CN105817241A - Method for preparing copper phosphotungstate@titanium dioxide core-shell structured nanomaterial - Google Patents
Method for preparing copper phosphotungstate@titanium dioxide core-shell structured nanomaterial Download PDFInfo
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- CN105817241A CN105817241A CN201610338137.7A CN201610338137A CN105817241A CN 105817241 A CN105817241 A CN 105817241A CN 201610338137 A CN201610338137 A CN 201610338137A CN 105817241 A CN105817241 A CN 105817241A
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- phosphotungstic acid
- acid copper
- titanium dioxide
- dioxide core
- nano material
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 50
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 43
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 12
- 238000000034 method Methods 0.000 title abstract description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 230000008020 evaporation Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 230000010355 oscillation Effects 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 25
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 19
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 19
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 15
- 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
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 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 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 239000001048 orange dye Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000002798 spectrophotometry method 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MQZWLTQJBAHPGF-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Cu+2] Chemical compound [O-2].[O-2].[Ti+4].[Cu+2] MQZWLTQJBAHPGF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/39—
-
- B01J35/40—
Abstract
The invention belongs to the technical field of functional material preparation, and relates to a method for preparing a copper phosphotungstate@titanium dioxide core-shell structured nanomaterial .Soluble metal copper salt and phosphotungstic acid are fully mixed in alcohol/water solution, then hydrothermal reaction is conducted, and micro-spheres formed by copper phosphotungstate nanoparticles are obtained through heat treatment .The obtained copper phosphotungstate micro-spheres are stirred in isopropanol solution and subjected to ultrasonic oscillation, and then titanium acetylacetonate is added dropwise slowly; then stirring is conducted, and slow evaporation is conducted, so that a precursor is obtained; the target product is obtained after calcination of the precursor .The process is simple and easy to implement, purity is high, impurity content is low, preparation cost is low, performance is excellent, and bulk industrial production can be achieved .The prepared copper phosphotungstate@titanium dioxide core-shell structured nanomaterial can serve as a visible-light response photocatalyst, and has broad application prospects in the fields of dye wastewater and indoor harmful gas degradation and photocatalysis disinfection.
Description
Technical field
The invention belongs to the preparing technical field of functional material, concretely relate to the preparation method of a kind of phosphotungstic acid copper titanium dioxide core shell structural nano material.
Background technology
1972, Fujishima et al. delivered on Nature and has utilized TiO2After the experimental result of semi-conducting electrode photolysis water hydrogen making and oxygen, the research of conductor photocatalysis has quickly started upsurge and (has seen HondaK, FujishimaA.Electrochemicalphotolysisofwateratasemiconduc torelectrode.Nature, 1972,238,37 38).TiO2Because of its stable chemical nature, the catalysis activity advantage such as high, nontoxic, cheap, it is considered as the catalysis material having most exploitation potential quality in the decontamination system application of the different pollutant of degraded and eliminating bacteria.But TiO2Energy gap (3.2eV) wider, the utilization ratio for solar energy is relatively low.It is by the method compound with narrow gap semiconductor based on the maximally effective method of modifying of wide band gap semiconducter, the meaning of composite semiconductor is the semiconductive particles with different level structure, utilize the energy level difference between two kinds of quasiconductors that photo-generated carrier can be made to be injected on another kind of quasiconductor energy level by the energy level of a kind of semiconductor grain, result in effective separation of charge, it is possible not only to effectively to suppress the compound of light induced electron and hole, and extends spectral response scope.
The present invention announces the preparation method of a kind of phosphotungstic acid copper titanium dioxide core shell structural nano material.Core-shell particle is by chemical bond or other active forces, another kind of nano material to be coated with the ordered fabrication structure of the nanoscale formed that gets up by a kind of nano material." " in " phosphotungstic acid copper titanium dioxide " represents the meaning of cladding, often occurs in english literature, and meaning phosphotungstic acid copper is core, at center；Titanium dioxide is shell, at outer layer.Coating technology is cut out by internal karyomicrosome surface nature, changes core surface electric charge, functional group and response characteristic, improves stability and the dispersibility of kernel.Nucleocapsid structure is the most quite favored by investigation of materials personnel, especially nano-photo catalytic researcher.
Summary of the invention
It is contemplated that provide the preparation method of a kind of phosphotungstic acid copper titanium dioxide core shell structural nano material in place of overcoming the deficiencies in the prior art, the method purpose product yield and purity are high, preparation technology is simple and easy to do, mild condition, prepared phosphotungstic acid copper titanium dioxide core shell structural nano material has good photocatalysis performance, under visible light, under the process conditions of photocatalytic degradation of dye, within 60 minutes, degradation rate has reached more than 95.0%.
For reaching above-mentioned purpose, the present invention is realized in.
A kind of preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material, including three steps: soluble metal mantoquita and phosphotungstic acid are sufficiently mixed to continue in alcohol/aqueous solution and carry out hydro-thermal reaction by (1), after heat treatment, the micron ball assembled by phosphotungstic acid copper nano particles is i.e. obtained；(2) gained phosphotungstic acid copper micron ball is stirred and after sonic oscillation in isopropanol water solution, be slowly added dropwise titanium acetylacetone；Then being stirred for, continue slow evaporation, obtains predecessor；(3), after being calcined by gained predecessor, purpose product is obtained.
Further, in described step (1), soluble metal mantoquita is one or more the mixture in copper chloride, copper sulfate, copper nitrate or copper acetate.
Further, in described step (1), the alcohol in alcohol/aqueous solution is one or more the mixture in methanol, ethanol, ethylene glycol or isopropanol, and the volume ratio of alcohol and water is 1: 0.1～10.
Further, in described step (1), the molar concentration of soluble metal mantoquita and phosphotungstic acid is 0.01～2mol/L；Described soluble metal mantoquita is 1: 0.2～5 with the mol ratio of phosphotungstic acid.
Further, in described step (1), hydrothermal temperature is at 160～230 DEG C, and the response time is 6～48 hours.
Further, in described step (2), mixing time is 24～48 hours；Mixing speed is 900～1200 revs/min；The sonic oscillation time is 3～6 hours.
Further, in described step (2), titanium acetylacetone rate of addition is 10～60 droplets/minute；Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1: 0.2～5.
Further, the time being stirred in described step (2) is 6～48 hours；Being stirred for speed is 300～600 revs/min；The temperature of evaporation is 70～110 DEG C.
Further, in described step (3), calcining heat is 300～600 DEG C, and the time is 3～6 hours.
Compared with prior art, the present invention has following features.
(1) present invention develops and prepares phosphotungstic acid copper titanium dioxide core shell structural nano material new technology route, this technique preparation cost is low, easy to control, prepared nano material is nucleocapsid structure ball shaped nano material, center material be diameter in 20～50nm phosphotungstic acid copper ball shape nano materials, shell is that thickness 10～30nm is at titanium dioxide nano material.
(2) purpose product yield (99.5%～99.8%), product purity high (99.7%～99.9%) can meet the industrial application requirement to visible light catalytic material product.
(3) the purpose product phosphotungstic acid copper titanium dioxide core shell structural nano material that prepared by the present invention is in response to can be by the catalysis material of light, and within 60 minutes, degradation rate can reach (95.0%～99.5%), has higher catalysis activity.
Accompanying drawing explanation
The invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings.Protection scope of the present invention is not only limited to the statement of following content.
Fig. 1 is the SEM figure of the sphere material that the phosphotungstic acid copper nano particles prepared by the present invention assembles.
Fig. 2 is the SEM figure of the sphere material that the phosphotungstic acid copper nano particles prepared by the present invention assembles.
Fig. 3 is the SEM figure of the sphere material that the phosphotungstic acid copper nano particles prepared by the present invention assembles.
Fig. 4 is the X-ray diffractogram of the sphere material that the phosphotungstic acid copper nano particles prepared by the present invention assembles.
Fig. 5 is the TEM figure of the phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by the present invention.
Fig. 6 is the TEM figure of the phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by the present invention.
Detailed description of the invention
The present invention designs a kind of solution phase chemistries, by new chemical preparation approach in phosphotungstic acid copper nanosphere outer cladding layer of titanium dioxide nano material, thus constructs Core-shell structure material.The photocatalysis property of phosphotungstic acid copper titanium dioxide core shell structural nano material can be estimated by photocatalytic degradation of dye.
The present invention is sufficiently mixed in alcohol/aqueous solution with soluble metal mantoquita and phosphotungstic acid, continues and carries out hydro-thermal reaction, after heat treatment, i.e. obtains the micron ball assembled by phosphotungstic acid copper nano particles.Gained phosphotungstic acid copper micron ball is stirred and after sonic oscillation in isopropanol water solution, is slowly added dropwise titanium acetylacetone.Then being stirred for, continue slow evaporation, obtains predecessor.After being calcined by gained predecessor, obtain purpose product.
Preparation process of the present invention is.
(1) molar concentration of soluble metal mantoquita and phosphotungstic acid is 0.01～2mol/L；Described soluble metal mantoquita is 1: 0.2～5 with the mol ratio of phosphotungstic acid.Hydrothermal temperature is at 160～230 DEG C, and the response time is 6～48 hours, i.e. obtains the phosphotungstic acid copper micron ball assembled by phosphotungstic acid copper nano particles.
(2) being stirred in isopropanol water solution 24～48 hours by gained phosphotungstic acid copper micron ball, mixing speed is 900～1200 revs/min, and sonic oscillation 3～6 hours.Then being slowly added dropwise titanium acetylacetone, rate of addition is 10～60 droplets/minute.Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1: 0.2～5.Then being stirred for 6～48 hours, being stirred for speed is 300～600 revs/min.It is connected at 70～110 DEG C of slow evaporations, obtains predecessor.
(3) predecessor being put into Muffle furnace and carry out heat treatment, calcining heat is 300～600 DEG C, and the time is 3～6 hours, i.e. prepares phosphotungstic acid copper titanium dioxide core shell structural nano material.
(4) the phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by utilization is as photocatalyst (0.2g/L), the methyl orange solution of degraded 10mg/L.In photocatalysis experiment, light source used is 300W xenon lamp (simulated solar irradiation).Before irradiation, the methyl orange solution containing catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye concentration, calculate degradation rate.
See shown in Fig. 1～3, the phosphotungstic acid copper micron ball SEM figure assembled for the phosphotungstic acid copper nano particles of the present invention.As a result of which it is, the diameter of micron ball is in 1～3 μm, the diameter of phosphotungstic acid copper nano particles is 10～30nm.Fig. 4 is the X-ray diffractogram of the sphere material that the phosphotungstic acid copper nano particles prepared by the present invention assembles.See shown in Fig. 5 and 6, for the present invention phosphotungstic acid copper titanium dioxide core shell structural nano material TEM scheme, its result be the diameter of nuclear material phosphotungstic acid copper 10～30nm, the thickness of shell material is 5～10nm.
Embodiment 1.
The alcohol-water solution that concentration is 0.15mol/L copper acetate is slowly dropped in the alcohol-water solution that concentration is 0.1mol/L phosphotungstic acid.Wherein alcohol-water solution is that second alcohol and water is prepared according to v:v=1:1, and the mixed solution obtained is carried out hydro-thermal reaction by the molar ratio computing of copper acetate/phosphotungstic acid=1.5:1, and hydrothermal temperature is at 180 DEG C, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction terminates, naturally cool to room temperature, after product reaction obtained filters washing, put in baking oven, under the conditions of 40 DEG C, be dried 4 hours, obtain the phosphotungstic acid copper micron ball that phosphotungstic acid copper nano particles assembles.Being stirred in isopropanol water solution 24 hours by gained phosphotungstic acid copper micron ball, mixing speed is 900 revs/min, and sonic oscillation 6 hours.Then being slowly added dropwise titanium acetylacetone, rate of addition is 60 droplets/minute.Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1:1.Then being stirred for 24 hours, being stirred for speed is 600 revs/min.It is connected at 100 DEG C of slow evaporations, obtains predecessor.Predecessor being put into Muffle furnace and carries out heat treatment, calcining heat is 300 DEG C, and the time is 3 hours, i.e. prepares phosphotungstic acid copper titanium dioxide core shell structural nano material.
The yield of its product is 99.8%.Product purity is not less than 99.9%, impurity content: carbon is less than 0.1%.Phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by utilization is as photocatalyst (0.2g/L), the methyl orange solution of degraded 10mg/L.In photocatalysis experiment, light source used is 300W xenon lamp (simulated solar irradiation).Before irradiation, the methyl orange solution containing catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye concentration, calculate degradation rate.In the test of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 99.5%, and the degradation rate of 120 minutes is 99.9%.
Embodiment 2.
The alcohol-water solution that concentration is 0.15mol/L copper chloride is slowly dropped in the alcohol-water solution that concentration is 0.1mol/L phosphotungstic acid.Wherein alcohol-water solution is that second alcohol and water is prepared according to v:v=1:1, and the mixed solution obtained is carried out hydro-thermal reaction by the molar ratio computing of copper chloride/phosphotungstic acid=1.5:1, and hydrothermal temperature is at 180 DEG C, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction terminates, naturally cool to room temperature, after product reaction obtained filters washing, put in baking oven, under the conditions of 40 DEG C, be dried 4 hours, obtain the phosphotungstic acid copper micron ball that phosphotungstic acid copper nano particles assembles.Being stirred in isopropanol water solution 24 hours by gained phosphotungstic acid copper micron ball, mixing speed is 900 revs/min, and sonic oscillation 6 hours.Then being slowly added dropwise titanium acetylacetone, rate of addition is 60 droplets/minute.Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1:1.Then being stirred for 24 hours, being stirred for speed is 600 revs/min.It is connected at 100 DEG C of slow evaporations, obtains predecessor.Predecessor being put into Muffle furnace and carries out heat treatment, calcining heat is 300 DEG C, and the time is 3 hours, i.e. prepares phosphotungstic acid copper titanium dioxide core shell structural nano material.
The yield of its product is 99.5%.Product purity is not less than 99.7%, impurity content: carbon is less than 0.3%.Phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by utilization is as photocatalyst (0.2g/L), the methyl orange solution of degraded 10mg/L.In photocatalysis experiment, light source used is 300W xenon lamp (simulated solar irradiation).Before irradiation, the methyl orange solution containing catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye concentration, calculate degradation rate.In the test of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 95.0%, and the degradation rate of 120 minutes is 97.5%.
Embodiment 3.
The alcohol-water solution that concentration is 0.15mol/L copper nitrate is slowly dropped in the alcohol-water solution that concentration is 0.1mol/L phosphotungstic acid.Wherein alcohol-water solution is that second alcohol and water is prepared according to v:v=1:1, and the mixed solution obtained is carried out hydro-thermal reaction by the molar ratio computing of copper nitrate/phosphotungstic acid=1.5:1, and hydrothermal temperature is at 180 DEG C, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction terminates, naturally cool to room temperature, after product reaction obtained filters washing, put in baking oven, under the conditions of 40 DEG C, be dried 4 hours, obtain the phosphotungstic acid copper micron ball that phosphotungstic acid copper nano particles assembles.Being stirred in isopropanol water solution 24 hours by gained phosphotungstic acid copper micron ball, mixing speed is 900 revs/min, and sonic oscillation 6 hours.Then being slowly added dropwise titanium acetylacetone, rate of addition is 60 droplets/minute.Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1:1.Then being stirred for 24 hours, being stirred for speed is 600 revs/min.It is connected at 100 DEG C of slow evaporations, obtains predecessor.Predecessor being put into Muffle furnace and carries out heat treatment, calcining heat is 300 DEG C, and the time is 3 hours, i.e. prepares phosphotungstic acid copper titanium dioxide core shell structural nano material.
The yield of its product is 99.6%.Product purity is not less than 99.8%, impurity content: carbon is less than 0.2%.Phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by utilization is as photocatalyst (0.2g/L), the methyl orange solution of degraded 10mg/L.In photocatalysis experiment, light source used is 300W xenon lamp (simulated solar irradiation).Before irradiation, the methyl orange solution containing catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye concentration, calculate degradation rate.In the test of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 98.9%, and the degradation rate of 120 minutes is 99.4%.
Embodiment 4.
The alcohol-water solution that concentration is 0.15mol/L copper acetate is slowly dropped in the alcohol-water solution that concentration is 0.1mol/L phosphotungstic acid.Wherein alcohol-water solution is that isopropyl alcohol and water is prepared according to v:v=1:2, and the mixed solution obtained is carried out hydro-thermal reaction by the molar ratio computing of copper acetate/phosphotungstic acid=1.5:1, and hydrothermal temperature is at 180 DEG C, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction terminates, naturally cool to room temperature, after product reaction obtained filters washing, put in baking oven, under the conditions of 40 DEG C, be dried 4 hours, obtain the phosphotungstic acid copper micron ball that phosphotungstic acid copper nano particles assembles.Being stirred in isopropanol water solution 36 hours by gained phosphotungstic acid copper micron ball, mixing speed is 1200 revs/min, and sonic oscillation 3 hours.Then being slowly added dropwise titanium acetylacetone, rate of addition is 60 droplets/minute.Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1:1.Then being stirred for 24 hours, being stirred for speed is 600 revs/min.It is connected at 100 DEG C of slow evaporations, obtains predecessor.Predecessor being put into Muffle furnace and carries out heat treatment, calcining heat is 300 DEG C, and the time is 3 hours, i.e. prepares phosphotungstic acid copper titanium dioxide core shell structural nano material.
The yield of its product is 99.7%.Product purity is not less than 99.8%, impurity content: carbon is less than 0.2%.Phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by utilization is as photocatalyst (0.2g/L), the methyl orange solution of degraded 10mg/L.In photocatalysis experiment, light source used is 300W xenon lamp (simulated solar irradiation).Before irradiation, the methyl orange solution containing catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye concentration, calculate degradation rate.In the test of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 99.4%, and the degradation rate of 120 minutes is 99.8%.
Embodiment 5.
The alcohol-water solution that concentration is 0.30mol/L copper acetate is slowly dropped in the alcohol-water solution that concentration is 0.2mol/L phosphotungstic acid.Wherein alcohol-water solution is that first alcohol and water is prepared according to v:v=1:3, and the mixed solution obtained is carried out hydro-thermal reaction by the molar ratio computing of copper acetate/phosphotungstic acid=1.5:1, and hydrothermal temperature is at 200 DEG C, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction terminates, naturally cool to room temperature, after product reaction obtained filters washing, put in baking oven, under the conditions of 40 DEG C, be dried 4 hours, obtain the phosphotungstic acid copper micron ball that phosphotungstic acid copper nano particles assembles.Being stirred in isopropanol water solution 24 hours by gained phosphotungstic acid copper micron ball, mixing speed is 900 revs/min, and sonic oscillation 6 hours.Then being slowly added dropwise titanium acetylacetone, rate of addition is 60 droplets/minute.Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1:1.Then being stirred for 24 hours, being stirred for speed is 600 revs/min.It is connected at 100 DEG C of slow evaporations, obtains predecessor.Predecessor being put into Muffle furnace and carries out heat treatment, calcining heat is 300 DEG C, and the time is 3 hours, i.e. prepares phosphotungstic acid copper titanium dioxide core shell structural nano material.
The yield of its product is 99.7%.Product purity is not less than 99.8%, impurity content: carbon is less than 0.2%.Phosphotungstic acid copper titanium dioxide core shell structural nano material prepared by utilization is as photocatalyst (0.2g/L), the methyl orange solution of degraded 10mg/L.In photocatalysis experiment, light source used is 300W xenon lamp (simulated solar irradiation).Before irradiation, the methyl orange solution containing catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye concentration, calculate degradation rate.In the test of photocatalysis evaluation catalysis activity, the degradation rate of 60 minutes is 97.6%, and the degradation rate of 120 minutes is 98.8%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (9)
1. the preparation method of a phosphotungstic acid copper titanium dioxide core shell structural nano material, it is characterised in that comprise the steps of:
(1) soluble metal mantoquita and phosphotungstic acid are sufficiently mixed in alcohol/aqueous solution, continue and carry out hydro-thermal reaction, after heat treatment, i.e. obtain the phosphotungstic acid copper micron ball assembled by phosphotungstic acid copper nano particles；
(2) step (1) gained phosphotungstic acid copper micron ball is stirred and after sonic oscillation in isopropanol water solution, be slowly added dropwise titanium acetylacetone；Then being stirred for, continue slow evaporation, obtains predecessor；
(3), after being calcined by step (2) gained predecessor, purpose product is obtained.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 1, it is characterised in that: in described step (1), soluble metal mantoquita is one or more the mixture in copper chloride, copper sulfate, copper nitrate or copper acetate.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 2, it is characterized in that: in described step (1), the alcohol in alcohol/aqueous solution is one or more the mixture in methanol, ethanol, ethylene glycol or isopropanol, and the volume ratio of alcohol and water is 1: 0.1～10.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 3, it is characterised in that: in described step (1), the molar concentration of soluble metal mantoquita and phosphotungstic acid is 0.01～2mol/L；Described soluble metal mantoquita is 1: 0.2～5 with the mol ratio of phosphotungstic acid.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 4, it is characterised in that: in described step (1), hydrothermal temperature is at 160～230 DEG C, and the response time is 6～48 hours.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 5, it is characterised in that: in described step (2), mixing time is 24～48 hours；Mixing speed is 900～1200 revs/min；The sonic oscillation time is 3～6 hours.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 6, it is characterised in that: in described step (2), titanium acetylacetone rate of addition is 10～60 droplets/minute；Titanium acetylacetone with the mol ratio of phosphotungstic acid copper is: 1: 0.2～5.
The preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material the most according to claim 7, it is characterised in that: the time being stirred in described step (2) is 6～48 hours；Being stirred for speed is 300～600 revs/min；The temperature of evaporation is 70～110 DEG C.
9. according to the preparation method of the arbitrary described phosphotungstic acid copper titanium dioxide core shell structural nano material of claim 1～8, it is characterised in that: in described step (3), calcining heat is 300～600 DEG C, and the time is 3～6 hours.
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