CN105921149B - A kind of method of solvent hot preparation copper modified titanic oxide nanometer rods - Google Patents
A kind of method of solvent hot preparation copper modified titanic oxide nanometer rods Download PDFInfo
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- CN105921149B CN105921149B CN201610313734.4A CN201610313734A CN105921149B CN 105921149 B CN105921149 B CN 105921149B CN 201610313734 A CN201610313734 A CN 201610313734A CN 105921149 B CN105921149 B CN 105921149B
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- nanometer rods
- titanic oxide
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- 239000010949 copper Substances 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 44
- -1 copper modified titanic oxide Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002904 solvent Substances 0.000 title claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000013019 agitation Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229920002620 polyvinyl fluoride Polymers 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000012153 distilled water Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000005406 washing Methods 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 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 238000006303 photolysis reaction Methods 0.000 claims description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 46
- 239000000243 solution Substances 0.000 description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 13
- 239000002073 nanorod Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005562 fading Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 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 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 5
- 229910003068 Ti(C4H9O)4 Inorganic materials 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/72—Copper
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/176—Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Abstract
The present invention relates to a kind of method of solvent hot preparation copper modified titanic oxide nanometer rods, methods described comprises the following steps：S1：Mantoquita is added in ethylene glycol solution, is sufficiently stirred, titanium-containing compound is then added into solution, strong agitation, it is standby to obtain mixed liquor；S2：Mixed liquor obtained by step S1 is transferred in the hydrothermal reaction kettle of the polyvinyl fluoride of liner four, and hydrothermal reaction kettle is placed in drying condition and keeps reacting under 200 DEG C of conditions above of constant temperature, is subsequently cooled to room temperature；S3：Step S2 products therefroms are filtered, washed, are drying to obtain copper modified titanic oxide nanometer rods.The copper modified titanic oxide nanometer rods size that solvent method provided by the invention is prepared is controllable, uniform in size, has excellent photocatalytic activity.
Description
Technical field
The present invention relates to technical field of preparation for inorganic material, and in particular to a kind of solvent hot preparation copper modified titanic oxide is received
The method of rice rod.
Background technology
Environmental pollution and energy shortage are to perplex two hang-ups of current world economy development.The use of a large amount of fossil fuels
Huge pollution not only is caused to global environment and ecology, and these energy are non-renewable resources, and global storage contains
Amount estimates that the middle of this century will be exhausted.Solar energy is inexhaustible regenerative resource, utilizes solar energy
Water hydrogen manufacturing and environment degradable is catalytically decomposed, is to solve one of energy crisis and the maximally effective approach of environmental problem of increasingly significant,
And China realize the Sustainable Development Strategy and uplift the people's living standard there is an urgent need to.From Japanese Scientists in 1972
Honda and Fujishima etc. has found TiO2Since Single Crystalline Electrodes have certain redox property in the presence of light, attract
Countries in the world scientist constantly to go to explore and study.Therefore, conductor photocatalysis material research is carried out in a deep going way fundamentally
Solving the energy and environmental problem has important Research Significance.
TiO2It is not soluble in water, have resistance to corrosion it is strong, it is cheap and conveniently handle, biological function, photochemical properties are stable,
The advantages that environmentally safe, it is a kind of preferable photochemical catalyst.But TiO2Band gap be 3.2 eV, can be less than in wavelength
380 below nm ultraviolet light responds, and in solar spectrum ultraviolet light less than 5%, and wavelength be 400~750 nm it is visible
Light accounts for 45% or so, and this fundamentally constrains TiO2Photocatalyst applications.At present, researcher is multiple by doping, semiconductor
The methods of conjunction, dye sensitization, noble-metal-supported, widens TiO2Light absorbs band edge, improve photocatalytic activity.Noble-metal-supported
It is to TiO2A kind of modified effective method, it can not only promote TiO2Light absorbs band edge red shift, and TiO can be improved2
Photocatalytic activity；The domestic existing relevant report of Cu modified titanic oxides nanometer rods, but existing method mostly using two steps or
Three one step process：Titanium dioxide nano-rod is prepared in alkaline solution first, then Direct precipitation elemental copper；Or deposited oxide
Copper, then reduction treatment is carried out in hydrogen atmosphere.As follows stand outstanding person etc. and pass through NaBH4Reduce CuCl2In TiO2The surface of nanometer rods into
Work(has loaded Cu nano particles.Wan et al. prepares Cu (OH) in the basic conditions first2/TiO2Nanometer rods, then again in H2/
400 DEG C of calcining 4h in Ar atmosphere, in H2300 DEG C of reduction treatment 2h, obtain Cu/TiO in/Ar atmosphere2Nanometer rods.In strong basicity bar
Under part, Ag (NH are reduced using glucose3)2+Obtain Ag/TiO2Nanometer rods, this method is in Ag (NH3)2+When solution concentration is smaller,
Obtained silver nano-grain is than more uniform, with Ag (NH3)2+The increase of concentration, Argent grain size are very uneven.
Two-step method or three-step approach prepare that noble metal modified titanium dioxide nanometer rods have complex process, complex steps are asked
Topic, and the size for the titanium dioxide nano-rod being prepared is uneven, and photocatalytic activity is poor, and this largely limits two
The use of TiOx nano rod；Therefore, still need to seek it is a kind of prepare size uniform that is simple, obtaining titanium dioxide nano-rod with
And the method that photocatalytic activity is good.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of solvent hot preparation copper modified titanic oxide to receive
The method of rice rod, the copper modified titanic oxide nanometer rods size that solvent method provided by the invention is prepared is controllable, uniform in size,
With excellent photocatalytic activity.
The titanium dioxide nano-rod being prepared another object of the present invention is to provide above-mentioned preparation method.
It is organic in photolysis water hydrogen, degraded another object of the present invention is to provide above-mentioned copper modified titanic oxide nanometer rods
Application in pollutant.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of method of solvent hot preparation copper modified titanic oxide nanometer rods, methods described comprise the following steps：
S1：Mantoquita is added in ethylene glycol solution, is sufficiently stirred, titanium-containing compound is then added into solution, strongly
Stir mixed liquor is standby；
S2：Mixed liquor obtained by step S1 is transferred in the hydrothermal reaction kettle of the polyvinyl fluoride of liner four, and by hydro-thermal reaction
Kettle, which is placed in drying condition, to be kept reacting under 200 DEG C of conditions above of constant temperature, is subsequently cooled to room temperature；
S3：Step S2 products therefroms are filtered, washed, are drying to obtain copper modified titanic oxide nanometer rods.
The present invention selects mantoquita as raw material, using the good titanium-containing compound of the dissolubility in ethylene glycol as titanium source, using second
Glycol is solvent, is reacted in solvent thermal environment, and copper modified titanic oxide nanometer rods can be prepared in a step；The present invention
The good TiO of crystallization degree is directly prepared using the step of solvent method one2Nanometer rods and simple substance copper nano particles.Products therefrom need not
High-temperature process, high-temperature process is avoided to TiO2The pattern of product and the influence of stability, while elemental copper is it also avoid by oxygen
Change.The Cu/TiO that the present invention is prepared2Nanometer rods size is controllable, uniform in size；Copper particle diameter is about below 5nm, distribution
Uniformly, modification amount size is controllable, and the Cu/TiO being prepared2Nanometer rods have excellent visible light catalysis activity, in light
The fields such as the hydrogen manufacturing of solution water, degradable organic pollutant are with a wide range of applications.
There is significant difference in solvent-thermal method provided by the invention, the present invention is from ethylene glycol as anti-with other solvent-thermal methods
Solvent is answered, the boiling point of ethylene glycol is higher, is 197 DEG C, it can be heated to more than 200 DEG C, in the reaction of method provided by the invention
During, ethylene glycol not only as solvent but also was used as reducing agent, and it can be by Cu2+Simple substance Cu is reduced into, without adding any go back
Former agent.When as reaction dissolvent, the Cu/TiO of similar effects of the present invention can not be prepared from the alcohols such as ethanol or glycerine2
Nanometer rods；Preparing Ag/TiO in the prior art2Nanometer rods or Au/TiO2Usually require to add in right amount during nanometer rods
Reducing agent, such as sodium borohydride, but add such reducing agent and bring difficulty to the purifying of product.The present invention selects ethylene glycol
As reaction dissolvent, without adding other reducing agents, the elemental copper nano-particle diameter that reduces to obtain is about below 5nm, size
Controllable, uniform in size, modification amount size is controllable, and gained Cu/TiO2The purity of nanometer rods is high.
Preferably, ethylene glycol selected in the present invention is pure, purity >=99.5% of analysis.
Preferably, mantoquita described in step S1 is the one or more in copper acetate, copper chloride or copper nitrate；It is more highly preferred to
Ground, the mantoquita are copper acetate；Most preferably, the copper acetate（Cu(CH3COO)2∙H2O）To analyze pure, purity 99.0%.
Preferably, the titanium-containing compound in step S1 is the good titanium-containing compound of dissolubility in ethylene glycol；It is more highly preferred to
Ground, the titanium-containing compound in step S1 is butyl titanate and/or isopropyl titanate；Most preferably, the titanium-containing compound is titanium
Acid butyl ester, the butyl titanate（Ti(C4H9O)4）To analyze pure, purity >=99.0%.
Preferably, the mixing time in step S1 is 15~30min.
Preferably, the reaction time in step S2 is 24~48h.
Preferably, washing described in step S3 is respectively to wash precipitation three times using distilled water, absolute ethyl alcohol.
Preferably, dried described in step S3 to be dried in vacuo under the conditions of 60 DEG C.
The copper modified titanic oxide nanometer rods that the above method is prepared.
The size for the copper modified titanic oxide nanometer rods that method provided by the invention is prepared is controllable, uniform in size, tool
There is excellent visible light catalysis activity, be with a wide range of applications in fields such as photolysis water hydrogen, degradable organic pollutants.
Application of the copper modified titanic oxide nanometer rods in photolysis water hydrogen, degradable organic pollutant.
Compared with prior art, the present invention has the advantages that：
The present invention directly prepares the good TiO of crystallization degree using the step of solvent-thermal method one2Nanometer rods and elemental copper nanometer
Particle, products therefrom avoid high-temperature process to TiO without high-temperature process2The pattern and stability influence of product, and avoid
Elemental copper is oxidized, while reduces energy consumption；The diameter of simple substance copper nano particles prepared by an of the invention step solvent method is about
Below 5nm, it is evenly distributed, modification amount size is controllable, and the Cu/TiO prepared2Nanometer rods have excellent visible light catalytic
Activity, it is with a wide range of applications in fields such as photolysis water hydrogen, degradable organic pollutants；It is prepared by method provided by the invention
Technique is simple, reproducible, has larger application value.
Brief description of the drawings
Fig. 1 is Cu/TiO produced by the present invention2Nanometer rods X- powder diffractions（XRD）Figure；
Fig. 2 is Cu/TiO produced by the present invention2Nanometer rods SEM（SEM）And transmission electron microscope picture：(a)Cu/
TiO2Nanometer rods SEM schemes；(b)Cu/TiO2Nanometer rods TEM schemes；(c)Cu/TiO2Nanometer rods HRTEM schemes；(d) oxygen element mapping graph
Picture（Elemental Mapping Images）；(e) titanium elements mapping graph picture；(f) copper mapping graph picture；
Fig. 3 is Cu/TiO produced by the present invention2Nanometer rods photoelectron spectroscopy（XPS）Collection of illustrative plates；
Fig. 4 is Cu/TiO produced by the present invention2Nanometer rods（e）With nitrogen-doped titanium dioxide（N-P25）（a）, reference examples 1 make
Standby Cu/TiO2Nanometer rods（b）, reference examples 2 prepare Cu/TiO2Nanometer rods（c）The Ag/TiO prepared with reference examples 32Nanometer rods
（d）The effect for having carried out photo-catalytic degradation of methyl-orange under visible light action compares figure.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Experimental method used in following embodiments is such as without spy
Different explanation, is conventional method：Used raw material, auxiliary agent etc., unless otherwise specified, being can be from business such as conventional market purchases
The raw material and auxiliary agent that approach obtains.
Embodiment 1：The preparation of photochemical catalyst 1
In 100 ml beaker, 188 mg copper acetates will be added（（Cu(CH3COO)2∙H2O, 99.0%））To filling 25
Ml ethylene glycol（HO-CH2-CH2- OH, purity >=99.5%）In solution, after being sufficiently stirred, 0.365 ml butyl titanates are slowly dropped into
（Ti(C4H9O)4, purity >=99.0%）Solution, strong agitation 30min, it is then transferred into the polyvinyl fluoride reactor of 50ml liners four
In 200 DEG C of constant temperature keep 24h, naturally cool to room temperature, products therefrom is filtered, and precipitation wash respectively with distilled water, absolute ethyl alcohol
Three times, then at 60 DEG C, 24 h are dried in vacuo, Cu/TiO is made2Nanometer rods.TiO is prepared using this step2The length of nanometer rods
Degree is about 200nm, and diameter is about 20nm, and surface, which can be clearly visible, has copper nano particles, and size is about 3~5 nm.
The preparation of the photochemical catalyst 2 of embodiment 2
In 100 ml beaker, 376 mg copper nitrates will be added（（Cu(CH3COO)2∙H2O, 99.0%））To filling 25
Ml ethylene glycol（HO-CH2-CH2- OH, purity >=99.5%）In solution, after being sufficiently stirred, 0.365 ml butyl titanates are slowly dropped into
（Ti(C4H9O)4, purity >=99.0%）Solution, strong agitation 30min, it is then transferred into the polyvinyl fluoride reactor of 50ml liners four
In 200 DEG C of constant temperature keep 36 h, naturally cool to room temperature, products therefrom is filtered, and precipitation is washed with distilled water, absolute ethyl alcohol
Respectively three times, then at 60 DEG C, 24 h are dried in vacuo, Cu/TiO is made2Nanometer rods.TiO is prepared using this step2Nanometer rods
Length is about 200nm, and diameter is about 20nm, and surface, which can be clearly visible, has copper nano particles, and size is about 3~5 nm, particle
Showed increased.
The preparation of the photochemical catalyst 3 of embodiment 3
In 100 ml beaker, 564 mg copper chlorides will be added（（Cu(CH3COO)2∙H2O, 99.0%））To filling 25
Ml ethylene glycol（HO-CH2-CH2- OH, purity >=99.5%）In solution, after being sufficiently stirred, 0.365 ml metatitanic acid isopropyls are slowly dropped into
Ester,（Purity >=99.0%）Solution, strong agitation 30min, 200 DEG C is then transferred into the polyvinyl fluoride reactor of 50ml liners four
Constant temperature keeps 48 h, naturally cools to room temperature, and products therefrom is filtered, washs precipitation respectively three times with distilled water, absolute ethyl alcohol, so
Afterwards at 60 DEG C, 24 h are dried in vacuo, Cu/TiO is made2Nanometer rods.TiO is prepared using this step2The length of nanometer rods is about
200nm, diameter are about 20nm, and surface, which can be clearly visible, has copper nano particles, and size is about 3~5 nm, and particle rolls up.
The preparation of the photochemical catalyst 4 of embodiment 4
In 100 ml beaker, 188 mg copper acetates will be added（Cu(CH3COO)2∙H2O, 99.0%）To filling 25 ml
Ethylene glycol（HO-CH2-CH2- OH, purity >=99.5%）In solution, after being sufficiently stirred, 0.730 ml isopropyl titanates are slowly dropped into
（Purity >=99.0%）Solution, strong agitation 30min, it is then transferred into 200 DEG C of perseverances in the polyvinyl fluoride reactor of 50ml liners four
Temperature keeps 24h, naturally cools to room temperature, and products therefrom is filtered, washs precipitation respectively three times with distilled water, absolute ethyl alcohol, then
At 60 DEG C, 24 h are dried in vacuo, Cu/TiO is made2Nanometer rods.TiO is prepared using this step2The length of nanometer rods is about
200nm, diameter are about 20nm, and surface, which can be clearly visible, has copper nano particles, and size is about 3~5 nm.
The preparation of the photochemical catalyst 5 of embodiment 5
In 100 ml beaker, 188 mg copper chlorides will be added（（Cu(CH3COO)2∙H2O, 99.0%））To filling 25
Ml ethylene glycol（HO-CH2-CH2- OH, purity >=99.5%）In solution, after being sufficiently stirred, 1.095ml butyl titanates are slowly dropped into
（Ti(C4H9O)4, purity >=99.0%）Solution, strong agitation 30min, it is then transferred into the polyvinyl fluoride reactor of 50ml liners four
In 200 DEG C of constant temperature keep 24 h, naturally cool to room temperature, products therefrom is filtered, and precipitation is washed with distilled water, absolute ethyl alcohol
Respectively three times, then at 60 DEG C, 24 h are dried in vacuo, Cu/TiO is made2Nanometer rods.TiO is prepared using this step2Nanometer rods
Length is about 200nm, and diameter is about 20nm, and surface, which can be clearly visible, has copper nano particles, and size is about 3~5 nm.
The two step method of reference examples 1 prepares Cu/TiO2Nano-rod photo-catalyst
（1）TiO2The preparation of nanometer rods：Weigh 0 .5g nano-TiOs2(P25), it is placed on the water heating kettle of polytetrafluoroethylene (PTFE)
In inner bag, 15mL 10mol/L NaOH solution is added, being sufficiently stirred makes to seal water heating kettle after it is well mixed, and is put
In drying box, 12h is handled in 180 DEG C of incubation water heatings.Room temperature is cooled to after completion of the reaction, and reactant is taken out, and with 0
.1mol/ it is 7 that L hydrochloric acid and distilled water wash to pH values repeatedly, is placed in product after washing 3 times with 15mL absolute ethyl alcohols dry
In 60 DEG C of drying in dry case, 3h finally is calcined in 350 DEG C in Muffle furnace, obtains T iO2Nanorods Samples.
（2）Cu/TiO2The preparation of nanometer rods：By the TiO of synthesis2Nanometer rods are with 2 % mass fraction ultrasonic disperse in 5mL
In distilled water, by the .05mol/ L of 2mL 0 CuCl2Solution adds TiO2In nanometer rods suspension system, after magnetic agitation 1h,
The CuCl by adsorption2TiO2It is scattered in again in 5mL distilled water after nanometer rods centrifuge washing, and adds 5mL 0
.05mol/ L NaBH4Solution, the magnetic agitation 1h under room temperature condition, 24h is aged, obtains the TiO of Cu nano particles cladding2
Nanometer rods.By regulating and controlling CuCl in experimentation2Solution concentration can reach the purpose of regulation and control Cu load capacity.
The three-step approach of reference examples 2 prepares Cu/TiO2Nano-rod photo-catalyst
（1）TiO2The preparation of nanometer rods：Weigh 0 .5g nano-TiOs2(P25), it is placed on the water heating kettle of polytetrafluoroethylene (PTFE)
In inner bag, 15mL 10mol/L NaOH solution is added, being sufficiently stirred makes to seal water heating kettle after it is well mixed, and is put
In drying box, 12h is handled in 180 DEG C of incubation water heatings.Room temperature is cooled to after completion of the reaction, and reactant is taken out, and with 0
.1mol/ it is 7 that L hydrochloric acid and distilled water wash to pH values repeatedly, is placed in product after washing 3 times with 15mL absolute ethyl alcohols dry
In 60 DEG C of drying in dry case, 3h finally is calcined in 350 DEG C in Muffle furnace, obtains T iO2Nanorods Samples.
（2）Cu(OH)2/TiO2The preparation of nanometer rods：By the TiO of synthesis2Nanometer rods are with 2 % mass fraction ultrasonic disperse
In 5mL distilled water, by the .05mol/ L of 2mL 0 Cu (NO3)2Solution adds TiO2In nanometer rods suspension system, magnetic force stirs
After mixing 1h, the Cu (NO by adsorption3)2TiO2It is scattered in 5mL distilled water, obtains again after nanometer rods centrifuge washing
Cu(OH)2The TiO of nano particle cladding2Nanometer rods.
（3）Cu/TiO2The preparation of nanometer rods：By the Cu prepared (OH)2/TiO2Nanometer rods are placed in tube furnace, in H2/
Ar（H2Account for the volume 5% of mixture）300 DEG C of reductase 12 h in mixed-gas atmosphere.Cu/TiO will be obtained2Nanometer rods.
Reference examples 3 prepare Ag/TiO2Nano-rod photo-catalyst
（1）TiO2The preparation of nanometer rods：Weigh 0 .5g nano-TiOs2(P25), it is placed on the water heating kettle of polytetrafluoroethylene (PTFE)
In inner bag, 15mL 10mol/L NaOH solution is added, being sufficiently stirred makes to seal water heating kettle after it is well mixed, and is put
In drying box, 12h is handled in 180 DEG C of incubation water heatings.Room temperature is cooled to after completion of the reaction, and reactant is taken out, and with 0
.1mol/ it is 7 that L hydrochloric acid and distilled water wash to pH values repeatedly, is placed in product after washing 3 times with 15mL absolute ethyl alcohols dry
In 60 DEG C of drying in dry case, 3h finally is calcined in 350 DEG C in Muffle furnace, obtains T iO2Nanorods Samples.
（2）Ag/TiO2The preparation of nanometer rods：By the TiO of synthesis2Nano wire is steamed with 2 wt% concentration ultrasonic disperse in 5 ml
In distilled water, by the Ag (NH that 4 ml concentration are 0.4 mol/L3)2 +Solution adds to TiO2In nanowire suspended system, magnetic agitation
After 6h, the Ag (NH by adsorption3)2 +TiO2Nano wire centrifuge washing for several times after, it is scattered in again 5 ml distillation
In water, and the glucose solution that 5 ml concentration are 0.5 mol/L is added, under room temperature condition after the h of magnetic agitation 3, obtained
The TiO of Ag nano particles cladding2Nano wire.
The Cu/TiO that the embodiment 1 of test example 1 is prepared2The pattern of nanometer rods and structural analysis
To Cu/TiO made from the method using the offer of the embodiment of the present invention 12Nanometer rods use LEO1530VP type Flied emissions
SEM（SEM）Pattern and structural analysis are carried out with Japan Electronics Corporation JEOL-2010 types transmission electron microscope,
Measurement result is please respectively referring to Figure of description 1 and accompanying drawing 2. from Fig. 1 and Fig. 2, the gained Cu/TiO of embodiment 12Nanometer rods
The elements such as Cu, Ti, O, TiO be present in sample2In club shaped structure, length is 100~200nm, and diameter is about 20nm, and surface can be obvious
See copper nano particles being present, size is about 3~5nm.
XPS analysis are carried out to obtained material using Britain VG ESM-LAB photoelectricity power spectrum, measurement result refer to
Figure of description 3, as shown in Figure 3, Cu/TiO2Tri- kinds of elements of Cu, Ti and O, wherein Cu2p energy levels electronics knot in nanometer rods be present
Conjunction can be 932.5 eV and 952.2 eV, and the Cu particles for illustrating load are present in the form of simple substance.
Test example 2：The Cu/TiO that embodiment 1 is prepared2The photocatalytic activity evaluation of nanometer rods
Photocatalytic activity evaluation reaction is 200 ml quartz glass reactors using volume, in XPS-VII type reaction units
Upper progress（Xujiang Electromechanical Plant, Nanjing, China produces）.Using 1000 W xenon lamps as ultraviolet-visible radiant, and use self-control filtrate
Ultraviolet source is absorbed so as to obtain visible light source, and filtrate uses 2 M NaNO3Carry out the light that absorbing wavelength is less than 400 below nm.
Interlayer of the solution layer between fluorescent tube and recirculated cooling water, so after water layer further absorbs ultraviolet light so that purple
Outer absorptivity is up to more than 98%.Catalyst obtained by 20 mg is added in 200 ml methyl orange solutions (20 mg/l), first existed
The min of ultrasonic disperse 15 is to obtain preferable dispersity in darkroom, in order to reach desorption-adsorption equilibrium, before turning on light, logical
Magnetic agitation adsorbs 1 h in the case of entering 200 ml/min air, then carries out light-catalyzed reaction at room temperature.Course of reaction
In, 8 ml samples are taken at regular intervals once, and the suspension of acquirement centrifuges 10 min to remove in solution in supercentrifuge
The catalyst that left floating, supernatant liquor is taken to test its concentration in Hitachi's UV-3010 spectrophotometers.
The decolorizing efficiency of methyl orange can be calculated by equation below：
X% = (A0-A)/A0×100%；
Wherein：A0It is absorbances of the 20 mg/l MO at 465 nm：
A is the absorbance that different time takes out sample methyl orange；
X values are bigger to represent that photocatalytic degradation effect is better.
To Cu/TiO made from the method for the embodiment of the present invention 12Nanometer rods, nitrogen-doped titanium dioxide（N-P25）And control
The Cu/TiO that example 1 and reference examples 2 are prepared2Nanometer rods have carried out the effect ratio of photo-catalytic degradation of methyl-orange under sun light action
Compared with, specifically can referring to accompanying drawing 4, wherein（a）For nitrogen-doped titanium dioxide（N-P25）、（b）The Cu/TiO prepared for reference examples 12Receive
Rice rod,（c）The Cu/TiO prepared for reference examples 22Nanometer rods,（d）Ag/TiO is prepared for reference examples 32Nanometer rods,（e）For the present invention
Cu/TiO made from embodiment 12Nanometer rods.
As shown in Figure 4, the Cu/TiO that the present invention is prepared2Nanometer rods colour fading rate reaches 98.7%, prepared by reference examples 1
Cu/TiO2Nanometer rods colour fading rate only has 60%, Cu/TiO prepared by reference examples 22Nanometer rods colour fading rate is 70%, N doping titanium dioxide
Titanium（N-P25）Colour fading rate only has 50.8%.And with similar photochemical catalyst Ag/TiO2Nanometer rods compare, and reference examples 3 prepare Ag/TiO2
The colour fading rate of nanometer rods under equal conditions is only 85%.It follows that the Cu/TiO that the present invention is prepared2Nanometer rods have
The effect of preferable degradable organic pollutant.
Claims (9)
- A kind of 1. method of solvent hot preparation copper modified titanic oxide nanometer rods, it is characterised in that methods described includes following step Suddenly：S1：Mantoquita is added in ethylene glycol solution, is sufficiently stirred, titanium-containing compound, strong agitation are then added into solution It is standby to obtain mixed liquor；S2：Mixed liquor obtained by step S1 is transferred in the hydrothermal reaction kettle of the polyvinyl fluoride of liner four, and hydrothermal reaction kettle is put Keep reacting under 200 DEG C of conditions above of constant temperature in drying condition, be subsequently cooled to room temperature；S3：Step S2 products therefroms are filtered, washed, are drying to obtain copper modified titanic oxide nanometer rods；Wherein, the titanium-containing compound in step S1 is the good titanium-containing compound of dissolubility in ethylene glycol.
- 2. the method for solvent hot preparation copper modified titanic oxide nanometer rods according to claim 1, it is characterised in that step S1 Described in mantoquita be copper acetate, copper chloride or copper nitrate in one or more.
- 3. the method for solvent hot preparation copper modified titanic oxide nanometer rods according to claim 1, it is characterised in that step S1 In titanium-containing compound be butyl titanate and/or isopropyl titanate.
- 4. the method for solvent hot preparation copper modified titanic oxide nanometer rods according to claim 1, it is characterised in that step S1 In mixing time be 15~30min.
- 5. the method for solvent hot preparation copper modified titanic oxide nanometer rods according to claim 1, it is characterised in that step S2 In reaction time be 24~48h.
- 6. the method for solvent hot preparation copper modified titanic oxide nanometer rods according to claim 1, it is characterised in that step S3 Described in washing be using distilled water, absolute ethyl alcohol respectively wash precipitation three times.
- 7. the method for solvent hot preparation copper modified titanic oxide nanometer rods according to claim 1, it is characterised in that step S3 Described in dry to be dried in vacuo under the conditions of 60 DEG C.
- 8. the copper modified titanic oxide nanometer rods that any methods described of claim 1~7 is prepared.
- 9. application of the copper modified titanic oxide nanometer rods in photolysis water hydrogen, degradable organic pollutant described in claim 8.
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