CN105536826B - A kind of Ag, AgCl and TiO2One one step preparation method of composite photocatalyst fiber - Google Patents
A kind of Ag, AgCl and TiO2One one step preparation method of composite photocatalyst fiber Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 41
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 4
- 239000005457 ice water Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 101710089042 Demethyl-4-deoxygadusol synthase Proteins 0.000 abstract description 2
- 239000012453 solvate Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 7
- 229910003074 TiCl4 Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 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 description 1
- AKMXMQQXGXKHAN-UHFFFAOYSA-N titanium;hydrate Chemical compound O.[Ti] AKMXMQQXGXKHAN-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B01J35/39—
-
- B01J35/58—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
-
- 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
- B01J37/344—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 electromagnetic wave energy
- B01J37/345—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 electromagnetic wave energy of ultraviolet wave energy
Abstract
A kind of Ag, AgCl and TiO2One one step preparation method of composite photocatalyst fiber, comprises the following steps：(1) TiCl is taken4, distilled water and acetylacetone,2,4-pentanedione be completely dissolved in methanol solvate, mix in ice-water bath, completed to hydrolytic-polymeric reaction；(2) triethylamine is added into system, adds the tetrahydrofuran that can be completely dissolved DDGS, filters and removes insoluble matter；(3) tetrahydrofuran is boiled off, obtains poly- acetyl acetone titanium precursors；(4) adding methanol is completely dissolved it, adds containing AgNO3The methanol solution of the aqueous solution, is concentrated to give spinning solution, and spinning obtains precursor fibre；(5) precursor fibre is calcined, obtains AgCl and TiO2Composite fibre；(6) composite fibre is positioned under ultraviolet light and carries out photoreduction, obtain Ag/AgCl/TiO2Composite photocatalyst fiber.This invention simplifies preparation technology, synthesizes advantage of lower cost, can obtain practicality and visible light-responded all good high efficiency photocatalysis composite fibre.
Description
Technical field
The present invention relates to one kind to utilize TiCl4Prepare Ag, AgCl and TiO2The method of composite photocatalyst fiber, belonging to has
The composite photocatalyst technical field of fiber preparation of visible light activity.
Background technology
In recent years, photocatalysis as a kind of new water process and potential new energy correlation technique by increasingly extensive
Concern.In conventional semiconductor light-catalyst, TiO2Because having the advantages that fast light burn into resistant to chemical etching and nontoxic and
Gain great popularity.It is well known that TiO2Energy gap it is wider (3.2eV), can only absorbing wavelength it is ultraviolet less than 387.5nm
Light, visible ray can not be effectively utilized, already as classical TiO2Photocatalysis water technology is promoted withered with the fetters of application.In the sun
In the illumination of radiation, ultraviolet light is generally less than 5%, and be in leading position is visible ray and near infrared light.It can be seen that, it is intended to seek
Seek enhancing TiO2The method of modifying research of visible light catalysis activity has academic and application value concurrently.
AgCl is both traditional photosensitive material, is new catalysis material again, but when carrying out light-catalyzed reaction, because of hair
Give birth to serious photoetch and can not be applied as stable photochemical catalyst.Research is found, AgCl particles is carried out in advance purple
Outer lamp or xenon lamp irradiate, then the part Ag on its surface+The nanometer Ag of simple substance will be reduced to0Particle, shown in visible region peculiar
Surface plasma resonance, thus obtain that there is visible light-responded Ag/AgCl plasma photocatalysis agent.Surface plasma
Ripple is a kind of electromagnetic surface wave, is caused metal surface electronic when electromagnetic wave is in metal and dielectric surface propagation
Dilatational wave.Under incident light electric field action, the free electron of nano-noble metal particle surface can produce collective oscillation, work as optical frequency
When rate is identical with the frequency of oscillation of free electron, that is, produce surface plasmon resonance effect.This resonance is macroscopically with regard to table
It is now absorption of the metal nanoparticle to special wavelength light.
In recent years, further to promote the separation of photo-generated carrier, by Ag/AgCl plasma loads in TiO2Surface system
Standby visible response type photochemical catalyst, already as the study hotspot for the treatment of function new material.At present, prepare Ag/AgCl with
TiO2Composite photo-catalyst mainly takes chemical precipitation method, i.e., by AgCl nanoparticle depositions various forms TiO2Surface, should
Method need to purchase or prepare in advance TiO2, then the AgCl particles of formation are deposited on by TiO by chemical precipitation method2Surface, raw material utilize
Rate is low and complex steps.In addition, the TiO that relevant Ag/AgCl is modified in document2Composite catalyst is nearly all micro-/ nano film
Or dusty material, and the recycling that is unfavorable for photocatalysis water treatment applications after lower than surface.
Wide material sources, cheap TiCl4It is to prepare TiO2A kind of raw material that can be selected but and be of little use, this because of
Its unique chemical property, such as there is heat, water decomposition heat release is met, discharges the intrinsic drawback such as poisonous corrosive gas.Especially
It is noted that the Elements C l in its molecule is generally viewed as being difficult to the harmful element being utilized and need to try to remove.
The content of the invention
A kind of it is an object of the present invention to deficiency existing for existing composite photo-catalyst technology of preparing, there is provided activity
It is high, cost is low, flow is short, is easy to Ag, AgCl and TiO of recovery2One one step preparation method of composite photocatalyst fiber, this method exist
It need not introduce under conditions of additional Cl sources, directly utilize TiCl4In Elements C l as unique Cl sources.
Ag, AgCl and TiO of the present invention2One one step preparation method of composite photocatalyst fiber, comprises the following steps：
(1) ︰ 1 of 1 ︰ 2 ratio measures TiCl in molar ratio4, distilled water and acetylacetone,2,4-pentanedione, three kinds of materials are completely dissolved in first
In alcoholic solvent, mix in ice-water bath, completed to hydrolytic-polymeric reaction；
(2) by triethylamine and TiCl in step (1)4The ︰ 1 of mol ratio 0.95 ratio, triethylamine is added into system, then added
Enter the tetrahydrofuran that can be completely dissolved DDGS, filter and remove insoluble matter, the Cl of residual-As being synthesized in subsequent step
AgCl Cl sources；
(3) rotary evaporation concentrates solution in 50 DEG C~60 DEG C of water-bath, removes tetrahydrofuran, obtains poly- acetylacetone,2,4-pentanedione
Close titanium colloidal sol；
(4) methanol is added into poly- acetyl acetone titanium colloidal sol is completely dissolved it, adds containing AgNO3Water and first
Mixed alkoxide solution, AgNO in the mixed solution3Concentration is 1.55g/L, and the volume ratio of methanol and water is 50：1, wherein AgNO3With step
Suddenly TiCl in (1)4Mol ratio be 0.05 ︰ 1；Carry out revolving processing again afterwards, solution is concentrated into viscosity and reach 5 Pas
~10Pas, spinning solution is obtained, carry out dry method centrifugal spinning, obtain precursor fibre；
Centrifugal spinning mould can be used disclosed in CN2873805Y《TiO 2 sol rotates swaying wire equipment》.
(5) precursor fibre is subjected to temperature programming heat treatment, from room temperature to 600 DEG C with organics removal, 600
Temperature fall after being incubated 2 hours at DEG C, obtain AgCl and TiO2Composite fibre intermediate；
The step (5), control following procedure are warming up to 600 DEG C：
25 DEG C~100 DEG C：30 minutes；
100 DEG C~200 DEG C：12 minutes；
200 DEG C~400 DEG C：120 minutes；
400 DEG C~500 DEG C：30 minutes；
500 DEG C~600 DEG C：120 minutes.
(6) obtained composite fibre intermediate is placed in 8~12mWcm of light intensity-2Ultraviolet light under, lasted
The photoreduction of 1.5 hours~2 hours, obtain Ag/AgCl/TiO2Composite photocatalyst fiber product.
Above mentioned chemicals is that analysis is pure, and water is distilled water.
The present invention possesses following characteristics：
(1) Ag/AgCl/TiO can be prepared with a step2Photocatalytic fiber, with needing first to prepare TiO at present2, then in its table
Face deposition Ag/AgCl two steps or multistep are prepared and compared, and this method is simplified, and improves technique, is simplified process and is improved
Feed stock conversion；
(2)TiCl4Ti sources and Cl sources are used as simultaneously, greatlys save the input and its utilization rate of raw material.With the fourth of metatitanic acid four
The conventional organic titanium source such as ester, isopropyl titanate is compared, TiCl4It is wide material sources, cheap, it is prepared into so as to be greatly reduced
This；
(3) TiCl is being utilized4Prepare TiO2Hydrolysis in can generate substantial amounts of by-product hydrochloric acid, if not handling or locating
It is improper to manage, and not only bad for the polycondensation reaction of hydrate titanium ion, and produces and damages great acid mist to environment and health of human body
And acid waste water.It is contemplated that turning waste into wealth, by-product hydrochloric acid is used, the synchronous Cl sources as generation AgCl, made
Itself and AgNO3Generation metathesis reaction, original position prepare AgCl particles and are synchronously deposited on the TiO generated already2Colloid surface.
Preparation process meets the green chemistry process principle of " raising atom utilization "；
(4) present invention can be by controlling AgNO3Addition control Ag and Ti stoichiometric proportion, obtain Ag and Ti
Optimum chemical metering ratio so that the photocatalysis effect of prepared composite fibre is optimal.
Embodiment
Embodiment 1
The present embodiment prepares Ag/AgCl/TiO by procedure below2Composite photocatalyst fiber：
(1) ︰ 1 of 1 ︰ 2 ratio measures TiCl in molar ratio410.0mL, distilled water 5mL and acetylacetone,2,4-pentanedione 9.5mL.In frozen water
Under stirring condition in bath：1. by TiCl4Be added dropwise in 50mL methanol, then be added dropwise thereto containing 5mL distilled water and
(distilled water is 1 with methanol volume ratio to 25mL methanol composition Water-Methanol System:5), continue stirring 20 minutes, obtain mixed liquor A；
2. 9.5mL acetylacetone,2,4-pentanediones are dissolved in 180mL methanol, mixed liquid B is obtained, 3. mixed liquid B is added dropwise in mixed liquor A, after
Continuous stirring obtains mixed liquor C to hydrolysis condensation reaction balance is reached.
(2) a certain amount of triethylamine is added dropwise dropwise into mixed liquor C so that triethylamine and TiCl in step (1)4Mole
Than for 0.95 ︰ 1, adding tetrahydrofuran, the addition of tetrahydrofuran so that polymerization titanium dissolving, by filter remove it is insoluble
Triethylamine hydrochloride white precipitate.Remaining Cl in the liquid phase-As the Cl sources that AgCl is prepared in subsequent step.
(3) rotary evaporation is carried out under 50 DEG C of water-baths, tetrahydrofuran is removed, obtains poly- acetyl acetone titanium colloidal sol.
(4) methanol is added, is completely dissolved poly- acetyl acetone titanium colloidal sol, the methanol for obtaining poly- acetyl acetone titanium is molten
Liquid.Configuration concentration is 1.55g/L AgNO3Methanol-water mixed solution (VMethanol/VWater=50) 20mL, wherein AgNO are measured and3With step
Suddenly TiCl in (1)4Mol ratio be 0.05 ︰ 1, obtain mixed liquor D.
(5) poly- acetyl acetone titanium colloidal sol is placed in ultrasonic generator, makes a diameter of 13mm titanium alloy ultrasonic probe
2~3cm of immersed in liquid level, ultrasound condition is set as amplitude 40%, the ︰ 1 of dutycycle 1, bath temperature is kept for 50 DEG C, opens separatory funnel
Switch, mixed liquor D is slowly dropped in the methanol solution of poly- acetyl acetone titanium precursors, continual ultrasonic 1 hour.Revolve afterwards
Steaming makes viscosity reach 5Pas, obtains poly- acetyl acetone titanium and the spinning liquid as precursor of AgCl mixing.Centrifuged and spun using dry method
Silk, under room temperature, 10000r/min speed conditions, the spinneret orifice high speed for being about 0.2mm from aperture by spinning liquid as precursor
Spin, obtain precursor fibre.
(6) precursor fibre is put into tube furnace and is warming up to 600 DEG C of roastings by following procedure, to remove having in fiber
Machine thing：
25 DEG C~100 DEG C：30 minutes；
100 DEG C~200 DEG C：12 minutes；
200 DEG C~400 DEG C：120 minutes；
400 DEG C~500 DEG C：30 minutes；
500 DEG C~600 DEG C：120 minutes.
2 hours are incubated at 600 DEG C and Temperature fall, obtain white AgCl and TiO2Composite fibre.
(7) composite fibre is placed under the 120W high-pressure sodium lamps of unlatching at 0.5m, and control surface light intensity is maintained at 8
mW·cm-2, the photoreduction for lasting 1.5 hours~2 hours is carried out under conditions of ultraviolet light so that at fiber surface
AgCl parts are reduced into Ag0, it is deposited on AgCl surfaces, forms tensile strength 110MPa~1.0GPa, 4 μm~15 μm of diameter,
Monofilament continuous length 3cm~40cm, BET specific surface area 90m2/ g~200m2/ g Ag/AgCl/TiO2Composite short fiber (TiO2
Crystalline phase is Anatase).
(8) obtained fiber product is placed in diameter 145mm, high 70mm crystallising dish bottom, forms oneself used in experiment
Fixed-bed type photo catalysis reactor processed.Photocatalytic degradation experiment is carried out with interval batch mode under sunshine irradiation, uses 100mL
Concentration is that 20mg/L methylene blue solution makees simulated wastewater, and with wriggling pump circulation, is by spinner flowmeter coutroi velocity
100mL/min, the available depth 20mm of simulated wastewater.Lucifuge is handled 30 minutes before reaction, will after reaching adsorption-desorption balance
Added with 0.1g Ag/AgCl/TiO2The open field that the reactor of composite photocatalyst chopped fiber is placed in no veil carries out day CD-ROM drive
Dynamic light-catalyzed reaction, irradiation time are the ︰ 00 of 12 ︰ 00~14 under the conditions of the fair weather in May of Jinan, and this is measured using illumination photometer
The sunlight intensity of period concentrates on 570~592Wm-2In the range of.Sampled after reaction in 2 hours, utilize ultraviolet-visible point
Light photometer carries out analysis measure.Maximum absorption wavelength (the λ of methylene bluemax) at 665 ± 2nm, therefore with wavelength
Concentration C at 665nm and the C-A standard curves that absorbance A is established measure concentration before and after reaction and calculate percent of decolourization, calculate
As a result it is 91.3%.
Embodiment 2
The present embodiment and embodiment 1 by the bath temperature of the rotary evaporation in step (3) except that be changed to 55 DEG C, step
Suddenly the AgNO in (4)3The aqueous solution is changed to concentration 3.85g/L, and the viscosity in step (5) reaches 7.5Pas, in step (7)
Surface intensity control is in 10mWcm-2。
That obtain is 100MPa~1.0GPa, and 4 μm~15 μm of diameter, monofilament continuous length 5cm~40cm, BET compare surface
Product 100m2/ g~200m2/ g Ag/AgCl/TiO2Composite short fiber.
The composite short fiber that the present embodiment is obtained carries out photocatalytic degradation experiment, the methylene for being 30mg/L with 50mL concentration
Base indigo plant solution makees simulated wastewater, and reaction condition is identical with (8) the step of embodiment 1.Sampling analysis after reaction is carried out 2 hours, meter
Obtained percent of decolourization is 98.9%.
Embodiment 3
The present embodiment and embodiment 1 by the bath temperature of the rotary evaporation in step (3) except that be changed to 60 DEG C, step
Suddenly the AgNO in (4)3The aqueous solution is concentration 7.80g/L, and the viscosity in step (5) reaches 10Pas, the surface in step (7)
Intensity control is in 12mWcm-2。
That obtain is 100MPa~900MPa, and 4 μm~20 μm of diameter, monofilament continuous length 3cm~35cm, BET compare surface
Product 100m2/ g~180m2/ g Ag/AgCl/TiO2Composite short fiber.
The composite short fiber that the present embodiment is obtained carries out photocatalytic degradation experiment, the methylene for being 30mg/L with 50mL concentration
Base indigo plant solution makees simulated wastewater, and reaction condition is identical with (8) the step of embodiment 1.Sampling analysis after reaction is carried out 2 hours, meter
Obtained percent of decolourization is 92.2%.
Claims (2)
1. a kind of Ag, AgCl and TiO2One one step preparation method of composite photocatalyst fiber, it is characterized in that, comprise the following steps：
(1) ︰ 1 of 1 ︰ 2 ratio measures TiCl in molar ratio4, distilled water and acetylacetone,2,4-pentanedione, it is molten that three kinds of materials are completely dissolved in methanol
In agent, mix in ice-water bath, completed to hydrolytic-polymeric reaction；
(2) by triethylamine and TiCl in step (1)4The ︰ 1 of mol ratio 0.95 ratio, add triethylamine, add can make it is solvable
The tetrahydrofuran that thing is completely dissolved, filter and remove insoluble matter, the Cl of residual-As the Cl sources that AgCl is synthesized in subsequent step；
(3) rotary evaporation concentrates solution in 50 DEG C~60 DEG C of water-bath, removes tetrahydrofuran, obtains poly- acetyl acetone titanium
Colloidal sol；
(4) methanol is added into poly- acetyl acetone titanium colloidal sol is completely dissolved it, adds containing AgNO3Water mixed with methanol
Solution is closed, AgNO in the mixed solution3Concentration is 1.55g/L, and the volume ratio of methanol and water is 50：1, wherein AgNO3With step
(1) TiCl in4Mol ratio be 0.05 ︰ 1；Carry out revolving processing again afterwards, make solution be concentrated into viscosity reach 5Pas~
10Pas, spinning solution is obtained, carry out dry method centrifugal spinning, obtain precursor fibre；
(5) precursor fibre is subjected to temperature programming heat treatment, from room temperature to 600 DEG C with organics removal, at 600 DEG C
Temperature fall after being incubated 2 hours, obtain AgCl and TiO2Composite fibre intermediate；
(6) obtained composite fibre intermediate is placed in 8~12mWcm of light intensity-2Ultraviolet light under, carry out lasting 1.5 small
When~photoreduction of 2 hours, obtain Ag/AgCl/TiO2Composite photocatalyst fiber product.
2. Ag/AgCl/TiO according to claim 12One one step preparation method of composite photocatalyst fiber, it is characterized in that, institute
State in step (5) and be warming up to 600 DEG C by following procedure：
25 DEG C~100 DEG C：30 minutes；
100 DEG C~200 DEG C：12 minutes；
200 DEG C~400 DEG C：120 minutes；
400 DEG C~500 DEG C：30 minutes；
500 DEG C~600 DEG C：120 minutes.
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|---|---|---|---|---|
| US6162759A (en) * | 1998-02-13 | 2000-12-19 | Sumitomo Chemical Company, Ltd. | Method for producing a catalyst component-carrying titania fiber |
| CN1584156A (en) * | 2004-06-11 | 2005-02-23 | 山东大学 | Preparing method for titanium dioxide fibre |
| CN102350366A (en) * | 2011-08-25 | 2012-02-15 | 武汉理工大学 | Preparation method of Ag-AgCl-TiO2/rectorite composite photochemical catalyst |
| CN103111274A (en) * | 2013-02-28 | 2013-05-22 | 山东大学 | Preparation method of graphene/TiO2 fiber |
| CN103193265A (en) * | 2013-04-09 | 2013-07-10 | 河海大学 | Preparation method of spiral titanium dioxide (TiO2) nano wire doped with silver/silver chloride (Ag/AgCl) |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162759A (en) * | 1998-02-13 | 2000-12-19 | Sumitomo Chemical Company, Ltd. | Method for producing a catalyst component-carrying titania fiber |
| CN1584156A (en) * | 2004-06-11 | 2005-02-23 | 山东大学 | Preparing method for titanium dioxide fibre |
| CN102350366A (en) * | 2011-08-25 | 2012-02-15 | 武汉理工大学 | Preparation method of Ag-AgCl-TiO2/rectorite composite photochemical catalyst |
| CN103111274A (en) * | 2013-02-28 | 2013-05-22 | 山东大学 | Preparation method of graphene/TiO2 fiber |
| CN103193265A (en) * | 2013-04-09 | 2013-07-10 | 河海大学 | Preparation method of spiral titanium dioxide (TiO2) nano wire doped with silver/silver chloride (Ag/AgCl) |
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