CN114749201A - Modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes and preparation method and application thereof - Google Patents
Modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes and preparation method and application thereof Download PDFInfo
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- CN114749201A CN114749201A CN202210535549.5A CN202210535549A CN114749201A CN 114749201 A CN114749201 A CN 114749201A CN 202210535549 A CN202210535549 A CN 202210535549A CN 114749201 A CN114749201 A CN 114749201A
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- modified hydroxyapatite
- efficiently degrading
- photocatalyst capable
- hydroxyapatite nanorod
- nanorod photocatalyst
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical class [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 239000000975 dye Substances 0.000 title claims abstract description 35
- 230000000593 degrading effect Effects 0.000 title claims abstract description 32
- 239000002073 nanorod Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229940012189 methyl orange Drugs 0.000 claims abstract description 20
- 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 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 claims abstract description 16
- 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 claims abstract description 16
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 16
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 150000003608 titanium Chemical class 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 24
- 230000015556 catabolic process Effects 0.000 claims description 20
- 238000006731 degradation reaction Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- -1 comprise physical Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- BFBPISPWJZMWJN-UHFFFAOYSA-N methyl 2-[(7-hydroxy-3,7-dimethyloctylidene)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1N=CCC(C)CCCC(C)(C)O BFBPISPWJZMWJN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/40—
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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 discloses a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, and a preparation method and application thereof, and belongs to the field of water treatment. The invention first uses g-C3N4Calcium salt, titanium salt, dihydric phosphate, polyvinylpyrrolidone, ethanol and urea under alkaline conditions. The catalyst prepared by the invention can generate free radicals under the irradiation of ultraviolet light to rapidly degrade methyl orange, acid golden yellow G, rose bengal B and methylene blue in water,high catalytic efficiency, repeated use, no secondary pollution, convenient operation and higher economic benefit.
Description
Technical Field
The invention belongs to the technical field of water treatment, relates to a photocatalyst suitable for repairing methyl orange, acid golden yellow G, rose bengal B and methylene blue polluted water, and particularly relates to a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes, and a preparation method and application thereof.
Background
Methyl orange, acid golden yellow G, rose bengal B and methylene blue are common industrial dyes and typical toxic hydrophilic organic compounds, are widely applied in the fields of paper making, textile, printing, pharmacy, cosmetics and the like, and are widely researched due to the acknowledged carcinogenicity, teratogenicity and mutagenicity on the health of human beings and animals. At present, the treatment methods of dye wastewater mainly comprise physical, chemical and biological methods, but have the defects of poor universality, high cost, difficult operation, high energy consumption, long period, easy generation of secondary pollution and the like, so that the development of a reusable and stable photocatalyst for efficiently oxidizing and degrading various dyes has important significance for treating dye pollution.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, which is simple to operate.
The invention also aims to provide the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, which is prepared by the method and can rapidly degrade methyl orange, acid golden yellow G, rose bengal B and methylene blue in water under the irradiation of ultraviolet light.
The invention also aims to provide the application of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, which has the advantages of efficient degradation, low economic cost and no secondary pollution.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a preparation method of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes, which comprises the following steps:
(1) g to C3N4Adding urea into water, stirring to uniformly disperse the urea in the water, then adding the polyvinylpyrrolidone/ethanol mixed solution under the stirring condition, and continuing stirring for 5 minutes;
(2) then adding a mixed solution containing calcium salt and titanium salt with certain concentration under the condition of stirring, and continuing stirring for 5 minutes;
(3) heating the solution obtained in the step (2) to 60-80 ℃ in a water bath, keeping the temperature constant, dropwise adding a dihydric phosphate aqueous solution according to a set molar ratio of Ca/P under the stirring condition, controlling the pH of the system to be 9-10 in real time, and continuously stirring for reaction for 2 hours after the dropwise addition is finished;
(4) and (4) putting the solution obtained in the step (3) into a reaction kettle, reacting for 3 hours at the temperature of 100 ℃ and 150 ℃, naturally cooling to room temperature, filtering, washing and drying to obtain the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes.
Preferably, said g-C in step (1)3N4The mass ratio of the urea to the urea is 1:3-1: 1.
Preferably, the mass ratio of the polyvinylpyrrolidone to the ethanol in the polyvinylpyrrolidone/ethanol mixed solution in the step (1) is 1: 10.
Preferably, in the step (2), the calcium salt is selected from calcium nitrate or calcium chloride, the titanium salt is selected from titanium sulfate or titanium tetrachloride, and the molar ratio of Ca/Ti in the mixed solution of the calcium salt and the titanium salt is 12-24: 1.
Preferably, the Ca/P molar ratio in step (3) is 1:1 to 1: 1.6.
Preferably, the dihydrogen phosphate in step (3) is selected from ammonium dihydrogen phosphate or sodium dihydrogen phosphate.
In a second aspect, the invention provides a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes, which is prepared by the preparation method.
The photocatalyst comprises hydroxyapatite and g-C loaded on the surface of the hydroxyapatite3N4The hydroxyapatite is rod-shaped, the diameter is about 12-15nm, and titanium ions are doped in the hydroxyapatite crystal lattice.
In a third aspect, the invention provides an application of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes in catalytic degradation of methyl orange, acid golden yellow G, rose bengal B and methylene blue.
The specific application steps comprise: adding a catalyst into the wastewater containing one or more of methyl orange, acid golden yellow G, rose bengal B and methylene blue to be treated, irradiating by using an ultraviolet lamp, and stirring and reacting for 1-2 hours at room temperature.
The concentration of the methyl orange, the acid golden yellow G, the rose bengal B and the methylene blue in the system is 20mg/L, and the addition amount of the catalyst is 0.5G/L.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst of the invention has simple and economic synthesis and can be produced industrially;
2. the photocatalyst can generate free radicals under the irradiation of ultraviolet light to quickly degrade methyl orange, acid golden yellow G, rose bengal B and methylene blue in water, has high catalytic efficiency, can achieve better removal effect at normal temperature, has no secondary pollution, is convenient to operate, can be repeatedly used for many times, and has higher economic benefit.
Drawings
FIG. 1 is an X-ray diffraction diagram of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes, prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope photograph of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, prepared in example 1 of the present invention;
FIG. 4 is an X-ray energy spectrum picture of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes prepared in examples 1-4 of the present invention;
FIG. 5 is the degradation curves of methyl orange, acid golden yellow G, rose bengal B and methylene blue of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes prepared in example 1 of the present invention;
fig. 6 is a stability test of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1: preparation of the catalyst
(1) 0.46g g-C3N4Adding 0.6g of urea into 50mL of pure water, stirring for 30 minutes to uniformly disperse the urea in the water, adding 5mL of polyvinylpyrrolidone/ethanol mixed solution with the mass ratio of 1:10 under the stirring condition, and continuing stirring for 5 minutes;
(2) adding 25-50g Ca (NO)3)2And 3g Ti (SO)4)2Adding the mixture into 250mL of pure water to obtain a mixed solution, taking 50mL of the mixed solution, adding the mixed solution into the solution obtained in the step (1) under the condition of stirring, and continuing stirring for 5 minutes;
(3) putting the solution in the step (2) into a water bath kettle, heating to 60 ℃, keeping the temperature constant, and dropwise adding 0.6mol/L NH under the stirring condition4H2PO4Adding 50mL of solution, adding 1% ammonia water in real time in the adding process to control the pH to be 9-10, and continuously stirring for reacting for 2 hours after finishing dripping;
(4) and (3) putting the solution into a high-temperature high-pressure reaction kettle, reacting for 3 hours at 100 ℃, naturally cooling to room temperature, washing with absolute ethanol and pure water, and drying for 2 hours at 105 ℃ to obtain the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes.
The aim of introducing titanium ions is to ensure that the titanium ions enter crystal lattices in the synthesis process of hydroxyapatite to achieve doping at the atomic level to obtain Ca10-xTix(PO3)6OH2X is Ti4+Doped with Ca2+Mole percent of (c).
FIG. 1 is an X-ray diffraction diagram of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes, prepared in example 1 of the present invention; from FIG. 1 it can be seen that hydroxyapatite and g-C are present in the catalyst3N4Indicates thatThe target product is successfully synthesized.
FIG. 2 is an infrared spectrum of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, prepared in example 1 of the present invention; from FIG. 2 it can be seen that hydroxyapatite and g-C are present in the catalyst3N4Multiple functional group characteristic peaks.
FIG. 3 is a scanning electron microscope photograph of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, prepared in example 1 of the present invention; from fig. 3, it can be seen that the catalyst exhibits a nanorod structure.
FIG. 4 is an x-ray energy spectrum of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes, prepared in example 1 of the present invention; as can be seen from FIG. 4, the catalyst contains C, N, O, Ca, P and Ti elements.
Example 2: ultraviolet light catalytic degradation of methyl orange
0.5g of the modified hydroxyapatite photocatalyst prepared in example 1 was added to 1L of wastewater with a methyl orange concentration of 20mg/L, and the mixture was irradiated with an ultraviolet lamp and stirred for 2 hours, and fig. 5 including a graph of the degradation of methyl orange measured in this example shows that methyl orange is rapidly degraded, and the degradation rate after 2 hours is 92.3%.
Example 3: ultraviolet light catalytic degradation of acid golden yellow G
0.5G of the modified hydroxyapatite photocatalyst prepared in example 1 was added to 1L of wastewater having a concentration of 20mg/L of acid aurantium G, and the mixture was irradiated with an ultraviolet lamp and stirred to react for 2 hours, and as shown in fig. 5 including the degradation curve of acid aurantium G measured in this example, it was found that acid aurantium G was rapidly degraded, and the degradation rate after 2 hours was 96.4%.
Example 4: ultraviolet light catalytic degradation rose bengal B
0.5g of the modified hydroxyapatite photocatalyst prepared in example 1 was added to 1L of wastewater containing rose bengal B at a concentration of 20mg/L, and the mixture was irradiated with an ultraviolet lamp and stirred for 2 hours, and as shown in FIG. 5, the degradation curve of rose bengal B measured in this example was included, it was found that rose bengal B was rapidly degraded, and the degradation rate was 99.37% after 2 hours.
Example 5: ultraviolet light catalytic degradation of methylene blue
0.5g of the modified hydroxyapatite photocatalyst prepared in example 1 was added to 1L of wastewater having a methylene blue concentration of 20mg/L, and the mixture was irradiated with an ultraviolet lamp and stirred for 2 hours, and as shown in fig. 5 including a methylene blue degradation curve measured in this example, it was found that methylene blue was rapidly degraded, and the degradation rate was 93.11% after 2 hours.
Example 6: methyl orange cycle degradation experiment
Five methyl orange cyclic degradation experiments are carried out by using 0.5g/L of the modified hydroxyapatite photocatalyst prepared in example 1, the concentration of methyl orange is 20mg/L, ultraviolet lamps are used for irradiation, each stirring reaction is carried out for 150 minutes, and fig. 6 shows that the methyl orange degradation curve measured by the implementation is high in degradation rate and good in stability through five repeated experiments.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A preparation method of a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes is characterized by comprising the following steps:
(1) g to C3N4Adding urea into water, stirring to uniformly disperse the urea in the water, adding the polyvinylpyrrolidone/ethanol mixed solution under the stirring condition, and continuously stirring for 5 minutes;
(2) then adding a mixed solution containing calcium salt and titanium salt with certain concentration under the stirring condition, and continuously stirring for 5 minutes;
(3) heating the solution obtained in the step (2) to 60-80 ℃ in a water bath, keeping the temperature constant, dropwise adding a dihydric phosphate aqueous solution according to a set molar ratio of Ca/P under the stirring condition, controlling the pH of the system to be 9-10 in real time, and continuously stirring for reaction for 2 hours after the dropwise addition is finished;
(4) and (4) putting the solution obtained in the step (3) into a reaction kettle, reacting for 3 hours at the temperature of 100 ℃ and 150 ℃, naturally cooling to room temperature, filtering, washing and drying to obtain the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading various dyes.
2. The method for preparing the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes according to claim 1, wherein the g-C in the step (1)3N4The mass ratio of the urea to the urea is 1:3-1: 1.
3. The method for preparing a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes according to claim 1, wherein the mass ratio of polyvinylpyrrolidone to ethanol in the polyvinylpyrrolidone/ethanol mixed solution in the step (1) is 1: 10.
4. The method for preparing a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes according to claim 1, wherein in the step (2), the calcium salt is selected from calcium nitrate or calcium chloride, the titanium salt is selected from titanium sulfate or titanium tetrachloride, and the molar ratio of Ca to Ti in a mixed solution of the calcium salt and the titanium salt is 12-24: 1.
5. The preparation method of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes according to claim 1, wherein the molar ratio of Ca to P in the step (3) is 1:1-1: 1.6.
6. The method for preparing a modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes according to claim 1, wherein the dihydrogen phosphate in the step (3) is selected from ammonium dihydrogen phosphate or sodium dihydrogen phosphate.
7. The modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading a plurality of dyes, prepared by the preparation method of any one of claims 1 to 6.
8. The use of the modified hydroxyapatite nanorod photocatalyst capable of efficiently degrading multiple dyes according to claim 7 in catalytic degradation of methyl orange, acid golden yellow G, rose bengal B and methylene blue.
9. The use according to claim 8, wherein the catalyst is added to the wastewater to be treated containing one or more of methyl orange, acid golden yellow G, rose bengal B and methylene blue, followed by irradiation with an ultraviolet lamp and reaction with stirring at room temperature for 1-2 hours.
10. The use of claim 9, wherein the concentration of methyl orange, acid golden yellow G, rose bengal B and methylene blue in the system is 20mg/L, and the catalyst is added in an amount of 0.5G/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701845A (en) * | 2005-03-31 | 2005-11-30 | 上海交通大学 | Method for preparing TiO2/titanium supported hydroxyapatite complex phase absorption and disinfection nano material |
| CN109954506A (en) * | 2019-04-04 | 2019-07-02 | 四川轻化工大学 | A kind of catalyst LaHAP and its application |
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2022
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| CN1701845A (en) * | 2005-03-31 | 2005-11-30 | 上海交通大学 | Method for preparing TiO2/titanium supported hydroxyapatite complex phase absorption and disinfection nano material |
| CN109954506A (en) * | 2019-04-04 | 2019-07-02 | 四川轻化工大学 | A kind of catalyst LaHAP and its application |
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| TIANHONG XU等: "New and stable g-C3N4/HAp composites as highly efficient photocatalysts for tetracycline fast degradation", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 李心昕: "多孔钛磷灰石复合材料的制备及其对醛类污染物的净化作用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 王俊忠: "卤化氧铋复合材料对醛类污染物的降解作用及其应用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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