal synthesis process of the hydroxyapatite, so that the problem that the nano titanium dioxide is easy to agglomerate can be solved, the strong adsorption effect of the hydroxyapatite can be utilized, and then the titanium dioxide is subjected to photocatalytic degradation to form an adsorption-decomposition dynamic mechanism, the defect of weak adsorption capacity of the titanium dioxide is overcome to a certain extent, the synergistic action capacity of nano hydroxyapatite adsorption and titanium dioxide photocatalysis is fully exerted, a better photocatalytic effect is obtained, the photocatalytic efficiency and the service life of the titanium dioxide are favorably improved, and the application range of the titanium dioxide is expanded;
2) copper and silver are uniformly deposited on the surface of the nano titanium dioxide, the introduction of copper promotes the transfer of electrons, the efficient separation of photon-generated carriers is realized, and the surface ion resonance effect (SPR) of nano copper particles enables the composite photocatalytic material to show high photocatalytic performance under the irradiation of visible light, the adsorption and photocatalytic degradation efficiency of the composite photocatalytic material is obviously superior to that of monomer titanium dioxide, the Ag electron-withdrawing capability is strong, and electrons generated by light excitation are enabled to be separated from TiO2Transfer to Ag and stay the photo-excited holes in TiO2Therefore, the aim of inhibiting the recombination of electrons and holes is fulfilled, and the photocatalytic efficiency of the catalyst is improved;
3) the use amount of noble metal silver is greatly reduced by reasonably controlling the proportion of copper and silver, the noble metal silver is replaced by the cheap metal copper with high natural abundance, glucose is used as a reducing agent of copper, any toxic reducing agent is not introduced, the preparation process is simple and easy to operate, and the copper-silver alloy is green and environment-friendly, meets the requirement of actual production and has larger application potential.
The photocatalytic composite material and the preparation method thereof provided by the invention have the beneficial effects that:
1) the synergistic cooperation of hydroxyapatite, titanium dioxide, copper and silver is fully utilized, and the photocatalytic efficiency and the service life of the composite material are superior to those of the existing material;
2) because the metal copper is used for replacing most of metal silver, the production cost is low, any toxic reducing agent is not introduced, the preparation process is simple and easy to operate, the environment is protected, and the application potential is larger.
Drawings
FIG. 1 is a TEM image of the composite photocatalytic material obtained in example 1 (the scale in the image is 200 nm).
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, solvent absolute ethyl alcohol and dispersant polyvinylpyrrolidone to obtain suspension A, wherein the use amount of the polyvinylpyrrolidone is 1% of the mass of the titanium dioxide; dissolving copper nitrate, silver nitrate and glucose in water to prepare a mixed salt solution B, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1:3, and the molar ratio of the copper nitrate to the silver nitrate to the glucose is 5:1:5 for later use;
2) respectively preparing a calcium nitrate tetrahydrate aqueous solution and a monoammonium phosphate aqueous solution, mixing the calcium nitrate aqueous solution and the monoammonium phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1:2, after being uniformly mixed, carrying out hydrothermal reaction for 5 hours at 145 ℃, cooling and standing, drying at 80 ℃ after centrifugal separation to obtain the titanium dioxide coated sheet hydroxyapatite;
4) and (3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding a sodium hydroxide solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding until the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum at 50 ℃ to obtain the titanium dioxide composite material.
The TEM of the composite photocatalytic material obtained in example 1 is shown in fig. 1, and as can be seen from fig. 1, the titanium dioxide with nano-sized dots is distributed on the surface of the flake-shaped hydroxyapatite, and no obvious agglomeration phenomenon occurs.
Example 2:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, solvent absolute ethyl alcohol and dispersant polyvinylpyrrolidone to obtain a suspension A, wherein the dosage of the polyvinylpyrrolidone is 0.5% of the mass of the titanium dioxide; dissolving copper sulfate, silver nitrate and glucose in water to prepare a mixed salt solution B, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1:2, and the molar ratio of the copper sulfate, the silver nitrate and the glucose is 3:1:3 for later use;
2) respectively preparing a calcium chloride aqueous solution and a diammonium hydrogen phosphate aqueous solution, mixing the calcium chloride aqueous solution and the diammonium hydrogen phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1:5, after uniformly mixing, carrying out hydrothermal reaction for 8 hours at 130 ℃, cooling and standing, drying at 80 ℃ after centrifugal separation to obtain the titanium dioxide coated sheet-shaped hydroxyapatite;
4) and (3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding a potassium hydroxide solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding until the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum at 50 ℃ to obtain the titanium dioxide composite material.
Example 3:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, a solvent of absolute ethyl alcohol and a dispersant of sodium dodecyl sulfate to obtain a suspension A, wherein the amount of the sodium dodecyl sulfate is 3% of the mass of the titanium dioxide; dissolving copper sulfate, silver nitrate and glucose in water to prepare a mixed salt solution B, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1:4, and the molar ratio of the copper sulfate, the silver nitrate and the glucose is 3:1:3 for later use;
2) respectively preparing a calcium chloride aqueous solution and a diammonium hydrogen phosphate aqueous solution, mixing the calcium chloride aqueous solution and the diammonium hydrogen phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1: 0.5, after being uniformly mixed, carrying out hydrothermal reaction for 3 h at 160 ℃, cooling and standing, drying at 80 ℃ after centrifugal separation to obtain the titanium dioxide coated sheet hydroxyapatite;
4) and 3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding an ammonia water solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding when the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum at 50 ℃ to obtain the titanium dioxide composite material.
Comparative example 1:
1) uniformly stirring and mixing titanium dioxide with the particle size of 10-30 nm, solvent absolute ethyl alcohol and dispersant polyvinylpyrrolidone to obtain suspension A, wherein the dosage of the polyvinylpyrrolidone is 0.5% of the mass of the titanium dioxide for later use;
2) respectively preparing a calcium chloride aqueous solution and a diammonium hydrogen phosphate aqueous solution, mixing the calcium chloride aqueous solution and the diammonium hydrogen phosphate aqueous solution, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, and controlling the molar ratio of titanium dioxide to hydroxyapatite to be 1:2, after being uniformly mixed, carrying out hydrothermal reaction for 8 hours at the temperature of 130 ℃, cooling and standing, and carrying out centrifugal separation and drying to obtain the titanium dioxide coated sheet hydroxyapatite.
Comparative example 2: nano titanium dioxide with the particle size of 10-30 nm;
the photocatalytic composite material prepared in the embodiment is subjected to performance test, and the test process and the method are as follows:
(1) a comparative test is carried out on example 1 and comparative examples 1 and 2 by taking GB/T23762-2009 (purification test method of a photocatalytic material aqueous solution system) as a performance detection method of a photocatalytic material, and the performance effect of the example 1 and the comparative examples 1 and 2 on treating methylene blue waste liquid is shown in Table 1.
Table 1 performance effect of example 1 and comparative example on treatment of methylene blue waste liquid
As can be seen from the data in table 1, the photocatalytic removal rate of the photocatalytic composite material prepared by the method is 99%, the photocatalytic stability is 98%, and thus, compared with the titanium dioxide/hydroxyapatite composite material in comparative example 1, the photocatalytic removal rate of the product in example 1 on methylene blue is improved by 24%; compared with the pure nano titanium dioxide in the comparative example 2, the photocatalytic removal rate of the composite photocatalytic material prepared in the example 1 on methylene blue is improved by 31%.
As can be seen from the data in Table 1, the photocatalytic stability of the product of example 1 is 98%, 85% and 82% compared with that of comparative examples 1 and 2, respectively, and the composite photocatalytic material prepared in example 1 has better stability and longer service life compared with titanium dioxide/hydroxyapatite composite material and pure titanium dioxide.
(2) Adsorption experiment: in the experimental process, ibuprofen and carbamazepine are selected as pollutants for representing PPCPs (the PPCPs are globally called Pharmaceutical and Personal Care Products and are emerging pollutants, the PPCPs comprise various antibiotics, artificially synthesized musk, analgesics, antihypertensive drugs, contraceptive drugs, hypnotics, weight-reducing drugs, hair spray, hair dye, bactericide and the like), the initial concentration of the ibuprofen and the carbamazepine is 5mg/L, the stirring speed is 100rpm, the ultraviolet light intensity is 12W and 365nm, the adding amount of the photocatalytic adsorption material prepared in the examples 1-3 and the comparative examples 1 and 2 is 5g/L, and the reaction time is 45 min. The removal rate of contaminants before and after the reaction was calculated by high performance liquid chromatography, and the results are shown in table 2.
TABLE 2 removal of carbamazepine and ibuprofen by the materials of examples 1-3 and comparative examples
The data in table 2 show that the adsorption removal effects of the composite photocatalytic materials obtained in examples 1 to 3 on carbamazepine and ibuprofen are far better than those of comparative examples 1 and 2, which shows that the synergistic interaction of hydroxyapatite, copper, silver and nano titanium dioxide obtains a good technical effect, the adsorption performance of the composite materials is improved, the photocatalytic efficiency of the composite materials is improved, the overall performance is excellent, and the application potential is huge.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The composite photocatalytic material is characterized by comprising flake hydroxyapatite and titanium dioxide coated on the hydroxyapatite, wherein the length of the hydroxyapatite is 0.5-3 mu m, the particle size of the titanium dioxide is 10-30 nm, and copper and silver are deposited on the surface of the titanium dioxide.
2. The composite photocatalytic material according to claim 1, wherein the molar ratio of titanium dioxide to hydroxyapatite is 1: (0.5-5).
3. The composite photocatalytic material according to claim 1 or 2, wherein the molar ratio of copper to silver is (3-5): 1.
4. The composite photocatalytic material of claim 3, wherein the molar ratio of the total amount of copper and silver to titanium dioxide is 1: (2-4).
5. The method for preparing the composite photocatalytic material of claim 1, characterized by comprising the following steps:
1) uniformly stirring and mixing the nano titanium dioxide, a solvent and a dispersant to obtain a suspension A; dissolving copper salt, silver salt and glucose in water to prepare a mixed salt solution B for later use;
2) respectively preparing a calcium salt solution and a solution of a phosphorus-containing substance, mixing the calcium salt solution and the solution of the phosphorus-containing substance, controlling the molar ratio of calcium to phosphorus to be 5:3, and then adjusting the pH to be 2-3 to obtain a mixed solution C;
3) adding the suspension A into the mixed solution C, uniformly mixing, carrying out hydrothermal reaction at 130-160 ℃ for 3-8 h, cooling, standing, and carrying out centrifugal separation and drying to obtain titanium dioxide-coated flaky hydroxyapatite;
4) and 3) adding the mixed salt solution B into the hydroxyapatite obtained in the step 3), stirring uniformly, then dropwise adding sodium hydroxide, potassium hydroxide or ammonia water solution, precipitating copper ions and silver ions on the surface of titanium dioxide, stopping dropwise adding when the pH value is more than or equal to 10, cleaning to be neutral, and then drying in vacuum to obtain the titanium dioxide.
6. The method for preparing the composite photocatalytic material as recited in claim 5, wherein in step 1), the solvent is absolute ethanol, and the dispersant is sodium dodecyl sulfate or polyvinylpyrrolidone.
7. The method for preparing the composite photocatalytic material according to claim 5, wherein in the step 1), the copper salt is copper nitrate, copper sulfate or copper chloride, and the silver salt is silver nitrate.
8. The method for preparing the composite photocatalytic material according to claim 5, wherein in step 2), the calcium salt is calcium nitrate tetrahydrate or calcium chloride, and the phosphorus-containing substance is ammonium dihydrogen phosphate or ammonium hydrogen phosphate.
9. The method for preparing the composite photocatalytic material according to any one of claims 5 to 8, wherein the addition amount of the dispersing agent is 0.5 to 3% by mass of the nano titanium dioxide, the molar ratio of the glucose to the copper salt is 1:1, and the particle size of the nano titanium dioxide is 10 to 30 nm.
10. The use of the composite photocatalytic material of claim 1 in the field of photocatalytic degradation of PPCPs.
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| CN114832821A (en) * | 2022-04-25 | 2022-08-02 | 山东大学 | Preparation method of in-situ photo-assisted copper deposition photocatalyst and atomic layer deposition device |
| CN116037171A (en) * | 2022-12-23 | 2023-05-02 | 青岛农业大学 | Hap/CuFeO with visible light response 2 Photocatalytic material and preparation method thereof |
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