CN109225196A - The precipitation method prepare the method and its application of Zinc modified bismuth oxide composite photo-catalyst - Google Patents
The precipitation method prepare the method and its application of Zinc modified bismuth oxide composite photo-catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 239000011701 zinc Substances 0.000 title claims abstract description 21
- 238000001556 precipitation Methods 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- -1 Zinc modified bismuth oxide Chemical class 0.000 title claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 14
- 239000005457 ice water Substances 0.000 claims abstract description 14
- 150000001621 bismuth Chemical class 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 4
- 239000013049 sediment Substances 0.000 claims abstract description 4
- 239000010865 sewage Substances 0.000 claims abstract description 3
- 238000013019 agitation Methods 0.000 claims description 17
- 238000004090 dissolution Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 239000001045 blue dye Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 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 1
- 229960000907 methylthioninium chloride Drugs 0.000 claims 1
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 28
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 28
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 150000003751 zinc Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000002045 lasting effect Effects 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical class [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910006362 δ-Bi2O3 Inorganic materials 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
-
- 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
- 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
-
- 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
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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 belongs to photochemical catalyst preparation technical field, it is related to the preparation method of bismuth oxide composite photo-catalyst, in particular to the precipitation method method and its application that prepare Zinc modified bismuth oxide composite photo-catalyst.The present invention prepares the mixed solution A of bismuth salt and zinc salt first, then prepares precipitant solution B；Then solution A is persistently stirred in ice-water bath, B solution is not added dropwise at line at drop；It is centrifugated out after sediment is washed till neutrality and dries, then at 350~550 DEG C of 1~4 h of temperature calcination to obtain the final product.The present invention prepares nanometer bismuth oxide composite material using liquid-phase precipitation method, and at low cost, easy to operate, made product grain is evenly distributed, and particulates' properties are high, and Particle dispersity is good, and pattern is good, is suitble to industrialized production.The bismuth oxide composite material of the method preparation according to the present invention is used for sewage of the photocatalytic degradation containing dyestuffs such as Congo red, methylene blues as photochemical catalyst, and catalytic efficiency is higher.
Description
Technical field
The invention belongs to photochemical catalyst preparation technical fields, are related to the preparation method of bismuth oxide composite photo-catalyst,
In particular to the precipitation method method and its application that prepare Zinc modified bismuth oxide composite photo-catalyst.
Background technique
With the progress of society and the development of science and technology, also being asked facing to serious environment while science and technology changes life
Topic.Currently, the mode that extensive style develops and utilizes traditional energy has been no longer appropriate for present development.So far, people are successfully
Develop various new energy and new device.But desertification of land, air pollution caused by before, water pollution, temperature
The serious environmental problem such as room effect is continuing always, and which results in the concerns of scientific research personnel.Therefore, processing pollutant is developed
New material, device and technology etc. it is extremely urgent.
Bismuth oxide (bismuth oxide) sterling has α type, β type and δ type.α type is yellow monoclinic system crystal, relative density
8.9,825 DEG C of fusing point, it is dissolved in acid, not soluble in water and alkali.β type is glassy yellow to orange, tetragonal system, and relative density 8.55 melts
860 DEG C of point, is dissolved in acid, not soluble in water；It is easy to be reduced to bismuth metal by hydrogen, hydro carbons etc..δ-Bi2O3It is a kind of special crystalline substance
Body has cubic fluorite mine type structure, and having 1/4 oxonium ion position in lattice is vacancy, thus has very high oxygen
Ionic conducting property.Mainly electronic ceramics powder body material, electrolyte, photoelectric material, high-temperature superconductor material are done in application to bismuth oxide
Material, catalyst etc..
Currently, the preparation method of bismuth oxide nano material have very much, according to preparation principle can be divided into chemical method and
Physical method can be divided into vapor phase method, solid phase method and liquid phase method according to material state.Wherein, vapor phase method energy consumption is high, complex process, at
This height, the unfavorable factors such as environmental pollution is serious, limit large-scale industrial production；Solid-phase process preparation is simple, it is at low cost, produce
Amount is big, but low efficiency, easily being mixed into the unfavorable factors such as impurity limits its development；Liquid phase method is present bismuth oxide synthesis
Main method, and sol-gel method, hydro-thermal method, the precipitation method can be divided into etc..Wherein, sol-gel method has reactant ingredient easy
In precise controlling, the advantages such as particle size is small, reaction time is shorter, deficiency is hard aggregation easy to form after gel drying, dry
When shrink it is big；Although the crystal good dispersion of hydro-thermal method synthesis, particle purity is high, thermal stress are smaller, poor safety performance, to anti-
Answering equipment and operating technology also has very high requirement；Since the precipitation method have to consersion unit of less demanding, at low cost, technique stream
The advantages that journey is simple, thus the present invention synthesizes bismuth oxide using liquid-phase precipitation method using Zn-ef ficiency as additive, and to shape
Looks are controllably debugged.
Summary of the invention
The purpose of the present invention is using metallic element zinc as additive, by changing its different ratio, with liquid-phase precipitation
Method synthesizes nanometer bismuth oxide composite photo-catalyst.
Technical solution is as follows:
The method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, includes the following steps:
(1) according to 0~30 % gold that 1~5 mmol bismuth salt is successively added in every 30~80 mL deionized water, accounts for bismuth salt molal quantity
Belong to salt, magnetic agitation makes its uniform dissolution be configured to solution A, preferably 2 mmol bismuth salts: accounting for 15 % metal salts of bismuth salt molal quantity:
40 mL deionized waters；
(2) according to 3~10 mmol precipitating reagents are added in every 20~60 mL deionized water, magnetic agitation prepares its uniform dissolution
At B solution, preferably 7 mmol precipitating reagents: 40 mL deionized waters；
(3) solution A is persistently stirred in ice-water bath, B solution is added dropwise, be not added dropwise at line at drop, react 1~4 h, preferably
2 h are reacted, taking-up is cooled to room temperature, wherein the volume ratio of the solution A and B solution is 3~8:2~6, preferably 1:1；
(4) it is centrifugated out sediment, is respectively washed 3~4 times with deionized water and dehydrated alcohol respectively, its pH value is made to reach neutral,
In 40~80 DEG C of bakings 16~36 h, preferably 80 DEG C 20 h of baking；
(5) dry after product in Muffle furnace in 350~550 DEG C of 1~4 h of temperature calcination to obtain the final product, preferably 450 DEG C calcining 2
h。
In a more excellent disclosed example of the invention, step (1) described bismuth salt is five nitric hydrate bismuths, bismuth acetate or bismuth chloride
In any one.
In a more excellent disclosed example of the invention, step (1) described metal salt is zinc nitrate hexahydrate, Zinc vitriol
Or any one in zinc chloride.
In a more excellent disclosed example of the invention, step (2) described precipitating reagent is sodium bicarbonate, sodium hydroxide or ammonium carbonate
In any one.
Bismuth oxide composite material (the ZnO@Bi that the method is prepared according to the present invention2O3), purity is high, crystal form
Well, impurity content is few, pattern is good, is evenly distributed.
Another object of the present invention, the bismuth oxide composite material that the method is prepared according to the present invention is as light
Catalyst is used for sewage of the photocatalytic degradation containing dyestuffs such as Congo red, methylene blues.
It is Congo red that nanometer bismuth oxide composite material obtained by the present invention is used for photocatalytic degradation by laboratory simulation
Solution, steps are as follows:
(1) 10 mgL are prepared-1400 ml of Congo red solution, and be added 45 mg made from nanometer bismuth oxide composite wood
Material, 15 min of magnetic agitation keep its evenly dispersed, are placed in 30 min of unglazed stirring in multifunctional chemical reaction instrument, reach object
Reason absorption and desorption equilibrium open light source later and carry out catalysis reaction, take a sample every 10 min, carry out to the sample taken
It is centrifuged at a high speed, is measured at 497 nm using 8454 type ultraviolet-visible spectrophotometer (Agilent company of the U.S.) of Cary
The absorbance (A) of each sample supernatant liquor seeks Congo red degradation rate according to the variation of absorbance value.
(2) degradation rate: α=(A0- A)/A0× 100%,
Wherein A0It is the initial absorbance of Congo red solution adsorption equilibrium, A is the absorbance after Congo red solution degradation.
The present invention is using metal salt (zinc nitrate hexahydrate, Zinc vitriol or zinc chloride) as additive, with bismuth salt (five
Nitric hydrate bismuth, bismuth acetate or bismuth chloride) and precipitating reagent (sodium bicarbonate, sodium hydroxide or ammonium carbonate) be raw material, pass through adjusting
The content of additive and its dependent variable, and nanometer bismuth oxide composite photo-catalyst is prepared using liquid-phase precipitation method.Heavy
The metal salt of addition different content can play the role of steric hindrance during forming sediment, and directly contact between reduction particle, reduce surface
Power reduces surface energy, so that reducing disperse system leads to the degree of aggregation because of the effect of hydrogen bond or Van der Waals force, keeps dispersion
System is relatively stable, effectively regulates and controls to the size of nanoparticle and pattern.According to the present invention the method prepare three
Aoxidize two bismuth composite materials, there is preferable catalytic performance, there is synergistic effect mainly between composite material, between material into
Row has complementary advantages, to reach optimal catalytic performance, realizes the effect of 1+1 > 2, finally improves the catalytic of homogenous material
Energy.
This experiment reagent used is all that analysis is pure, is commercially available.
Beneficial effect
The present invention is using metallic element zinc as additive, by changing different reaction conditions, prepares nanometer using liquid-phase precipitation method
Bismuth oxide composite material.Its operating condition is easily controllable, and equipment is simple, environmentally friendly and low in cost, made product grain point
Cloth is uniform, and particle dispersion can be good, and reunion degree is low, and pattern is good, it is easy to accomplish industrialization.According to the present invention prepared by the method
Bismuth oxide composite material out is used for dirt of the photocatalytic degradation containing dyestuffs such as Congo red, methylene blues as photochemical catalyst
Water, catalytic efficiency are higher.
Detailed description of the invention
Fig. 1 is Fourier transform infrared spectroscopy (FTIR), in which:
A is nanometer bismuth oxide material prepared by the present invention,
B is nanometer bismuth oxide composite material prepared by the present invention.
Fig. 2 is X ray diffracting spectrum (XRD), in which:
A is nanometer bismuth oxide material prepared by the present invention,
B is nanometer bismuth oxide composite material prepared by the present invention.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but the invention is not limited to following embodiments.
Embodiment 1
2 mmol, five nitric hydrate bismuth is weighed at room temperature in beaker, and 50 mL deionized waters, magnetic agitation are added into beaker
10 min make its uniform dissolution, form solution A；Then 6 mmol sodium hydroxides are weighed at room temperature in beaker, are added 30
ML deionized water, 10 min of magnetic agitation make its uniform dissolution, form B solution.The beaker for filling A liquid is put into ice water bath
In, it is lasting to stir, and A liquid is added dropwise in B liquid, 1 h is reacted under ice-water bath, filters and washs, in 50 DEG C of constant temperature ovens
16 h are dried, later in Muffle furnace in 400 DEG C of 3 h of temperature lower calcination, obtain product bismuth oxide, FTIR a as shown in figure 1
Shown, for XRD spectrum as shown in a in Fig. 2, which meets XRD standard card (the JCPDS No. 27- of bismuth oxide
0050), illustrate successfully to prepare bismuth oxide.
45 mg product manufactured in the present embodiment is to the Congo red solution of 400 mL (10 mgL-1) degradation rate be 48.5%.
Embodiment 2
The zinc nitrate hexahydrate of 2 mmol, five nitric hydrate bismuth and 15 % are weighed at room temperature in beaker, and 40 are added into beaker
ML deionized water, 10 min of magnetic agitation make its uniform dissolution, form solution A；Then 7 mmol bicarbonates are weighed at room temperature
40 mL deionized waters are added in beaker in sodium, and 10 min of magnetic agitation makes its uniform dissolution, form B solution.A liquid will be filled
Beaker be put into ice water bath, it is lasting to stir, and A liquid is added dropwise in B liquid, 2 h are reacted under ice-water bath, filters and washes
It washs, dries 20 h in 80 DEG C of constant temperature ovens, obtain the oxidation of product three in 450 DEG C of 2 h of temperature lower calcination in Muffle furnace later
Two bismuth composite materials, FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2.
45 mg product manufactured in the present embodiment is to the Congo red solution of 400 mL (10 mgL-1) degradation rate be 92%.
Embodiment 3
The zinc chloride of 5 mmol bismuth acetates and 30 % are weighed at room temperature in beaker, and 80 mL deionized waters are added into beaker,
10 min of magnetic agitation makes its uniform dissolution, forms solution A；Then 10 mmol sodium bicarbonates are weighed at room temperature in beaker
In, 60 mL deionized waters are added, 10 min of magnetic agitation makes its uniform dissolution, forms B solution.The beaker for filling A liquid is put
Enter in ice water bath, it is lasting to stir, and A liquid is added dropwise in B liquid, 3 h are reacted under ice-water bath, filters and washs, in 60 DEG C
24 h are dried in constant temperature oven, obtain product bismuth oxide composite wood in 500 DEG C of 1 h of temperature lower calcination in Muffle furnace later
Material, FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2.
45 mg product manufactured in the present embodiment is to the Congo red solution of 400 mL (10 mgL-1) degradation rate be 89.5%.
Embodiment 4
The Zinc vitriol of 1 mmol bismuth chloride and 2 % are weighed at room temperature in beaker, and be added into beaker 30 mL go from
Sub- water, 10 min of magnetic agitation make its uniform dissolution, form solution A；Then 3 mmol sodium hydroxides are weighed at room temperature in burning
In cup, 20 mL deionized waters are added, 10 min of magnetic agitation makes its uniform dissolution, forms B solution.The beaker of A liquid will be filled
It is put into ice water bath, it is lasting to stir, and A liquid is added dropwise in B liquid, 4 h are reacted under ice-water bath, are filtered and are washed, in 70
18 h are dried in DEG C constant temperature oven, it is multiple to obtain product bismuth oxide in 550 DEG C of 1.5 h of temperature lower calcination in Muffle furnace later
Condensation material, FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2.
45 mg product manufactured in the present embodiment is to the Congo red solution of 400 mL (10 mgL-1) degradation rate be 81.9%.
Embodiment 5
The zinc nitrate hexahydrate of 3 mmol bismuth chlorides and 10 % are weighed at room temperature in beaker, and 50 mL are added into beaker and go
Ionized water, 10 min of magnetic agitation make its uniform dissolution, form solution A；Then 5 mmol ammonium carbonates are weighed at room temperature in burning
In cup, 35 mL deionized waters are added, 10 min of magnetic agitation makes its uniform dissolution, forms B solution.The beaker of A liquid will be filled
It is put into ice water bath, it is lasting to stir, and A liquid is added dropwise in B liquid, 2 h are reacted under ice-water bath, are filtered and are washed, in 40
36 h are dried in DEG C constant temperature oven, it is compound to obtain product bismuth oxide in 350 DEG C of 4 h of temperature lower calcination in Muffle furnace later
Material, FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2.
45 mg product manufactured in the present embodiment is to the Congo red solution of 400 mL (10 mgL-1) degradation rate be 86.1%.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (10)
1. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, which comprises the steps of:
(1) according to 0~30 % gold that 1~5 mmol bismuth salt is successively added in every 30~80 mL deionized water, accounts for bismuth salt molal quantity
Belong to salt, magnetic agitation makes its uniform dissolution be configured to solution A；
(2) according to 3~10 mmol precipitating reagents are added in every 20~60 mL deionized water, magnetic agitation prepares its uniform dissolution
At B solution；
(3) solution A is persistently stirred in ice-water bath, B solution is added dropwise, be not added dropwise at line at drop, react 1~4 h, taken out
It is cooled to room temperature, wherein the volume ratio of the solution A and B solution is 3~8:2~6；
(4) it is centrifugated out sediment, is respectively washed 3~4 times with deionized water and dehydrated alcohol respectively, its pH value is made to reach neutral,
In 40~80 DEG C of 16~36 h of baking；
(5) dry after product in Muffle furnace in 350~550 DEG C of 1~4 h of temperature calcination to obtain the final product.
2. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: step (1) described bismuth salt is any one in five nitric hydrate bismuths, bismuth acetate or bismuth chloride, and the metal salt is six water
Close any one in zinc nitrate, Zinc vitriol or zinc chloride.
3. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: step (2) described precipitating reagent is any one in sodium bicarbonate, sodium hydroxide or ammonium carbonate.
4. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: step (1) is described according to the 15 % metals that 2 mmol bismuth salts are successively added in every 40 mL deionized water, account for bismuth salt molal quantity
Salt, magnetic agitation make its uniform dissolution be configured to solution A.
5. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: step (2) is described according to 7 mmol precipitating reagents are added in every 40 mL deionized water, and magnetic agitation prepares its uniform dissolution
At B solution.
6. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: step (3) is described persistently to stir solution A in ice-water bath, and B solution is added dropwise, and is not added dropwise at line at drop, reacts 2 h,
Taking-up is cooled to room temperature；The volume ratio of the solution A and B solution is 1:1.
7. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: step (4) is set forth in 80 DEG C of 20 h of baking.
8. the method that the precipitation method prepare Zinc modified bismuth oxide composite photo-catalyst, feature exist according to claim 1
In: product after step (5) described drying in Muffle furnace in 450 DEG C of 2 h of calcining to obtain the final product.
9. Zinc modified bismuth oxide composite photo-catalyst made from -8 any the methods according to claim 1.
10. the application of Zinc modified bismuth oxide composite photo-catalyst described in a kind of claim 9, it is characterised in that: made
For photochemical catalyst for photocatalytic degradation containing Congo red, methylene blue dye sewage.
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| CN111569858A (en) * | 2020-04-27 | 2020-08-25 | 沈阳工业大学 | Preparation method and application of delta bismuth oxide catalytic material |
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