CN108187756A - A kind of preparation method of memory-type photocatalytic fiber element microballoon - Google Patents
A kind of preparation method of memory-type photocatalytic fiber element microballoon Download PDFInfo
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- CN108187756A CN108187756A CN201810003328.7A CN201810003328A CN108187756A CN 108187756 A CN108187756 A CN 108187756A CN 201810003328 A CN201810003328 A CN 201810003328A CN 108187756 A CN108187756 A CN 108187756A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000835 fiber Substances 0.000 title claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 83
- 229920002678 cellulose Polymers 0.000 claims abstract description 81
- 239000001913 cellulose Substances 0.000 claims abstract description 77
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 41
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000002159 nanocrystal Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 229920000875 Dissolving pulp Polymers 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 43
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 238000005286 illumination Methods 0.000 abstract description 10
- 230000006870 function Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007334 memory performance Effects 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 abstract 5
- 229960001296 zinc oxide Drugs 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 69
- 239000010949 copper Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 206010001497 Agitation Diseases 0.000 description 15
- 238000013019 agitation Methods 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 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 11
- 229940012189 methyl orange Drugs 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000011160 research Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000005374 membrane filtration Methods 0.000 description 6
- 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 6
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910000474 mercury oxide Inorganic materials 0.000 description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/51—
-
- B01J35/61—
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to chemical field more particularly to a kind of preparation methods of memory-type photocatalytic fiber element microballoon.Utilize ZnO and Cu2Electronic saving function between O realizes the catalytic degradation function under non-illumination condition.This method prepares Regenerated cellulose microspheres to dissolve pulp fibres as raw material, with antiphase emulsifiable method, then induces Cu2O predecessors prepare Cu through reduction method2O/ cellulose microspheres, then through hydro-thermal method, in Cu2O/ cellulose microsphere area load ZnO nano crystal.ZnO/Cu prepared by the present invention2O cellulose composite microspheres can replace existing Zinc-oxide-based catalysis material, utilize ZnO and Cu2Electronic saving function between O realizes the catalytic degradation function under non-illumination condition；Using the relatively rich permeability of cellulose microsphere, there is the composite photocatalyst prepared high-specific surface area, high hole to hold feature, show preferable photocatalytic degradation and memory performance, preparation process is simple, belongs to a kind of environmentally friendly material.
Description
Technical field
The invention belongs to chemical field more particularly to a kind of preparation methods of memory-type photocatalytic fiber element microballoon.
Background technology
With the rapid development of global economy and the excessive exploitation of resource, the fossil energy used for the mankind is increasingly
Few, energy problem is increasingly serious, and the ecological balance is seriously damaged, and the living environment of the mankind is worsening.Therefore Environment control
Pollution, exploitation new cleaning fuel and realizes economic sustainable development, has become that human society is urgently to be resolved hurrily to ask jointly
Topic.
Photocatalitic Technique of Semiconductor can directly convert light energy into chemical energy, promote the synthesis and degradation of compound, have
Low energy consumption, efficient, non-secondary pollution and it is reusable the advantages that, it has also become numerous scientific research field extensive concerns and research
Hot spot.1998, Tsujikawa et al. researchs found TiO2Protect carbon steel from corrosion, TiO in photocatalysis2/Fe2O3
Multilayer material can not only realize anti-corrosion under ultraviolet light, and remain to after light source is removed to maintain its anticorrosion, this phenomenon
It is considered as the reflection of energy storage characteristic.This accumulation energy type photocatalysis technology as extension of the photo-catalysis function under dark condition and
Expansion is valued by the people, and the catalysis material of Practical Project effectiveness is had more for exploitation, realizes that photocatalytic process is high
Effect runs to round-the-clock property and has a very important significance.
In recent years, scientific worker develops series of high efficiency visible-light photocatalyst, substantially increases by adulterating means
For the utilization ratio of solar energy, reduce since the cost that ultraviolet irradiation is brought must be used to increase and operation risk, favorably
Enter practical application in photocatalysis technology.However, existing efficient visible light catalysis material is in the energy for losing external light source
Electron-hole pair cannot be generated after supply, so as to generate active group, reactivity is lost rapidly, Wu Faji
It is continuous that pollutant in environment is handled.Therefore, existing efficient visible light catalysis material can not come merely with solar energy
Continue the pollutant in processing environment, it is necessary to which secondary light source is configured except solar energy could persistently have reaction in night
Activity.This can bring about both sides problem.On the one hand, auxiliary light source system necessarily increases cost and energy consumption；On the other hand, very
More environmental pollution treatment is simultaneously not suitable for illumination condition free of discontinuities.
Invention content
The technical problem to be solved in the present invention is to provide a kind of preparation method of memory-type photocatalytic fiber element microballoon,
Utilize ZnO and Cu2Electronic saving function between O realizes the catalytic degradation function under non-illumination condition.
The invention is realized in this way：To dissolve pulp fibres as raw material, Regenerated cellulose microspheres are prepared with antiphase emulsifiable method,
Then Cu is induced2O predecessors prepare Cu through liquid phase reduction2O/ cellulose microspheres, then through hydro-thermal method, in Cu2O/ celluloses are micro-
Ball surface loading ZnO nanocrystal.
Include the following steps：
(1), the preparation of Regenerated cellulose microspheres：
Using dissolving pulp as raw material, Na OH/ urea/H is dissolved at -9~-15 DEG C2O systems, using epoxychloropropane as friendship
Connection agent is prepared for Regenerated cellulose microspheres using emulsion method, and emulsifier is Span 80；
Wherein emulsification stirring speed is 500-1000r/min, and the mass ratio of dissolving pulp and crosslinking agent is 1-10：0.05-2,
The mass ratio of dissolving pulp and emulsifier is 1-10：1-10；
(2), Regenerated cellulose microspheres prepare Cu2O/ cellulose composite microspheres：
Using above-mentioned Regenerated cellulose microspheres as raw material, Cu is induced2O precursor Cs uCl2, using ascorbic acid as reducing agent, in alkali
Cu is prepared under the conditions of property2O/ cellulose composite microspheres；
Wherein per 0.1-0.5g Regenerated cellulose microspheres, (0.4-2) × 10 are added in-3mol CuCl2, add in (2-4) × 10- 3Mol NaOH add in (0.4-2) × 10-3Mol ascorbic acid；
(3)、Cu2O/ cellulose composite microsphere area load ZnO nano crystal：
With Cu obtained above2O/ cellulose composite microspheres are raw material, induce ZnO predecessor Zn (NO3)2, it is heavy using urea
Shallow lake agent prepares ZnO/Cu2O/ cellulose microspheres；
Wherein Cu2O/ cellulose composite microspheres and Zn (NO3)2, urea mass ratio be 0.1-0.5：0.1-0.5：0.5-1,
Hydrothermal temperature is 150-200 DEG C.
During for preparing Regenerated cellulose microspheres, regulation and control mixing speed, dosage of crosslinking agent and emulsifier can obtain
The cellulose microsphere that porosity, macropore hold, is conducive to Cu2The absorption of O and ZnO predecessors and crystalline growth；Regulate and control Cu2O and ZnO
Respective predecessor concentration ratio, alkali charge, reducing agent dosage, hydrothermal temperature, prepare spherical Cu respectively2O and hexagonal wurtzite type
ZnO is conducive to photocatalysis effect under illumination condition；Cu2O crystal will be grown in spreadability Regenerated cellulose microspheres table as far as possible
Face, and ZnO crystal needs are grown in Cu decoratively2On O planes of crystal, realize the energy storage effect between two kinds of crystal, help
In improving the photocatalysis efficiency under non-illuminated conditions.
The invention has the advantages that：ZnO/Cu prepared by the present invention2O cellulose composite microspheres can replace existing oxygen
Change zinc class catalysis material, utilize ZnO and Cu2Electronic saving function between O realizes the catalytic degradation work(under non-illumination condition
Energy；Using the relatively rich permeability of cellulose microsphere, the composite photocatalyst prepared has high-specific surface area, high Kong Rongte
Sign, shows preferable photocatalytic degradation and memory performance, preparation process is simple, belongs to a kind of environmentally friendly material.
Description of the drawings
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is Regenerated cellulose microspheres loaded Cu2The SEM figures of O/ZnO compounds, (a) SEM overall diagrams, (b) partial enlargement
Figure.
Specific embodiment
Embodiment 1
1st, the preparation of Regenerated cellulose microspheres：
It is 8 to prepare mass ratio:12:80 NaOH/ urea/water solution 200g, are cooled to -12 DEG C in advance, and it is molten to weigh 1g (over dry)
Solution slurry (chemical cellulose content >=95%) is distributed to 200g in the mixed solvents, adds in the crosslinking agent (epoxychloropropane) of 0.05g, hands over
Connection agent dosage accounts for the 5% of cellulose quality, and -12 DEG C of holding is temperature-resistant, and stirs 30min under 400r/min rotating speeds and handed over
Join cellulose solution.This solution obtains transparency cellulose solution after 25 DEG C of evacuation and centrifugal degassing 30min under 5000r/min rotating speeds and treats
With.The transparency cellulose solution of the above-mentioned preparations of 10g is taken, adds in the atoleine that 100g contains Span 80 (mass fraction accounts for 5%)
In solution, when being kept for 25 DEG C, stirring, emulsification 3h under 800r/min rotating speeds.Then, lotion pH is adjusted with the dilute hydrochloric acid of 0.1mol/L
It is 7.0 or so to be worth, and forms Regenerated cellulose microspheres.It stands, makes demixing, lower floor's water phase is respectively with deionized water, acetone
Filter wash twice, obtains porous regeneration cross-linked cellulose microballoon, for future use after last freeze-dried (- 50 DEG C, 24 hours).
2nd, porous cellulose microballoon prepares Cu2O/ cellulose composite microspheres：
Using the Regenerated cellulose microspheres obtained in step 1 as raw material, Cu is induced2O predecessors prepare Cu2O/ celluloses are micro-
Ball：0.5g cellulose microspheres are weighed, is placed in the 500ml three neck round bottom flask containing 200ml deionized waters, 5 is swollen at 25 DEG C
Hour, the CuCl of addition 10ml 0.04mol/L2Aqueous solution keeps 25 DEG C of temperature-resistant, 300r/min magnetic agitations 3 hours,
Cellulose microsphere is made fully to adsorb copper ion, then (1 drop/s) adds in the NaOH aqueous solutions of 5ml 0.4mol/L dropwise, then by
The ascorbic acid that (1 drop/s) adds in 10ml 0.2mol/L is dripped, keeps 25 DEG C of temperature-resistant, continuation 300r/min magnetic agitations 30
Minute, it is centrifuged through 8000r/min, obtains yellow mercury oxide, successively with deionized water, absolute ethyl alcohol filter wash twice, removal
Impurity obtains Cu2O/ cellulose composite microspheres, after freeze-dried (- 50 DEG C, 24 hours) for future use.
3、Cu2O/ cellulose composite microsphere area load ZnO nano crystal：
With Cu obtained in step 22O/ cellulose composite microspheres are raw material, induce ZnO predecessors, prepare ZnO/Cu2O/ is fine
The plain microballoon of dimension：Weigh 0.2g Cu2O/ cellulose microspheres are immersed in containing 0.1g Zn (NO3)270ml deionized waters in, 25 DEG C
Under, 300r/min magnetic agitations 3 hours make Cu2O/ cellulose microspheres are fully swollen and zinc ion saturation are adsorbed, then slowly add
Enter the urea of 0.5g, continue magnetic agitation (300r/min) after 30 minutes, be transferred to 100ml containing polytetrafluoroethyllining lining
It in water heating kettle, is reacted 12 hours in 180 DEG C of baking oven, the product finally obtained is successively with deionized water, absolute ethyl alcohol filter wash
Twice, freeze-drying (- 50 DEG C, 24 hours) obtains ZnO/Cu2O/ cellulose microspheres.
4、ZnO/Cu2O/ cellulose composite microsphere photocatalysis Memorability is tested：
The photocatalysis of sample and its " memory " performance are completed in light-catalyzed reaction case, the specific steps are：Weigh 50mg
The ZnO/Cu of preparation2O/ cellulose microspheres are added in the methyl orange aqueous solution that 100ml initial concentrations are 10mg/L (C0), are placed in dark
Place 1 hour, makes catalyst reach adsorption equilibrium.Then it is hanged with methyl orange of ultraviolet source (36W) irradiation containing photochemical catalyst
Supernatant liquid.It is stirred continuously with magnetic stirring apparatus in During Illumination, is taken respectively under 15min, 30min, 60min, 90min, 120min
Sample 4ml with 0.45 μm of membrane filtration, obtains filtrate, with ultraviolet-visible spectrophotometer in the case where wavelength is 664nm, to go
Ionized water is reference, measures the absorbance of methyl orange solution, determines residual concentration (C) according to standard curve, research photocatalysis is anti-
(t) and dyestuff residual concentration percentage (C/C between seasonable0), degradation percentage (1-C/C0) etc. relationships.Ultraviolet light light is studied respectively
After 30min, 60min, 90min, 120min, close light source respectively, continue magnetic agitation, 15min, 30min, 60min,
Separately sampled 4ml under 90min, 120min, with 0.45 μm of membrane filtration, obtains filtrate, uses ultraviolet-visible spectrophotometer
In the case where wavelength is 664nm, using deionized water as reference, the absorbance of methyl orange solution is measured, remnants are determined according to standard curve
Concentration (C), research light-catalyzed reaction time (t) and dyestuff residual concentration percentage (C/C0), degradation percentage (1-C/C0) etc. passes
System.
Embodiment 2
1st, the preparation of Regenerated cellulose microspheres：
It is 8 to prepare mass ratio:12:80 NaOH/ urea/water solution 200g, are cooled to -12 DEG C in advance, and it is molten to weigh 10g (over dry)
Solution slurry (chemical cellulose content >=95%) is distributed to 200g in the mixed solvents, adds in the crosslinking agent (epoxychloropropane) of 2g, crosslinking agent
Dosage accounts for the 20% of cellulose quality, and -12 DEG C of holding is temperature-resistant, and stirs 30min under 800r/min rotating speeds and be crosslinked
Cellulose solution.This solution obtains transparency cellulose solution after 15 DEG C of evacuation and centrifugal degassing 30min under 8000r/min rotating speeds and treats
With.The transparency cellulose solution of the above-mentioned preparations of 10g is taken, adds in the liquid stone that 100g contains Span 80 (mass fraction accounts for 10%)
In wax solution, when being kept for 25 DEG C, stirring, emulsification 5h under 1000r/min rotating speeds.Then, breast is adjusted with the dilute hydrochloric acid of 0.1mol/L
Liquid pH value is 7.0 or so, forms Regenerated cellulose microspheres.Stand, make demixing, lower floor's water phase respectively with deionized water,
Acetone filter wash twice, obtains porous regeneration cross-linked cellulose microballoon after last freeze-dried (- 50 DEG C, 24 hours), in case after
With.
2nd, porous cellulose microballoon prepares Cu2O/ cellulose composite microspheres：
Using the Regenerated cellulose microspheres obtained in step 1 as raw material, Cu is induced2O predecessors prepare Cu2O/ celluloses are micro-
Ball：0.5g cellulose microspheres are weighed, is placed in the 500ml three neck round bottom flask containing 200ml deionized waters, 5 is swollen at 25 DEG C
Hour, the CuCl of addition 50ml 0.04mol/L2Aqueous solution keeps 25 DEG C of temperature-resistant, 300r/min magnetic agitations 3 hours,
Cellulose microsphere is made fully to adsorb copper ion, then (1 drop/s) adds in the NaOH aqueous solutions of 10ml 0.4mol/L dropwise, then
(1 drop/s) adds in the ascorbic acid of 10ml 0.2mol/L dropwise, keeps 25 DEG C of temperature-resistant, continuation 300r/min magnetic agitations
It 30 minutes, is centrifuged through 10000r/min, obtains yellow mercury oxide, successively with deionized water, absolute ethyl alcohol filter wash twice, gone
Except impurity, Cu is obtained2O/ cellulose composite microspheres, after freeze-dried (- 50 DEG C, 24 hours) for future use.
3、Cu2O/ cellulose composite microsphere area load ZnO nano crystal：
With Cu obtained above2O/ cellulose composite microspheres are raw material, induce ZnO predecessors, prepare ZnO/Cu2O/ fibers
Plain microballoon：Weigh 0.5g Cu2O/ cellulose microspheres are immersed in containing 0.2g Zn (NO3)270ml deionized waters in, 25 DEG C
Under, 200r/min magnetic agitations 3 hours make Cu2O/ cellulose microspheres are fully swollen and zinc ion saturation are adsorbed, then slowly add
Enter the urea of 1g, continue magnetic agitation (200r/min) after 30 minutes, be transferred to the water containing polytetrafluoroethyllining lining of 100ml
It in hot kettle, is reacted 12 hours in 200 DEG C of baking oven, the product finally obtained is successively with deionized water, absolute ethyl alcohol filter wash two
Secondary, freeze-drying (- 50 DEG C, 24 hours) obtains ZnO/Cu2O/ cellulose microspheres.
4、ZnO/Cu2O/ cellulose composite microsphere photocatalysis Memorability is tested：
The photocatalysis of sample and its " memory " performance are completed in light-catalyzed reaction case, the specific steps are：Weigh 50mg
The ZnO/Cu of preparation2It is 10mg/L (C that O/ cellulose microspheres, which add in 100ml initial concentrations,0) methyl orange aqueous solution in, be placed in dark
Place 1 hour, makes catalyst reach adsorption equilibrium.Then it is hanged with methyl orange of ultraviolet source (36W) irradiation containing photochemical catalyst
Supernatant liquid.It is stirred continuously with magnetic stirring apparatus in During Illumination, is taken respectively under 15min, 30min, 60min, 90min, 120min
Sample 4ml with 0.45 μm of membrane filtration, obtains filtrate, with ultraviolet-visible spectrophotometer in the case where wavelength is 664nm, to go
Ionized water is reference, measures the absorbance of methyl orange solution, determines residual concentration (C) according to standard curve, research photocatalysis is anti-
(t) and dyestuff residual concentration percentage (C/C between seasonable0), degradation percentage (1-C/C0) etc. relationships.Ultraviolet light light is studied respectively
After 30min, 60min, 90min, 120min, close light source respectively, continue magnetic agitation, 15min, 30min, 60min,
Separately sampled 4ml under 90min, 120min, with 0.45 μm of membrane filtration, obtains filtrate, uses ultraviolet-visible spectrophotometer
In the case where wavelength is 664nm, using deionized water as reference, the absorbance of methyl orange solution is measured, remnants are determined according to standard curve
Concentration (C), research light-catalyzed reaction time (t) and dyestuff residual concentration percentage (C/C0), degradation percentage (1-C/C0) etc. passes
System.
Embodiment 3
1st, the preparation of Regenerated cellulose microspheres：
It is 8 to prepare mass ratio:12:80 NaOH/ urea/water solution 200g, are cooled to -12 DEG C in advance, and it is molten to weigh 5g (over dry)
Solution slurry (chemical cellulose content >=95%) is distributed to 200g in the mixed solvents, adds in the crosslinking agent (epoxychloropropane) of 0.5g, is crosslinked
Agent dosage accounts for the 10% of cellulose quality, and -12 DEG C of holding is temperature-resistant, and stirs 20min under 600r/min rotating speeds and handed over
Join cellulose solution.This solution obtains transparency cellulose solution after 20 DEG C of evacuation and centrifugal degassing 20min under 6000r/min rotating speeds and treats
With.The transparency cellulose solution of the above-mentioned preparations of 5g is taken, adds in the atoleine that 100g contains Span 80 (mass fraction accounts for 4%)
In solution, when being kept for 25 DEG C, stirring, emulsification 4h under 800r/min rotating speeds.Then, lotion pH is adjusted with the dilute hydrochloric acid of 0.1mol/L
It is 7.0 or so to be worth, and forms Regenerated cellulose microspheres.It stands, makes demixing, lower floor's water phase is respectively with deionized water, acetone
Filter wash twice, obtains porous regeneration cross-linked cellulose microballoon, for future use after last freeze-dried (- 50 DEG C, 24 hours).
2nd, porous cellulose microballoon prepares Cu2O/ cellulose composite microspheres：
Using Regenerated cellulose microspheres obtained in step 1 as raw material, Cu is induced2O predecessors prepare Cu2O/ celluloses are micro-
Ball：0.5g cellulose microspheres are weighed, is placed in the 500ml three neck round bottom flask containing 200ml deionized waters, 3 is swollen at 25 DEG C
Hour, the CuCl of addition 40ml 0.04mol/L2Aqueous solution keeps 25 DEG C of temperature-resistant, 300r/min magnetic agitations 3 hours,
Cellulose microsphere is made fully to adsorb copper ion, then (1 drop/s) adds in the NaOH aqueous solutions of 8ml 0.4mol/L dropwise, then by
The ascorbic acid that (1 drop/s) adds in 10ml 0.2mol/L is dripped, keeps 25 DEG C of temperature-resistant, continuation 300r/min magnetic agitations 20
Minute, it is centrifuged through 8000r/min, obtains yellow mercury oxide, successively with deionized water, absolute ethyl alcohol filter wash twice, removal
Impurity obtains Cu2O/ cellulose composite microspheres, after freeze-dried (- 50 DEG C, 24 hours) for future use.
3、Cu2O/ cellulose composite microsphere area load ZnO nano crystal：
With Cu obtained in step 22O/ cellulose composite microspheres are raw material, induce ZnO predecessors, prepare ZnO/Cu2O/ is fine
The plain microballoon of dimension：Weigh 0.5g Cu2O/ cellulose microspheres are immersed in containing 0.1g Zn (NO3)270ml deionized waters in, 25 DEG C
Under, 200r/min magnetic agitations 3 hours make Cu2O/ cellulose microspheres are fully swollen and zinc ion saturation are adsorbed, then slowly add
Enter the urea of 0.5g, continue magnetic agitation (300r/min) after 30 minutes, be transferred to 100ml containing polytetrafluoroethyllining lining
It in water heating kettle, is reacted 24 hours in 180 DEG C of baking oven, the product finally obtained is successively with deionized water, absolute ethyl alcohol filter wash
Twice, freeze-drying (- 50 DEG C, 24 hours) obtains ZnO/Cu2O/ cellulose microspheres.
4、ZnO/Cu2O/ cellulose composite microsphere photocatalysis Memorability is tested：
The photocatalysis of sample and its " memory " performance are completed in light-catalyzed reaction case, the specific steps are：Weigh 50mg
The ZnO/Cu of preparation2It is 10mg/L (C that O/ cellulose microspheres, which add in 100ml initial concentrations,0) methyl orange aqueous solution in, be placed in dark
Place 1 hour, makes catalyst reach adsorption equilibrium.Then it is hanged with methyl orange of ultraviolet source (36W) irradiation containing photochemical catalyst
Supernatant liquid.It is stirred continuously with magnetic stirring apparatus in During Illumination, is taken respectively under 15min, 30min, 60min, 90min, 120min
Sample 4ml with 0.45 μm of membrane filtration, obtains filtrate, with ultraviolet-visible spectrophotometer in the case where wavelength is 664nm, to go
Ionized water is reference, measures the absorbance of methyl orange solution, determines residual concentration (C) according to standard curve, research photocatalysis is anti-
(t) and dyestuff residual concentration percentage (C/C between seasonable0), degradation percentage (1-C/C0) etc. relationships.Ultraviolet light light is studied respectively
After 30min, 60min, 90min, 120min, close light source respectively, continue magnetic agitation, 15min, 30min, 60min,
Separately sampled 4ml under 90min, 120min, with 0.45 μm of membrane filtration, obtains filtrate, uses ultraviolet-visible spectrophotometer
In the case where wavelength is 664nm, using deionized water as reference, the absorbance of methyl orange solution is measured, remnants are determined according to standard curve
Concentration (C), research light-catalyzed reaction time (t) and dyestuff residual concentration percentage (C/C0), degradation percentage (1-C/C0) etc. passes
System.
As shown in Figure 1, Regenerated cellulose microspheres loaded Cu2After O/ZnO, its porous feature, surface have been still maintained
There are abundant hole, the Cu loaded on cellulose microsphere2O crystal is smaller compared with ZnO crystal.ZnO/Cu prepared by the present invention2O/ is fine
The plain complex microsphere of dimension has high-specific surface area (>=100m2/ g), Gao Kongrong (>=1cm3/ g) feature；For the methyl orange of 10mg/L
Aqueous solution, under ultraviolet light (36W), after 30 minutes, methyl orange removal rate is more than 70%, after sixty minutes, methyl orange removal
Rate is close to 100%；After removing illumination, after 30 minutes, methyl orange removal rate is more than 40%, and after sixty minutes, methyl orange removal rate surpasses
70% is crossed, shows preferable photocatalytic degradation and memory performance.
Although specific embodiments of the present invention have been described above, those familiar with the art should manage
Solution, our described specific embodiments are merely exemplary rather than for the restriction to the scope of the present invention, are familiar with this
The equivalent modification and variation that the technical staff in field is made in the spirit according to the present invention, should all cover the present invention's
In scope of the claimed protection.
Claims (5)
1. a kind of preparation method of memory-type photocatalytic fiber element microballoon, it is characterised in that：To dissolve pulp fibres as raw material, with anti-
Phase emulsion method prepares Regenerated cellulose microspheres, then induces Cu2O predecessors prepare Cu through liquid phase reduction2O/ cellulose microspheres,
Again through hydro-thermal method, in Cu2O/ cellulose microsphere area load ZnO nano crystal.
2. the preparation method of memory-type photocatalytic fiber element microballoon according to claim 1, it is characterised in that：Including as follows
Step：
(1), the preparation of Regenerated cellulose microspheres：
Using dissolving pulp as raw material, Na OH/ urea/H is dissolved at -9~-15 DEG C2O systems, using epoxychloropropane as crosslinking agent
Regenerated cellulose microspheres are prepared for using emulsion method, emulsifier is Span 80；
(2), Regenerated cellulose microspheres prepare Cu2O/ cellulose composite microspheres：
Using above-mentioned Regenerated cellulose microspheres as raw material, Cu is induced2O precursor Cs uCl2, using ascorbic acid as reducing agent, in alkaline item
Cu is prepared under part2O/ cellulose composite microspheres；
(3)、Cu2O/ cellulose composite microsphere area load ZnO nano crystal：
With Cu obtained above2O/ cellulose composite microspheres are raw material, induce ZnO predecessor Zn (NO3)2, using urea as precipitation
Agent prepares ZnO/Cu2O/ cellulose microspheres.
3. the preparation method of memory-type photocatalytic fiber element microballoon according to claim 2, it is characterised in that：Step (1)
Reaction condition be：Emulsification stirring speed is 500-1000r/min, and the mass ratio of dissolving pulp and crosslinking agent is 1-10：0.05-2,
The mass ratio of dissolving pulp and emulsifier is 1-10：1-10.
4. the preparation method of memory-type photocatalytic fiber element microballoon according to claim 2, it is characterised in that：Step (2)
Reaction condition be：Per 0.1-0.5g Regenerated cellulose microspheres, 0.4-2 × 10 are added in-3mol CuCl2, add in 2-4 × 10-3mol
NaOH adds in 0.4-2 × 10-3Mol ascorbic acid.
5. the preparation method of memory-type photocatalytic fiber element microballoon according to claim 2, it is characterised in that：Step (3)
Reaction condition be：Cu2O/ cellulose composite microspheres and Zn (NO3)2, urea mass ratio be 0.1-0.5：0.1-0.5：0.5-
1, hydrothermal temperature is 150-200 DEG C.
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| CN109134944A (en) * | 2018-08-28 | 2019-01-04 | 安徽聚欣新材料科技有限公司 | A kind of porous small ball and its application with different chemical functional groups |
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