CN108837832A - A kind of radiation preparation method in situ of the mesoporous single crystals TiO2 heterojunction photocatalyst of nanometer of Cu2O modification - Google Patents
A kind of radiation preparation method in situ of the mesoporous single crystals TiO2 heterojunction photocatalyst of nanometer of Cu2O modification Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000005855 radiation Effects 0.000 title claims abstract description 20
- 238000012986 modification Methods 0.000 title claims abstract description 18
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title abstract description 13
- 230000004048 modification Effects 0.000 title description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical class OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000013589 supplement Substances 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to sewage treatment, Photocatalyzed Hydrogen Production and photosensitive antibiotic and sterilizing technical field more particularly to a kind of nanometer of Cu2The mesoporous single crystals TiO of O modification2The radiation preparation method in situ of heterojunction photocatalyst.It includes the following steps：（1）By mesoporous single crystals TiO2It is scattered in containing Cu2+Emulsion system in；（2）To step（1）Obtained product is irradiated.The method realizes Cu2O and TiO2The synergy of photocatalysis performance, can be to TiO2It is effectively modified, to obtain can be applied to sewage treatment, the Cu of the technical fields such as Photocatalyzed Hydrogen Production and photosensitive antibiotic and sterilizing2O/TiO2Composite photocatalyst material.
Description
Technical field
The present invention relates to sewage treatment, Photocatalyzed Hydrogen Production and photosensitive antibiotic and sterilizing technical field more particularly to a kind of nanometers
Cu2The mesoporous single crystals TiO of O modification2The radiation preparation method in situ of heterojunction photocatalyst.
Background technique
1972, Tokyo Univ Japan professor Fujiashima and Honda discovery：Under the action of light, TiO2Monocrystalline electricity
It pole can be by H2O is decomposed into H2And O2, one brand-new approach is opened to the exploration of solar energy trans-utilization for people.TiO2Tool
There is the advantages that nontoxic, chemical stability is good, cheap and stronger photocatalysis performance, so that becoming most has researching value
Photochemical catalyst.But TiO2Itself has its limitation, greater band gap（E g=3.0~3.2 eV）, light absorption is limited only to ultraviolet region
Domain（λ<387 nm）, and the content of sunlight middle-ultraviolet lamp is less than 5 %, so that the utilization rate of solar energy is very low, light induced electron
Hole is easy to happen compound, and photocatalysis efficiency is low.In order to extend TiO2The spectral response range of photochemical catalyst is urged with its light is improved
Change efficiency, it is necessary to TiO2Effectively it is modified.
Extend TiO2In many method of modifying of photochemical catalyst absorption region, the relatively narrow semiconductor of compound band-gap, which becomes, most to be had
One of desired method.Cu2O, p-type semiconductor, 2.0 eV of forbidden bandwidth, at present in hydrogen manufacturing, superconductor, solar battery and light
Catalysis aspect is widely used.Cu2O is good visible light catalyst, has good photocatalysis performance and reserves are big, nontoxic
Inexpensively.But haves the defects that the carrier generated after illumination is unstable and it is compound to be easy, substantially reduce its photocatalysis efficiency.Pass through
Cu2O and TiO2Compound, the Cu of formation2O/TiO2Heterojunction photocatalyst will be enlarged by TiO2The response range of light is to visible light
Its photocatalysis performance is improved in area.Study Cu2O/TiO2The traditional preparation methods of composite photocatalyst material mainly have photochemical precipitation
Method, electrochemical deposition method, physical mixed method, immersion reduction method, hydro-thermal method etc., correlative study shows：Under visible light-inducing, institute
The Cu of preparation2O/TiO2The photocatalysis performance of composite photocatalyst material, than the Cu of one-component2O and TiO2It is urged with apparent light
Change activity.
Radiation method relative to traditional physico-chemical process carried out it is effective supplement and it is perfect, be embodied in：1. anti-
Process is answered not need to add any pair of toxic substance of human body, without adding the reaction reagents such as initiator, reducing agent；2. reacting item
Part is mild, can carry out at room temperature, easy to operate, reaction time is short；3. can by control polymers compositions and radiation parameter
Accurately to regulate and control Cu prepared by radiation reduction in situ2The important physical and chemical parameter such as content, particle size, the microscopic appearance of O；④
Cu prepared by radiation reduction in situ2O can be evenly distributed on mesoporous single crystals TiO2Surface, to mesoporous nano monocrystalline TiO2Had
It the modification of effect and not easily runs off.From the point of view of comprehensive and long-range, the warp that catalysis material is spent is prepared using irradiation technique
Cost is relatively low for Ji.Therefore, radiation synthetic technology has become the Research approach that catalysis material preparation is rich in prospect.
Summary of the invention
The invention solves the above problems, provide a kind of nanometer of Cu2The mesoporous single crystals TiO of O modification2Heterojunction photocatalyst
Radiation preparation method in situ, to TiO2Effectively it is modified.
The technical solution that the present invention solves the problems, such as is to provide a kind of nanometer of Cu2The mesoporous single crystals TiO of O modification2It is heterogeneous
The radiation preparation method in situ for tying photochemical catalyst, includes the following steps：（1）By mesoporous single crystals TiO2It is scattered in containing Cu2+Cream
In liquid system；（2）To step（1）Obtained product is irradiated.
Preferably, the mesoporous single crystals TiO2Preparation method：By mass parts by 5 parts ~ 40 parts titanium sources in alcohol dispersed phase
8 ~ 48 h are reacted at 80 ~ 120 DEG C, and obtained solution is centrifuged, is dried.
Preferably, described to contain Cu2+Emulsion system according to mass parts include 1 ~ 5 part of copper source, 0.1 ~ 2 part of P123 three block
Copolymer, 5 ~ 30 parts of polyhydric alcohol solutions, 0.5 ~ 5 part of emulsifier, 1 ~ 8 part of isopropanol, 10 ~ 60 parts of hexamethylenes.
Preferably, radiation parameter：Beam energy be 1 ~ 5MeV, dose of radiation be 10 ~ 120kGy, dosage rate be 5 ~
60kGy/pass。
Preferably, by the step（1）Obtained product ultrasonic mixing is passed through 0.5 ~ 2 h of nitrogen, and stands under negative pressure
Step is carried out after de-bubble（2）.
It preferably, further include step（3）The product obtained after irradiation is centrifuged, is washed, drying process.
Preferably, the titanium source is one or more of titanyl sulfate, titanium tetrachloride, potassium titanate, butyl titanate.
Preferably, copper source is one or more of copper nitrate, copper sulphate, copper chloride, copper acetate.
Preferably, the emulsifier is one of OP, OS, Triton X-10, Brij56, Spain, Tween or several
Kind.
Beneficial effects of the present invention：
1. utilizing the nanometer Cu of ionising radiation preparation in situ2O can effectively modify mesoporous nano monocrystalline TiO2Surface, from
And form nanometer Cu2The mesoporous single crystals TiO of O modification2Heterojunction photocatalyst realizes Cu2O and TiO2The association of photocatalysis performance
Same synergy.
2. having the characteristics that photocatalysis efficiency is high, at low cost, green easy, the Cu2O/TiO2Heterojunction photocatalyst is expected to
It is efficiently applied to sewage treatment, the technical fields such as Photocatalyzed Hydrogen Production and photosensitive antibiotic and sterilizing.
3. irradiation technique is nontoxic, reaction condition is mild, reaction process does not add crosslinking agent, initiator and any pair of human body
Toxic substance, can effectively avoid secondary pollution.
Specific embodiment
It is a specific embodiment of the invention below, technical scheme of the present invention will be further described, but the present invention
It is not limited to these examples.
Embodiment 1
According to mass parts, 5 parts of titanium tetrachlorides are mixed according to a certain percentage with the tert-butyl alcohol, stirring is uniformly mixed it, wherein uncle
For butanol as solvent, dosage those skilled in the art can be empirically determined.Reaction kettle equipped with above-mentioned mixed liquor is put into
In isothermal reaction case, at 80 DEG C, react 8 h, will solution is centrifuged, is dried, products obtained therefrom be mesoporous nano monocrystalline
TiO2.1 part of nitric acid copper powders and 0.1 part of P123 triblock copolymer are added in the solution containing 5 parts of neopentyl glycols, are made
It is uniformly mixed and forms stable dispersion.By the mixing comprising 0.5 part of OS emulsifier, 1 part of isopropanol, 10 parts of hexamethylenes
Solution is slowly injected into above-mentioned dispersion, forms new mixed dispersion.Take a certain amount of gained mesoporous nano monocrystalline TiO2
It will be added among the new mixed dispersion of above-mentioned gained, ultrasonic mixing is uniform, is passed through 0.5 h of nitrogen, and quiet under negative pressure
Set de-bubble.Gained sample is transferred in the PE hermetic bag of about 2 mm of thickness, is placed under electron beam and is carried out radioreaction in situ,
The beam energy selected is 1 MeV, and dose of radiation is 10 kGy, and dosage rate is 5 kGy/pass.By obtained product pass through from
After the heart, washing, drying, gained sample is Cu2O/TiO2Heterojunction photocatalyst.
Basis weight products are taken to put into the rhodamine B of 250 mL, 4 mg/L（Simulate organic pollutant）In, at room temperature, to mould
Quasi- object carries out photocatalytic degradation experiment, after reacting 2 h, measures degradation rate and reaches 87.6%.
Embodiment 2
According to mass parts, 10 parts of potassium titanates are mixed according to a certain percentage with the tert-butyl alcohol, stirring is uniformly mixed it, wherein uncle
For butanol as solvent, dosage those skilled in the art can be empirically determined.Reaction kettle equipped with above-mentioned mixed liquor is put into
In isothermal reaction case, at 100 DEG C, react 10 h, will solution is centrifuged, is dried, products obtained therefrom be mesoporous nano monocrystalline
TiO2.2 parts of copper sulphate powders and 0.2 part of P123 triblock copolymer are added in the solution containing 10 parts of glycerine, it is made
It is uniformly mixed and forms stable dispersion.It will be molten comprising 1 part of OS emulsifier, 2 parts of isopropanols, the mixing of 20 parts of hexamethylenes
Liquid is slowly injected into above-mentioned dispersion, forms new mixed dispersion.Take a certain amount of gained mesoporous nano monocrystalline TiO2It will
It is added among the new mixed dispersion of above-mentioned gained, ultrasonic mixing is uniform, is passed through 1 h of nitrogen, and stand remove under negative pressure
Bubble.Gained sample is transferred in the PE hermetic bag of about 2 mm of thickness, is placed under electron beam and is carried out radioreaction in situ, selection
Beam energy is 1 MeV, and dose of radiation is 20 kGy, and dosage rate is 10 kGy/pass.Obtained product is centrifuged, is washed
After washing, drying, gained sample is Cu2O/TiO2Heterojunction photocatalyst.
Basis weight products are taken to put into the rhodamine B of 250 mL, 4 mg/L（Simulate organic pollutant）In, at room temperature, to mould
Quasi- object carries out photocatalytic degradation experiment, after reacting 2 h, measures degradation rate and reaches 89.4%.
Embodiment 3
According to mass parts, 30 parts of titanyl sulfates are mixed according to a certain percentage with the tert-butyl alcohol, stirring is uniformly mixed it, wherein
For the tert-butyl alcohol as solvent, dosage those skilled in the art can be empirically determined.Reaction kettle equipped with above-mentioned mixed liquor is put
Enter in isothermal reaction case, at 120 DEG C, react 36 h, will solution is centrifuged, is dried, gained sample be mesoporous nano list
Brilliant TiO2.3 parts of acetic acid copper powders and 1 part of P123 triblock copolymer are added in the solution containing 20 parts of pentaerythrites, are made
It is uniformly mixed and forms stable dispersion.It will be molten comprising 3 parts of OS emulsifiers, 5 parts of isopropanols, the mixing of 40 parts of hexamethylenes
Liquid is slowly injected into above-mentioned dispersion, forms new mixed dispersion.Take a certain amount of gained mesoporous nano monocrystalline TiO2It will
It is added among the new mixed dispersion of above-mentioned gained, ultrasonic mixing is uniform, is passed through 2 h of nitrogen, and stand remove under negative pressure
Bubble.Gained sample is transferred in the PE hermetic bag of about 2 mm of thickness, is placed under electron beam and is carried out radioreaction in situ, selection
Beam energy be 1 MeV, dose of radiation be 90 kGy, dosage rate be 30 kGy/pass.Obtained product is centrifuged,
After washing, drying, gained sample is Cu2O/TiO2Heterojunction photocatalyst.
Basis weight products are taken to put into the rhodamine B of 250 mL, 4 mg/L（Simulate organic pollutant）In, at room temperature, to mould
Quasi- object carries out photocatalytic degradation experiment, after reacting 2 h, measures degradation rate and reaches 97.6 %.
Embodiment 4
According to mass parts, 40 parts of butyl titanates are mixed according to a certain percentage with the tert-butyl alcohol, stirring is uniformly mixed it,
In, the tert-butyl alcohol can be empirically determined as solvent, dosage those skilled in the art.The reaction kettle of above-mentioned mixed liquor will be housed
Be put into isothermal reaction case, at 120 DEG C, react 48 h, will solution is centrifuged, is dried, gained sample be mesoporous nano
Monocrystalline TiO2.5 parts of chlorination copper powders and 2 parts of P123 triblock copolymers are added in the solution containing 30 parts of pentaerythrites,
It is uniformly mixed it and forms stable dispersion.By the mixing comprising 5 parts of OS emulsifiers, 8 parts of isopropanols, 60 parts of hexamethylenes
Solution is slowly injected into above-mentioned dispersion, forms new mixed dispersion.Take a certain amount of gained mesoporous nano monocrystalline TiO2
It will be added among the new mixed dispersion of above-mentioned gained, ultrasonic mixing is uniform, is passed through 2 h of nitrogen, and stand under negative pressure
De-bubble.Gained sample is transferred in the PE hermetic bag of about 2 mm of thickness, is placed under electron beam and is carried out radioreaction in situ, choosing
The beam energy selected is 1 MeV, and dose of radiation is 120 kGy, and dosage rate is 60 kGy/pass.By obtained product pass through from
After the heart, washing, drying, gained sample is Cu2O/TiO2Heterojunction photocatalyst.
Basis weight products are taken to put into the rhodamine B of 250 mL, 4 mg/L（Simulate organic pollutant）In, at room temperature, to mould
Quasi- object carries out photocatalytic degradation experiment, after reacting 2 h, measures degradation rate and reaches 76.9%.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (9)
1. a kind of nanometer of Cu2The mesoporous single crystals TiO of O modification2The radiation preparation method in situ of heterojunction photocatalyst, feature exist
In：Include the following steps：（1）By mesoporous single crystals TiO2It is scattered in containing Cu2+Emulsion system in；（2）To step（1）It obtains
Product is irradiated.
2. a kind of nanometer of Cu according to claim 12The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：The mesoporous single crystals TiO2Preparation method：By mass parts by 5 parts ~ 40 parts titanium sources in alcohol point
8 ~ 48 h are reacted in dephasing at 80 ~ 120 DEG C, obtained solution is centrifuged, is dried.
3. a kind of nanometer of Cu according to claim 12The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：It is described to contain Cu2+Emulsion system according to mass parts include 1 ~ 5 part of copper source, 0.1 ~ 2 part
P123 triblock copolymer, 5 ~ 30 parts of polyhydric alcohol solutions, 0.5 ~ 5 part of emulsifier, 1 ~ 8 part of isopropanol, 10 ~ 60 parts of hexamethylenes.
4. a kind of nanometer of Cu according to claim 12The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：Radiation parameter：Beam energy is 1 ~ 5MeV, and dose of radiation is 10 ~ 120 kGy, dosage rate
For 5 ~ 60 kGy/pass.
5. a kind of nanometer of Cu according to claim 12The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：By the step（1）Obtained product ultrasonic mixing is passed through 0.5 ~ 2 h of nitrogen, and negative
Pressure carries out step after standing de-bubble（2）.
6. a kind of nanometer of Cu according to claim 12The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：It further include step（3）The product obtained after irradiation is centrifuged, is washed, drying process.
7. a kind of nanometer of Cu according to claim 22The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：The titanium source be one of titanyl sulfate, titanium tetrachloride, potassium titanate, butyl titanate or
It is several.
8. a kind of nanometer of Cu according to claim 32The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：Copper source is one or more of copper nitrate, copper sulphate, copper chloride, copper acetate.
9. a kind of nanometer of Cu according to claim 32The mesoporous single crystals TiO of O modification2The spoke in situ of heterojunction photocatalyst
Penetrate preparation method, it is characterised in that：The emulsifier is OP, one in OS, Triton X-10, Brij56, Spain, Tween
Kind is several.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773831A (en) * | 2009-11-27 | 2010-07-14 | 中国科学院广州地球化学研究所 | Micro-pore cuprous oxide visible light catalyst and preparation method and application thereof |
| CN104128197A (en) * | 2014-07-10 | 2014-11-05 | 上海大学 | Method for preparing nitrogen-doped titanium dioxide photocatalyst through electron beam irradiation |
-
2018
- 2018-07-12 CN CN201810764582.9A patent/CN108837832A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773831A (en) * | 2009-11-27 | 2010-07-14 | 中国科学院广州地球化学研究所 | Micro-pore cuprous oxide visible light catalyst and preparation method and application thereof |
| CN104128197A (en) * | 2014-07-10 | 2014-11-05 | 上海大学 | Method for preparing nitrogen-doped titanium dioxide photocatalyst through electron beam irradiation |
Non-Patent Citations (4)
| Title |
|---|
| JAKUB SURMACKI等: "Raman spectroscopy of visible-light photocatalyst – Nitrogen-doped titanium dioxide generated by irradiation with electron beam", 《CHEMICAL PHYSICS LETTERS》 * |
| 上海环境科学编辑部 编: "《上海环境科学集(第20辑)》", 30 June 2018, 上海科学技术出版社 * |
| 杨士国等: "乙二醇对反向微乳辐照法制备纳米级氧化亚铜形貌的影响 ", 《光谱学与光谱分析》 * |
| 林香凤: "微纳氧化亚铜及其复合物的电子束辐照制备及光催化性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675541A (en) * | 2019-01-28 | 2019-04-26 | 广东朗研科技有限公司 | A kind of preparation method of reproducibility meso-porous titanium oxide nano particle |
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