CN107456966A - The preparation method of the in-situ modified titanium dioxide of one metal ion species - Google Patents
The preparation method of the in-situ modified titanium dioxide of one metal ion species Download PDFInfo
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- CN107456966A CN107456966A CN201611140620.0A CN201611140620A CN107456966A CN 107456966 A CN107456966 A CN 107456966A CN 201611140620 A CN201611140620 A CN 201611140620A CN 107456966 A CN107456966 A CN 107456966A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 131
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001455 metallic ions Chemical class 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003518 caustics Substances 0.000 claims abstract description 11
- -1 wherein Substances 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004887 air purification Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000003344 environmental pollutant Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010667 large scale reaction Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The present invention provides the preparation method of the in-situ modified titanium dioxide of a metal ion species, belongs to material for air purification field, the technical scheme of use is that the preparation method comprises the following steps：（1）Titanium source, weak caustic solution are added under stirring at normal temperature into water, wherein, titanium source, water, the mass ratio of weak caustic solution are 1：10‑100：1 50, stir and produce dissolved colloidal state titania systems；（2）PH value is adjusted to 6 ~ 8, adds aqueous metallic ions into dissolved colloidal state titania systems under stirring, it is 0.00001 ~ 0.01 to control metal ion and titanium dioxide mass ratio：The 5h of stirring reaction 0.5 at 1,20 100 DEG C, obtains the metal ion-modified titanium dioxide aqueous solution.Beneficial effect is the addition opportunity and control material rate, temperature, pH and reaction time of each raw material of Comprehensive Control, and simple to operate, safe and reliable, green and working condition is gentle, is adapted to large-scale production.
Description
Technical field
The present invention relates to material for air purification field, and in particular to photocatalyst material, especially a metal ion species are former
The preparation method of position modifying titanium dioxide.
Background technology
TiO2As the catalysis material found earliest, there is nontoxic, catalytic activity（Degraded purification and water decomposition hydrogen manufacturing）
It is high, oxidability is strong, stability is good, cost is low, the characteristic such as environment-friendly, be most possible practical catalysis material, with
The rapid development of nanometer technology, preparation, modification and its application of nano titanium oxide are hot as the research of air purification field
Point.However, due to TiO2Wider energy gap（3.2 eV）Determine that it can only play photocatalytic activity under ultraviolet light, it is right
The utilization rate of sunshine is too low；On the other hand, nano titanium oxide is easily reunited, and these all greatly limit its application.
In order to improve the photocatalysis performance of titanium dioxide, ion doping is method of modifying more conventional at present, by mixing
It is miscellaneous that defective locations can be introduced on surface or change crystallinity, so as to influence the absorption ripple that is compound or expanding light of electronics and hole
Section, so as to improve the photocatalytic activity of titanium dioxide.At present, the preparation method of titanium dioxide and modifying titanium dioxide is more, such as
Alkoxide hydrolysis, Hydrothermal preparation method, sol-gal process, chemical precipitation method and solid phase method etc., wherein, sol-gal process prepares letter
It is single, operation is convenient, condition is easily-controllable etc., it is conventional preparation method.However, there is the problem of following in current preparation method, such as
Organic solvent and reagent be widely used, it is larger to endanger, and doping rate is low, and uniform doping is poor, bad dispersibility etc., turns into titanium dioxide
Preparation method technical field technical barrier urgently to be resolved hurrily.
The content of the invention
To solve, metal-doped titanium dioxide preparation process is complicated, organic solvent harmfulness is big, doping rate is low, uniform doping
Property poor, bad dispersibility technical problem, the present invention provide the in-situ modified titanium dioxide of a metal ion species preparation method, pass through
Dissolved colloidal state titania systems are prepared under alkaline environment with water-soluble titanium source, further Comprehensive Control reaction condition, hydrolyzed
Form ingenious choose the right moment in titanium dioxide process and add appropriate transition metal or the precious metal ion aqueous solution is molten, so as to molten
Colloidal titanium dioxide carries out in-situ modified, obtained uniform doping, the metal ion-modified nano titania of good dispersion
Grain, realizes simple operations, green reaction, and substantially increase the photocatalysis performance of material.
The technical solution adopted by the present invention is：The preparation method of the in-situ modified titanium dioxide of one metal ion species, the system
Preparation Method comprises the following steps：
（1）Titanium source, weak caustic solution are added under stirring at normal temperature into water, wherein, titanium source, water, the mass ratio of weak caustic solution are 1：10-
100：1-50, stir and produce dissolved colloidal state titania systems；
（2）PH value is adjusted to 6 ~ 8, aqueous metallic ions is added under stirring into dissolved colloidal state titania systems, controls metal
Ion is 0.00001 ~ 0.01 with titanium dioxide mass ratio：Stirring reaction 0.5-5h at 1,20-100 DEG C, is obtained metal ion-modified
The titanium dioxide aqueous solution.
Preferably, the speed 350-500r/min of the stirring.
The addition titanium source and addition aqueous metallic ions are to be added dropwise.
The aqueous metallic ions concentration is 0.5-1wt.%.
The aqueous metallic ions include but is not limited to transition metal or noble metal Cr, Mn, Fe, Co, Ni, Cu, Au,
The one or more of Ag, Pt, Pd aqueous solution.
The one kind or two of the titanium source in titanyl sulfate, titanium tetrachloride, titanium trichloride, titanium tetrafluoride or alkyl oxygen titanium
More than kind.
The weak caustic solution is the ammoniacal liquor of mass concentration 2.5%.
The dissolved colloidal state titania systems and/or the metal ion-modified titanium dioxide aqueous solution are by centrifugation or mistake
Filter, then will precipitate or filter cake is resuspended with the water of 1-5 times of volume and is uniformly further purified.
Preferably, the preparation method is：
（1）10g titanium sources, 100-130mL 2.5wt.% ammonia spirit are added under stirring at normal temperature into 400-600g water, stirring is equal
It is even to produce dissolved colloidal state titania systems；
（2）By dissolved colloidal state titania systems filter or with 8000-10000r/min centrifuge 8-15min, gained precipitation solid with
The concussion of 80-100ml water is resuspended and ultrasonic 15-30s, and control ph is 6 ~ 8, adds 0.8-1wt.% aqueous metallic ions, control
Metal ion is 0.0001 ~ 0.0003 with titanium dioxide mass ratio：3-4h is stirred at 1,20-40 DEG C, is obtained metal ion-modified
The titanium dioxide aqueous solution.
In above-mentioned technical proposal, there is provided the preparation method of the in-situ modified titanium dioxide of a metal ion species, this method use
Method in situ modification, prepares the titania nanoparticles of doped metal ion, specific method be under the conditions of stirring at normal temperature, with
Water is solvent, and titanium source, weak caustic solution are added into water, and it is 1 to control titanium source, water, the quality parts ratio of weak caustic solution：10-100：
1-50, now, reaction condition are alkalescence, stir and can obtain dissolved colloidal state titania systems, mixing time typically exists
More than 3min, if weak caustic solution addition is less, need mixing time proper extension；Stirring rapid regulation colloidal sol after terminating
The pH value of state titania systems is 6 ~ 8, and those skilled in the art's common method, such as centrifugation resuspension or quiet can be selected in adjusting method
Put and remove supernatant etc., a key as this method is the control that aqueous metallic ions add opportunity, should be selected
When being formed in dissolved colloidal state titanium dioxide forming process and/or just, now there is cotton-shaped suspension in system, and titanium dioxide is in amorphous
State, then adds aqueous metallic ions into uniform dissolved colloidal state titania systems, the added metal ion of control with
The mass ratio of titanium dioxide is 0.00001 ~ 0.01：1, the lower stirring 0.5-5h under 20-100 DEG C of temperature conditionss, you can obtain
The metal ion-modified titania nanoparticles aqueous solution.It is anti-by the addition opportunity of each raw material of synthesis and control in this method
Ratio, reaction temperature, pH and the reaction time of raw material are answered, obtains the metal-doped titanium dioxide that product morphology is homogeneous, activity is high
Photo-catalytic nano particle, under mass production conditions, this method stability is good, and repetitive rate is high, the 24h degradeds of product PARA FORMALDEHYDE PRILLS(91,95)
Efficiency is more than 90%.
The beneficial effects of the invention are as follows：（1）The addition opportunity of each raw material of method Comprehensive Control of the present invention and control reaction
In ratio, reaction temperature, pH and the reaction time of raw material, solvent and reaction reagent are green, safe, are that Green Chemistry is anti-
Should, and it is simple to operate, working condition is gentle, be adapted to large-scale production；（2）In further improved technical scheme, strict control
Mixing speed, aqueous metallic ions are added dropwise, realize doping reaction rate uniform, doping efficiency height, pattern is homogeneous, real
Showed course of reaction, the time it is controllable；It is 0.5-1wt.% aqueous metallic ions from concentration, the ammonia of mass concentration 2.5%
The reaction condition such as water, further comprehensive adjustment reaction density, reaction pH, ensure that the science and stability of preparation method,
And operating condition is safe and reliable；（3）This method raw material sources are extensive, cost is low, and economic benefit and social benefit are high；（4）This hair
Bright method energy consumption is low, reaction reagent and course of reaction are pollution-free, meets green concept.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the metal ion-modified titanium dioxide of the gained of the embodiment of the present invention 1.
Embodiment
The present invention provides the preparation method of the in-situ modified titanium dioxide of a metal ion species, detailed below by way of specific embodiment
The bright present invention is described in detail in order to understand, involved reagent unless otherwise instructed, can be bought by commercial sources and be obtained in embodiment
, institute's application method, it is conventional method unless otherwise instructed.
Embodiment 1：
10g titanyl sulfates are dissolved in 500ml water, the lower ammoniacal liquor for adding 110ml concentration 2.5wt.% are stirred, with 400 r/min's
Stop after speed stirring 10min, obtain dissolved colloidal state titania systems；30min is stood, is centrifuged with 8000-10000r/min, then
Upper liquid is removed, centrifugation gained solid precipitation is resuspended with 90ml water, adjusts pH to 6, the body after resuspension is made by stirring and ultrasound
System is uniform, obtains the dissolved colloidal state titania systems of purifying；
（2）Co (the NO that concentration is 1wt.% are added dropwise into the dissolved colloidal state titania systems of purifying3)2The aqueous solution, add dropwise
It is uneven to enter to avoid metal ion mixing, by controlling rate of addition and mixing speed metal ion mixing so as in situ
The reaction rate of modifying titanium dioxide is uniform, doping efficiency is high, and pattern is homogeneous, realizes course of reaction, controllable, the control of time
Co2+Mass ratio with titanium dioxide is 0.00001：1, it ensure that the ratio of the metal ion of doping and gained are metal ion-modified
The catalytic performance of titanium dioxide, preventing excess metal ion from causing, pattern is mixed and disorderly, doping is uneven, is stirred at 25 DEG C with 350r/min
3h is reacted, obtains the titania nanoparticles aqueous solution of cobalt ions modification, for scanning electron microscope (SEM) photograph referring to accompanying drawing 1, granularmetric analysis is average
Particle diameter 48nm.
Embodiment 2：
10g titanium tetrachlorides are dissolved in 300ml water, stir the lower ammoniacal liquor for adding the wt.% of 100ml concentration 2.5,450r/min stirrings
Stop after 6min, obtain dissolved colloidal state titania systems；50min is stood, is centrifuged with 8000-10000r/min, then removes upper strata
Liquid, centrifugation gained solid precipitation are resuspended with 100ml water, adjust pH to 7, shake 10min, ultrasonic 30s with spiral vortex mixer, make weight
System after outstanding is uniform, obtains the dissolved colloidal state titania systems of purifying；
（2）The MnCl that concentration is 0.8wt.% is added dropwise into the dissolved colloidal state titania systems of purifying2The aqueous solution, control manganese
The mass ratio of ion and titanium dioxide is 0.0001：With 400r/min speed stirring reaction 5h at 1,30 DEG C, obtain manganese ion and change
The titania nanoparticles aqueous solution of property.
Embodiment 3：
10g titanium trichlorides are dissolved in 300ml water, stir the lower ammoniacal liquor for adding the wt.% of 200ml concentration 2.5,500r/min stirrings
Stop after 3min, obtain dissolved colloidal state titania systems；Stand 30min, filter, gained filter cake with 100ml water be resuspended, regulation pH to
8,500r/min speed stir 5min to uniform, and 100Hz ultrasounds 20s makes the system after resuspension uniform, obtains the dissolved colloidal state two of purifying
Titanium oxide system；
（2）The CuCl that concentration is 0.8wt.% is added into the dissolved colloidal state titania systems of purifying2The aqueous solution, control copper ion
Mass ratio with titanium dioxide is 0.01：Stirring reaction 2h at 0 DEG C of Isosorbide-5-Nitrae, obtain the titanium dioxide aqueous solution of copper ion modified.
The in-situ modified photocatalyst of titanium dioxide nano particle of metal ion prepared using the inventive method can be used for formaldehyde
Purification, its purification efficiency test method are as follows：Prepare two identical 1.5m under equal conditions3Laboratory Module in, a conduct
Test chamber, another takes the resulting solution 100g of above-described embodiment 1 to spray to 1 1m as blank cabin2Inertia material
In base paper, it is suspended on respectively in test chamber after surface drying, untreated base paper is hung in blank cabin, and two identicals are delayed
The formaldehyde pollution source of On The Drug Release, it is respectively placed in Laboratory Module and closes Laboratory Module；The fan of Laboratory Module is then opened simultaneously, makes cabin
Interior pollutant cycle balance, close Laboratory Module fan；The concentration of pollutant in Laboratory Module is sampled simultaneously again after 24h, point
Analysis test, pollutants removal rate is calculated, computational methods are with reference to equation below：Pollutants removal rate=（Blank cabin pollutant concentration
Value-sample experiments cabin pollutant concentration value）÷ blank cabin pollutant concentration value × 100%, same method is to the various embodiments described above
Products obtained therefrom carries out the test of formaldehyde clearance, as a result see the table below 1.
The in-situ modified titanium dioxide 24h of embodiment 1-4 metal ions of table 1 formaldehyde clearance
。
Visible by above-mentioned specific embodiment, method raw material sources of the invention are extensive, cost is low, operating process is simple,
Working condition is gentle, and energy consumption is low, is adapted to large-scale production, and reaction reagent and course of reaction are pollution-free, meets green general
Read, more worth high praise, the in-situ modified titania nanoparticles uniform particle diameter of gained metal ion, as photocatalyst material
Material, high to contaminant removal efficiency, the clearance of 24h PARA FORMALDEHYDE PRILLS(91,95)s is more than 90%, or even more than 95%.
Claims (9)
1. the preparation method of the in-situ modified titanium dioxide of a metal ion species, it is characterised in that the preparation method includes following
Step：
（1）Titanium source, weak caustic solution are added under stirring at normal temperature into water, wherein, titanium source, water, the mass ratio of weak caustic solution are 1：10-
100：1-50, stir and produce dissolved colloidal state titania systems；
（2）PH value is adjusted to 6 ~ 8, aqueous metallic ions is added under stirring into dissolved colloidal state titania systems, controls metal
Ion is 0.00001 ~ 0.01 with titanium dioxide mass ratio：Stirring reaction 0.5-5h at 1,20-100 DEG C, is obtained metal ion-modified
The titanium dioxide aqueous solution.
2. preparation method according to claim 1, it is characterised in that the speed 350-500r/min of the stirring.
3. preparation method according to claim 1, it is characterised in that the addition titanium source and addition aqueous metallic ions
It is to be added dropwise.
4. preparation method according to claim 1, it is characterised in that the aqueous metallic ions concentration is 0.5-
1wt.%。
5. preparation method according to claim 1, it is characterised in that the aqueous metallic ions included but is not limited to
Cross the one or more of metal or noble metal Cr, Mn, Fe, Co, Ni, Cu, Au, Ag, Pt, Pd aqueous solution.
6. preparation method according to claim 1, it is characterised in that the titanium source is selected from titanyl sulfate, titanium tetrachloride, three
It is more than one or both of titanium chloride, titanium tetrafluoride or alkyl oxygen titanium.
7. preparation method according to claim 1, it is characterised in that the weak caustic solution is the ammonia of mass concentration 2.5%
Water.
8. preparation method according to claim 1, it is characterised in that the dissolved colloidal state titania systems and/or metal
The titanium dioxide aqueous solution of ion modification by centrifugation or filtering, then will precipitate or filter cake be resuspended with the water of 1-5 times of volume it is uniform
It is further purified.
9. preparation method according to claim 1, it is characterised in that the preparation method is：
（1）10g titanium sources, 100-130mL 2.5wt.% ammonia spirit are added under stirring at normal temperature into 400-600g water, stirring is equal
It is even to produce dissolved colloidal state titania systems；
（2）By dissolved colloidal state titania systems filter or with 8000-10000r/min centrifuge 8-15min, gained precipitation solid with
The concussion of 80-100ml water is resuspended and ultrasonic 15-30s, and control ph is 6 ~ 8, adds 0.8-1wt.% aqueous metallic ions, control
Metal ion is 0.0001 ~ 0.0003 with titanium dioxide mass ratio：3-4h is stirred at 1,20-40 DEG C, is obtained metal ion-modified
The titanium dioxide aqueous solution.
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