CN106391038B - A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials - Google Patents
A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials Download PDFInfo
- Publication number
- CN106391038B CN106391038B CN201610816596.1A CN201610816596A CN106391038B CN 106391038 B CN106391038 B CN 106391038B CN 201610816596 A CN201610816596 A CN 201610816596A CN 106391038 B CN106391038 B CN 106391038B
- Authority
- CN
- China
- Prior art keywords
- product
- thermal reaction
- copper
- solvent thermal
- composite nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 110
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 51
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 51
- 230000008520 organization Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 34
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 15
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000862 absorption spectrum Methods 0.000 claims description 7
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 6
- GEBVYLHOCNKBAH-UHFFFAOYSA-N copper;propan-2-one Chemical compound [Cu].CC(C)=O GEBVYLHOCNKBAH-UHFFFAOYSA-N 0.000 claims description 6
- 238000011175 product filtration Methods 0.000 claims description 6
- 238000011026 diafiltration Methods 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000010919 dye waste Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 13
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000005286 illumination Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F2101/38—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to inorganic non-metallic material preparation fields, more particularly to a kind of spherical hierarchical organization stannic oxide/copper oxide composite nano materials preparation method, its with by acetylacetone copper and tin tetrachloride in methanol solution after completely dissolution, carry out solvent thermal reaction, after being filtered, washed, up to spherical hierarchical organization stannic oxide/copper oxide composite nano materials after drying, calcining are cooling.Product of the present invention purity is high, preparation cost is low, and the size of the whole big ball of products obtained therefrom is 3 ~ 6 μm, and the size of nanoparticle is 20 ~ 30 nm, and the homogeneity and good dispersion of product, is easy to be mass produced.Spherical hierarchical organization stannic oxide/copper oxide composite nano materials visible light catalysis activity with higher prepared by the present invention, in degradation of dye waste water and indoor harmful gas, the fields such as photocatalysis disinfection are with a wide range of applications.
Description
Technical field
The invention belongs to the preparation technical fields of inorganic non-metallic material, concretely relate to a kind of spherical hierarchical organization
Stannic oxide/copper oxide composite nano materials preparation method.
Background technique
Stannic oxide (SnO2) be a kind of broad stopband, direct band gap n-type semiconductor, band gap width is 3.6-3.8
EV has excellent flame-retardant conductive performance, also has infrared radiation reflecting and shading, absorption, stable chemical performance, there is bloom
Catalytic activity etc..Due to the greater band gap of stannic oxide, responding to visible light spectrum is few, so directly being dropped using stannic oxide photocatalysis
The correlative study for solving pollutant is seldom.In order to improve the catalytic performance of stannic oxide, selection and the lesser semiconductor of other band gap
It is compound to be very effective one of method.Since stannic oxide is n-type semiconductor, so selecting itself and the lesser p-type of band gap half
Conductor indium copper (0.96 eV) is compound, prepares novel p-n heterojunction composite semiconductor stannic oxide/copper oxide nano material,
Primary study content as photocatalysis field.
Stannic oxide/copper oxide composite nano materials traditional preparation methods mainly have solid phase method and coprecipitation.Tradition
Solid-phase synthesis due to preparation process calcination temperature it is high, not only waste of resource, but also miscellaneous phase, size easily occur larger etc. for product
Disadvantage.In coprecipitation preparation process, it is also easy to produce miscellaneous phase, and use a large amount of precipitating reagent, so that preparation cost increases.Institute
The product purity of preparation is not high, and specific surface area is small, influences its service performance as catalyst.
Summary of the invention
The present invention is directed to provide a kind of simple process in place of overcome the deficiencies in the prior art, sintering temperature is low, and purpose produces
Object high income, preparation cost is low, the preparation of the high spherical hierarchical organization stannic oxide/copper oxide composite nano materials of product purity
Method.
In order to achieve the above objectives, the invention is realized in this way.
A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, is by acetylacetone copper
In methyl alcohol after completely dissolution with tin tetrachloride, solvent thermal reaction is carried out, after being filtered, washed, after drying, calcining are cooling
Up to purpose product.
As a preferred embodiment, the molar ratio of acetylacetone copper and tin tetrachloride of the present invention is 1:1.The acetyl
The molar concentration of acetone copper is 0.01~0.1 mol/L.
Further, for solvent thermal reaction temperature of the present invention at 110~220 DEG C, the reaction time is 6~48 hours.
Further, drying time of the present invention is 1~5 hour, and drying temperature is 60~150 DEG C, heating rate
It is 2~10 DEG C/min.
Further, calcination time of the present invention is 2~8 hours, and calcination temperature is 500~800 DEG C, heating speed
Rate is 2~20 DEG C/min.
The present invention utilizes solvent heat-calcining two-step method, has successfully prepared the higher spherical shape of purity under cryogenic
Hierarchical organization stannic oxide/copper oxide composite nano materials.
Compared with prior art, the present invention has following features.
(1) the preparation process route of spherical hierarchical organization stannic oxide/copper oxide composite nano materials is simple, preparation cost
Low, easy to control, production efficiency with higher, synthesis stannic oxide/copper oxide composite nano materials are spherical grades
Structural material is that a big ball is assembled by a large amount of nanoparticle.The size of big ball is 3 ~ 6 μm, and the size of nanoparticle is
10~30 nm。
(2) purpose product high income (99.0%~99.9%) can meet industrial application to spherical hierarchical organization dioxy
Change the requirement of tin/copper oxide composite nano materials product.
(3) purpose product spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, purity is high (99.95%~
99.98%), impurity content is low, and good dispersion (can be seen that) by SEM figure.
(4) purpose product spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention are ultraviolet
In visible absorption spectrum, there is stronger absorption peak at 340 ± 10 nm, 600 ± 10 nm and 720 ± 10 nm tri- respectively.
(5) purpose product spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention are used as light
Catalyst uses, and degradation rate can reach (98.5%~99.6%) within 60 minutes, catalytic activity with higher.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and specific embodiments.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is the SEM pattern of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Figure.
Fig. 2 is the SEM pattern of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Figure.
Fig. 3 is the SEM pattern of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Figure.
Fig. 4 is the SEM pattern of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Figure.
Fig. 5 is the SEM pattern of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Figure.
Fig. 6 is the SEM pattern of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Figure.
Fig. 7 is the X-ray diffraction of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Style figure.
Fig. 8 is the visible-ultraviolet of spherical hierarchical organization stannic oxide/copper oxide composite nano materials prepared by the present invention
Abosrption spectrogram.
Specific embodiment
In methyl alcohol after completely dissolution by acetylacetone copper and tin tetrachloride, carrying out solvent thermal reaction, (temperature exists the present invention
110~220 DEG C, the time is 6~48 hours), be filtered, washed, dry, calcine it is cooling after (drying time is purpose product to obtain the final product
1~5 hour, temperature was 60~120 DEG C, and heating rate is 2~10 DEG C/min.Calcination time is 2~8 hours, and temperature is
500~800 DEG C, heating rate is 2~20 DEG C/min).
Its preparation step is.
(1) it after by acetylacetone copper and tin tetrachloride according to certain molar ratio weighing, is put into methanol and sufficiently dissolves.It will
Obtained mixed solution at a certain temperature, carries out solvent thermal reaction, and solvent thermal reaction temperature is at 110~220 DEG C, solvent heat
Reaction time is 6~48 hours.
(2) solvent thermal reaction terminates, and after cooled to room temperature, is put into baking after the product that reaction obtains is filtered, washed
In case, programmed rate is 2~10 DEG C/min, 1~5 hour dry under the conditions of 60~120 DEG C.
(3) it is above-mentioned it is dried after, obtained product is directly calcined in Muffle furnace, the liter of temperature programming in Muffle furnace
Warm speed range is in 2~20 DEG C/min.Calcination time is 2~8 hours, and calcination temperature is 500~800 DEG C.After natural cooling i.e.
Spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials are made.
(4) using prepared spherical hierarchical organization stannic oxide/copper oxide composite nano materials as photochemical catalyst
(0.1g/L), the methyl orange solution for the 10mg/L that degrades.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain
The methyl orange solution of catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.It is measured with spectrophotometric
Determine the variation of methyl orange dye concentration.
Referring to shown in Fig. 1~6, for spherical hierarchical organization stannic oxide/copper oxide composite Nano material prepared by the present invention
Expect scanning electron microscope (SEM) figure carried out, products obtained therefrom spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, material
Good dispersion, the size of big ball is 3 ~ 6 μm, and the size of nanoparticle is 10 ~ 30 nm.Fig. 7 is ball prepared by the present invention
Shape hierarchical organization stannic oxide/copper oxide composite nano materials X-ray diffraction pattern figure, wherein SnO2PDF card number be
The PDF card number of 41-1415, CuO are 48-1548.Fig. 8 is spherical hierarchical organization stannic oxide/copper oxide prepared by the present invention
The visible uv absorption spectra of composite nano materials has stronger absorption at 340 nm, 600 nm and 720 nm tri- respectively
Peak.
Embodiment 1.
The ratio for being 1:1 according to molar ratio by acetylacetone copper and tin tetrachloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of acetylacetone copper are 0.01 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 200 DEG C, the solvent thermal reaction time is 24 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 5 DEG C/min of programmed rate, in 120 DEG C of items
It is 5 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 8 hours, and calcination temperature is 500 DEG C, heating rate
It is 10 DEG C/min.Spherical hierarchical organization stannic oxide/copper oxide composite nano materials are obtained after natural cooling.The ruler of big ball
Very little is 3 μm, and the size of nanoparticle is 20 nm, and the yield of product is 99.0%.Product purity is 99.95%, and carbon impurity contains
Amount is less than 0.05%.Product has at 330 nm, 590 nm and 710 nm tri- relatively strong respectively in UV-vis absorption spectrum
Absorption peak.
Using prepared spherical hierarchical organization stannic oxide/copper oxide composite nano materials as photochemical catalyst (0.1g/
L), degrade the methyl orange solution of 10mg/L.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain catalysis material
The methyl orange solution of material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.Catalytic activity is evaluated in photocatalysis
Experiment in, 60 minutes degradation rates are 98.9%.
Embodiment 2.
The ratio for being 1:1 according to molar ratio by acetylacetone copper and tin tetrachloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of acetylacetone copper are 0.02 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 110 DEG C, the solvent thermal reaction time is 48 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 5 DEG C/min of programmed rate, in 120 DEG C of items
It is 5 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 4 hours, and calcination temperature is 700 DEG C, heating rate
It is 10 DEG C/min.Spherical hierarchical organization stannic oxide/copper oxide composite nano materials are obtained after natural cooling.The ruler of big ball
Very little is 6 μm, and the size of nanoparticle is 30 nm, and the yield of product is 99.7%.Product purity is 99.97%, impurity carbon content
Less than 0.03%.Product has at 340 nm, 600 nm and 710 nm tri- stronger respectively in UV-vis absorption spectrum
Absorption peak.
Using prepared spherical hierarchical organization stannic oxide/copper oxide composite nano materials as photochemical catalyst (0.1g/
L), degrade the methyl orange solution of 10mg/L.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain catalysis material
The methyl orange solution of material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.Catalytic activity is evaluated in photocatalysis
Experiment in, 60 minutes degradation rates are 98.5%.
Embodiment 3.
The ratio for being 1:1 according to molar ratio by acetylacetone copper and tin tetrachloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of acetylacetone copper are 0.03 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 220 DEG C, the solvent thermal reaction time is 12 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 100 DEG C of items
It is 5 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 5 hours, and calcination temperature is 800 DEG C, heating rate
It is 10 DEG C/min.Spherical hierarchical organization stannic oxide/copper oxide composite nano materials are obtained after natural cooling.The ruler of big ball
Very little is 4 μm, and the size of nanoparticle is 25 nm, and the yield of product is 99.8%.Product purity is 99.96%, impurity carbon content
Less than 0.04%.Product has at 340 nm, 610 nm and 720 nm tri- stronger respectively in UV-vis absorption spectrum
Absorption peak.
Using prepared spherical hierarchical organization stannic oxide/copper oxide composite nano materials as photochemical catalyst (0.1g/
L), degrade the methyl orange solution of 10mg/L.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain catalysis material
The methyl orange solution of material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.Catalytic activity is evaluated in photocatalysis
Experiment in, 60 minutes degradation rates are 99.6%.
Embodiment 4.
The ratio for being 1:1 according to molar ratio by acetylacetone copper and tin tetrachloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of acetylacetone copper are 0.05 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 220 DEG C, the solvent thermal reaction time is 6 hours.After solvent thermal reaction, naturally cool to
Room temperature will be put into baking oven, 10 DEG C/min of programmed rate, in 120 DEG C of conditions after the obtained product filtration washing of reaction
Lower drying 1 hour.Then it is placed in Muffle furnace and calcines, calcination time is 2 hours, and calcination temperature is 800 DEG C, and heating rate is
20 DEG C/min.Spherical hierarchical organization stannic oxide/copper oxide composite nano materials are obtained after natural cooling.The size of big ball
It is 5.5 μm, the size of nanoparticle is 10 nm, and the yield of product is 99.1%.Product purity is 99.98%, and carbon impurity contains
Amount is less than 0.02%.Product has at 350 nm, 610 nm and 730 nm tri- relatively strong respectively in UV-vis absorption spectrum
Absorption peak.
Using prepared spherical hierarchical organization stannic oxide/copper oxide composite nano materials as photochemical catalyst (0.1g/
L), degrade the methyl orange solution of 10mg/L.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain catalysis material
The methyl orange solution of material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.Catalytic activity is evaluated in photocatalysis
Experiment in, 60 minutes degradation rates are 99.1%.
Embodiment 5.
The ratio for being 1:1 according to molar ratio by acetylacetone copper and tin tetrachloride, be put into after precise methanol (12C,
99.95%) stirring and dissolving in, the molar concentration of acetylacetone copper are 0.1 mol/L.Obtained mixed solution is subjected to solvent heat
Reaction, for solvent thermal reaction temperature at 200 DEG C, the solvent thermal reaction time is 12 hours.After solvent thermal reaction, natural cooling
To room temperature, will be put into baking oven after product filtration washing that reaction obtains, 10 DEG C/min of programmed rate, in 100 DEG C of items
It is 2 hours dry under part.Then it is placed in Muffle furnace and calcines, calcination time is 2 hours, and calcination temperature is 800 DEG C, heating rate
It is 10 DEG C/min.Spherical hierarchical organization stannic oxide/copper oxide composite nano materials are obtained after natural cooling.The ruler of big ball
Very little is 5 μm, and the size of nanoparticle is 20 nm, and the yield of product is 99.9%.Product purity is 99.97%, impurity carbon content
Less than 0.03%.Product has at 340 nm, 590 nm and 720 nm tri- stronger respectively in UV-vis absorption spectrum
Absorption peak.
Using prepared spherical hierarchical organization stannic oxide/copper oxide composite nano materials as photochemical catalyst (0.1g/
L), degrade the methyl orange solution of 10mg/L.Light source used is 300W xenon lamp in photocatalysis experiment.Before irradiation, contain catalysis material
The methyl orange solution of material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.Catalytic activity is evaluated in photocatalysis
Experiment in, 60 minutes degradation rates are 99.3%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, it is characterised in that: by acetyl
The ratio that acetone copper and tin tetrachloride are 1:1 according to molar ratio is put into stirring and dissolving in methanol, acetylacetone copper after precise
Molar concentration be 0.01 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 200 DEG C,
The solvent thermal reaction time is 24 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 5 DEG C/min of programmed rate, it is 5 hours dry under the conditions of 120 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 8 hours, and calcination temperature is 500 DEG C, and heating rate is 10 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization stannic oxide/copper oxide composite nano materials；The size of big ball is 3 μm, and the size of nanoparticle is 20
Nm, the yield of product are 99.0%；Product purity is 99.95%, and impurity carbon content is less than 0.05%；Product is in ultraviolet-visible
In absorption spectrum, there is stronger absorption peak at 330nm, 590 nm and 710 nm tri- respectively.
2. a kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, it is characterised in that: by acetyl
The ratio that acetone copper and tin tetrachloride are 1:1 according to molar ratio is put into stirring and dissolving in methanol, acetylacetone copper after precise
Molar concentration be 0.02 mol/L, by obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 110 DEG C,
The solvent thermal reaction time is 48 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 5 DEG C/min of programmed rate, it is 5 hours dry under the conditions of 120 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 4 hours, and calcination temperature is 700 DEG C, and heating rate is 10 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization stannic oxide/copper oxide composite nano materials；The size of big ball is 6 μm, and the size of nanoparticle is 30
Nm, the yield of product are 99.7%；Product purity is 99.97%, and impurity carbon content is less than 0.03%；Product is in ultraviolet-visible
In absorption spectrum, there is stronger absorption peak at 340 nm, 600 nm and 710 nm tri- respectively.
3. a kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, it is characterised in that: by acetyl
The ratio that acetone copper and tin tetrachloride are 1:1 according to molar ratio is put into stirring and dissolving in methanol, acetylacetone copper after precise
Molar concentration be 0.03 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 220 DEG C,
The solvent thermal reaction time is 12 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 5 hours dry under the conditions of 100 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 5 hours, and calcination temperature is 800 DEG C, and heating rate is 10 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization stannic oxide/copper oxide composite nano materials；The size of big ball is 4 μm, and the size of nanoparticle is 25
Nm, the yield of product are 99.8%；Product purity is 99.96%, and impurity carbon content is less than 0.04%；Product is in ultraviolet-visible
In absorption spectrum, there is stronger absorption peak at 340 nm, 610 nm and 720nm tri- respectively.
4. a kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, it is characterised in that: by acetyl
The ratio that acetone copper and tin tetrachloride are 1:1 according to molar ratio is put into stirring and dissolving in methanol, acetylacetone copper after precise
Molar concentration be 0.05mol/L；Obtained mixed solution is subjected to solvent thermal reaction, solvent thermal reaction temperature is molten at 220 DEG C
The agent thermal response time is 6 hours；After solvent thermal reaction, cooled to room temperature, the product filtration washing that reaction is obtained
After be put into baking oven, 10 DEG C/min of programmed rate, dry 1 hour under the conditions of 120 DEG C；Then it is placed in Muffle furnace
Calcining, calcination time are 2 hours, and calcination temperature is 800 DEG C, and heating rate is 20 DEG C/min；Ball is obtained after natural cooling
Shape hierarchical organization stannic oxide/copper oxide composite nano materials；The size of big ball is 5.5 μm, and the size of nanoparticle is 10
Nm, the yield of product are 99.1%；Product purity is 99.98%, and impurity carbon content is less than 0.02%；Product is in ultraviolet-visible
In absorption spectrum, there is stronger absorption peak at 350nm, 610 nm and 730 nm tri- respectively.
5. a kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials, it is characterised in that: by acetyl
The ratio that acetone copper and tin tetrachloride are 1:1 according to molar ratio is put into stirring and dissolving in methanol, acetylacetone copper after precise
Molar concentration be 0.1 mol/L；By obtained mixed solution carry out solvent thermal reaction, solvent thermal reaction temperature at 200 DEG C,
The solvent thermal reaction time is 12 hours；After solvent thermal reaction, the product that reaction obtains is crossed diafiltration by cooled to room temperature
It is put into baking oven after washing, 10 DEG C/min of programmed rate, it is 2 hours dry under the conditions of 100 DEG C；Then it is placed on Muffle furnace
Middle calcining, calcination time are 2 hours, and calcination temperature is 800 DEG C, and heating rate is 10 DEG C/min；It is obtained after natural cooling
Spherical hierarchical organization stannic oxide/copper oxide composite nano materials；The size of big ball is 5 μm, and the size of nanoparticle is 20
Nm, the yield of product are 99.9%；Product purity is 99.97%, and impurity carbon content is less than 0.03%；Product is in ultraviolet-visible
In absorption spectrum, there is stronger absorption peak at 340 nm, 590 nm and 720nm tri- respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610816596.1A CN106391038B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610816596.1A CN106391038B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106391038A CN106391038A (en) | 2017-02-15 |
| CN106391038B true CN106391038B (en) | 2019-02-05 |
Family
ID=57999989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610816596.1A Expired - Fee Related CN106391038B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106391038B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109422289A (en) * | 2017-08-23 | 2019-03-05 | 张家港市六福新材料科技有限公司 | A kind of copper oxide-stannic oxide catalyst powder and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776311A (en) * | 2016-05-23 | 2016-07-20 | 渤海大学 | Method for preparing copper oxide nano material |
-
2016
- 2016-09-12 CN CN201610816596.1A patent/CN106391038B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776311A (en) * | 2016-05-23 | 2016-07-20 | 渤海大学 | Method for preparing copper oxide nano material |
Non-Patent Citations (3)
| Title |
|---|
| Hydrothermal Synthesis of CuO-SnO2 and CuO-SnO2-Fe2O3 Mixed Oxides and their Electrochemical Characterization in Neutral Electrolyte;M. Jayalakshmi,et.al.;《Int. J. Electrochem. Sci.》;20090322;第4卷;第571-581页 |
| Photocatalytic degradation of Acid Blue 62 over CuO-SnO2 nanocomposite photocatalyst under simulated sunlight;XIA Hui-li,et.al.;《Journal of Environmental Sciences》;20071231;第19卷;第1142页Experimental，第1143页表1，第1144页图5 |
| Photocatalytic Degradation of Malachite Green and Rhodamine B Dye over SnO2-CuO Binary Metal Oxide Nanocomposite under UV Light;Jyoshna Marpally;《NATIONAL INSTITUTE OF TECHNOLOGY，ROURKELA论文》;20160309;第15页1.8节，第16页2.3节，第21-22页3.1.4节，图8 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106391038A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ali et al. | Effect of calcination temperature on the photoactivities of ZnO/SnO2 nanocomposites for the degradation of methyl orange | |
| CN106582765B (en) | A kind of the natrium doping graphite phase carbon nitride and its application of one-step synthesis preparation | |
| CN106824246B (en) | A kind of TiO2/g-C3N4The preparation method of composite visible light catalyst | |
| Han et al. | Controllable synthesis of Sn-doped BiOCl for efficient photocatalytic degradation of mixed-dye wastewater under natural sunlight irradiation | |
| CN105905940B (en) | A kind of preparation method of nickel titanate/titanium dioxide composite nano material | |
| CN105854906A (en) | BiOCl-TiO2/diatomite photocatalyst and preparation method thereof | |
| CN106391014B (en) | Titanium dioxide/copper oxide composite oxide nano-material preparation method | |
| Astuti et al. | Studying impact of different precipitating agents on crystal structure, morphology and photocatalytic activity of bismuth oxide | |
| CN104646003B (en) | Nd3-xCoxNbO7The preparation and application of the compound porous nano catalytic material of Si-Zn molecular sieve | |
| CN106955721A (en) | A kind of preparation method of the Bi5O7Br nano-photocatalyst materials of banded structure | |
| CN106365194B (en) | A kind of preparation method of lanthanium titanate nano material | |
| CN106693996B (en) | Preparation method and application of bismuth sulfide-bismuth ferrite composite visible-light-driven photocatalyst | |
| CN105854867B (en) | A kind of preparation method of zinc oxide/stancic oxide antimony composite nano materials | |
| Wang et al. | Large-scale synthesis of carbon dots/TiO 2 nanocomposites for the photocatalytic color switching system | |
| CN105645469A (en) | Nano rodlike lanthanum titanate powder and preparation method thereof | |
| CN103721699A (en) | NaInO2 photocatalyst and preparation method thereof | |
| CN106311240B (en) | A kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material | |
| CN100493708C (en) | High-activity phosphor doped peptide oxide light catalyst, its production and use | |
| CN109382088B (en) | SnO2/α～Bi2O3/β～Bi2O3Composite material and preparation method thereof | |
| CN103395834A (en) | Method used for preparing anatase type core-shell nanometer titanium dioxide and application of anatase type core-shell nanometer titanium dioxide in dye degradation | |
| CN106391038B (en) | A kind of preparation method of spherical shape hierarchical organization stannic oxide/copper oxide composite nano materials | |
| CN108654663B (en) | Boron-nitrogen co-doped single crystal mesoporous TiO prepared by mixed nitrate molten salt method2Method for catalyzing materials | |
| CN104226335B (en) | A kind of multilevel hierarchy bismuth sulfide and its preparation method and application | |
| CN107149939B (en) | A kind of g-C3N4/Al2O3/ZnO hetero-junctions of visible light catalysis activity and preparation method thereof | |
| CN106076311B (en) | A kind of preparation method of titanium dioxide/stannic oxide complex oxide ultrafine nano particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190205 Termination date: 20190912 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |