CN109499562A - Titania/silica photochemical catalyst and preparation method thereof - Google Patents
Titania/silica photochemical catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109499562A CN109499562A CN201811484282.1A CN201811484282A CN109499562A CN 109499562 A CN109499562 A CN 109499562A CN 201811484282 A CN201811484282 A CN 201811484282A CN 109499562 A CN109499562 A CN 109499562A
- Authority
- CN
- China
- Prior art keywords
- preparation
- silica
- acid
- added dropwise
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 143
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000019441 ethanol Nutrition 0.000 claims abstract description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 229960000583 acetic acid Drugs 0.000 claims abstract description 18
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000013019 agitation Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 37
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 10
- 239000005049 silicon tetrachloride Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 30
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 239000008187 granular material Substances 0.000 abstract description 14
- 230000036961 partial effect Effects 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 51
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 229960004756 ethanol Drugs 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 229960000935 dehydrated alcohol Drugs 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000000352 supercritical drying Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000008236 heating water Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CEVCTNCUIVEQOY-STXHBLNNSA-N fumagillol Chemical compound C([C@@H](O)[C@H](C1[C@]2(C)[C@H](O2)CC=C(C)C)OC)C[C@@]21CO2 CEVCTNCUIVEQOY-STXHBLNNSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
Abstract
The present invention relates to a kind of titania/silica photochemical catalysts and preparation method thereof, the preparation method, which is first passed through, is added dropwise water into titanate esters, ethyl alcohol and glacial acetic acid mixed system, control the hydrolysis rate of titanate esters, obtain the lesser unformed TiO 2 particles of partial size, acid with strong oxidizing property is added dropwise again to be reacted to obtain TiO 2 sol, unformed titanium dioxide is set to be changed into the titanium dioxide of anatase, the titanium dioxide granule partial size of preparation is small, Anatase purity is high is conducive to improve photocatalytic activity.It disperses TiO 2 sol particle ultrasonic agitation in silica dioxide gel, titanium dioxide granule is carried on silica dioxide granule after drying, since silica dioxide granule has biggish specific surface area, and silica is able to suppress the phase transformation of titanium dioxide, is conducive to further increasing for photocatalytic activity.Above method preparation condition is mild, without carrying out calcination processing, saves the energy, while obtaining good photocatalytic activity.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of titania/silica photochemical catalyst and its
Preparation method.
Background technique
Titanium dioxide is a kind of wide bandgap semiconductor, under the action of ultraviolet light, the titanium dioxide nano granule of Detitanium-ore-type
Son has preferable photocatalysis effect.The forbidden bandwidth of the titanium dioxide of Detitanium-ore-type is 3.2eV, is equivalent to the light of 387.5nm
Energy of a quantum, when the light by wavelength less than 387.5nm irradiates, the electronics in titanium dioxide is stimulated transition.Electronics and sky
After the separation of cave, is reacted with the oxygen of titanium dioxide surface and water, generate the free radical of strong oxidizing property, show titanium dioxide by force
Catalytic activity.The partial size of titanium dioxide is smaller, and specific surface area is bigger, is got over by the electronics that can generate when ultraviolet light, hole
More, catalytic activity is stronger.
It needs to combine high-temperature calcination after the titania gel of traditional sol-gel method preparation is dry to reach relatively good
Photocatalytic activity, but the nano particle diameter prepared is bigger than normal, and usually contains a certain amount of Rutile Type, is unfavorable for light and urges
Change active raising.
Summary of the invention
Based on this, the present invention provides a kind of titania/silica photochemical catalyst and its system with high catalytic activity
Preparation Method.
A kind of preparation method of titania/silica photochemical catalyst, which comprises the following steps:
Take titanate esters to be added in the mixed liquor of ethyl alcohol and glacial acetic acid, water be added dropwise while stirring, after being added dropwise 40 DEG C~
It is stirred to react at 65 DEG C, obtains hydrolyzate；
Acid with strong oxidizing property is added dropwise into the hydrolyzate, continues to be stirred to react at 60 DEG C~85 DEG C after being added dropwise, obtain
TiO 2 sol；
The TiO 2 sol is added in silica dioxide gel, ultrasonic agitation, it is dry to get.
Glacial acetic acid, titanate esters, the volume ratio of second alcohol and water are 1:(8~15 in one of the embodiments): (80~
150): (150~250).
The time for adding of water is 15min~30min in one of the embodiments, what water was stirred to react after being added dropwise
Time is 5min~30min.
The time for adding of the acid with strong oxidizing property is 5min~10min, the strong oxidizing property in one of the embodiments,
The time that acid is stirred to react after being added dropwise is 3h~6h.
The concentration of the acid with strong oxidizing property is 0.1mol/L~0.2mol/L, the strong oxygen in one of the embodiments,
The volume ratio of the property changed acid and the hydrolyzate is 1:(1.2~2).
The time of the ultrasonic agitation is 1h~3h in one of the embodiments,.
The silica dioxide gel is prepared by the method included the following steps in one of the embodiments:
Take volume ratio be 1:(4~10) silicon tetrachloride and water glass solution be stirred to react at 60 DEG C~100 DEG C, work as body
Be pH value be 12~13 when, stop stirring, aging 30min~60min to get.
The drying is dry under the conditions of postcritical in one of the embodiments,.
Drying includes: under the conditions of postcritical described in one of the embodiments,
The mixture of the TiO 2 sol and the silica dioxide gel is carried out solvent with ethyl alcohol to replace to obtain alcohol
The alcogel and ethyl alcohol are added in autoclave gel, and after being passed through inert gas discharge air, increasing temperature and pressure to ethyl alcohol surpasses
Critical value, heat-insulation pressure keeping 0.5h~2h；Temperature is maintained, pressure release to normal pressure is passed through inert gas purge 0.5h~2h, cools down, out
Material.
In one of the embodiments, the titanate esters in butyl titanate, titanium propanolate and tetraethyl titanate at least
It is a kind of.
The acid with strong oxidizing property is selected from least one of nitric acid, sulfuric acid in one of the embodiments,.
A kind of titania/silica photochemical catalyst that the preparation method by any of the above-described embodiment is prepared.
Compared with existing scheme, the invention has the following advantages:
The preparation method of above-mentioned titania/silica photochemical catalyst first passes through mixed to titanate esters, ethyl alcohol and glacial acetic acid
Water is added dropwise in zoarium system, controls the hydrolysis rate of titanate esters, obtains the lesser unformed TiO 2 particles of partial size, then is added dropwise strong
Oxidizing acid is reacted to obtain TiO 2 sol, and unformed titanium dioxide is made to be changed into the titanium dioxide of anatase,
The titanium dioxide granule partial size being prepared is small, and Anatase purity is high is conducive to improve photocatalytic activity.By the dioxy of preparation
Change titanium sol particles ultrasonic agitation to be scattered in silica dioxide gel, dry obtained photochemical catalyst.Titanium dioxide granule is carried on
On silica dioxide granule, since silica dioxide granule has biggish specific surface area, and silica is able to suppress titanium dioxide
Phase transformation, be conducive to further increasing for photocatalytic activity.Above method preparation condition is mild, without carrying out calcination processing, saves
The energy is saved, while obtaining good photocatalytic activity.
Detailed description of the invention
Fig. 1 is the electron microscope for the titania/silica photochemical catalyst that embodiment 1 is prepared；
Fig. 2 is the XRD test chart for the titania/silica photochemical catalyst that embodiment 1 is prepared.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough
Comprehensively.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The preparation method of the titania/silica photochemical catalyst of one embodiment of the invention, comprising the following steps:
(1) it takes titanate esters to be added in the mixed liquor of ethyl alcohol and glacial acetic acid, water is added dropwise while stirring, 40 after being added dropwise
DEG C~65 DEG C at be stirred to react, obtain hydrolyzate；
(2) acid with strong oxidizing property is added dropwise into hydrolyzate, continues to be stirred to react at 60 DEG C~85 DEG C after being added dropwise, obtains two
Titanium oxide sol；
(3) TiO 2 sol is added in silica dioxide gel, ultrasonic agitation, it is dry to get.
Above-mentioned preparation method, by the way that water is added dropwise into titanate esters, ethyl alcohol and glacial acetic acid system, to control metatitanic acid ester hydrolysis
Speed obtains the lesser unformed TiO 2 particles of partial size.In a wherein example, glacial acetic acid, titanate esters, second alcohol and water
Volume ratio be 1:(8~15): (80~150): (150~250), further, the time for adding of water are 15min~30min, can
Suitable hydrolysis rate is obtained, obtained titanium dioxide partial size is smaller.Water continue to be stirred to react after being added dropwise 5min~
30min, to be more sufficiently carried out hydrolysis.
Wherein, titanate esters can be selected from least one of butyl titanate, titanium propanolate and tetraethyl titanate.Acid with strong oxidizing property can
Selected from least one of nitric acid, sulfuric acid.
Acid with strong oxidizing property is added dropwise into hydrolyzate, unformed titanium dioxide is made to be changed into the titanium dioxide of anatase.
In a wherein example, the concentration of acid with strong oxidizing property is 0.1mol/L~0.2mol/L, the body of acid with strong oxidizing property and hydrolyzate
Product is than being 1:(1.2~2), acid with strong oxidizing property is added dropwise in 5min~10min, and acid with strong oxidizing property continues to stir after being added dropwise
3h~6h is reacted, suitable reaction speed is can get, prevents gel, control system is collosol state, and the titanium dioxide prepared
Titanium sol system has good stability, and can place the several months without sedimentation.
TiO 2 sol is added in silica dioxide gel, and the side Bian Chaosheng is stirred, and the time of ultrasonic agitation can be 1h
~3h is scattered in TiO 2 sol particle fully in silica dioxide gel.After being dried, titanium dioxide granule is i.e. negative
It is loaded on silica dioxide granule, obtains titania/silica photochemical catalyst.
In a wherein example, silica dioxide gel is prepared by the method included the following steps: taking silicon tetrachloride
It is stirred to react at 60 DEG C~100 DEG C with water glass solution, when system pH is 12~13, stops stirring, aging 30min~
60min to get.The volume ratio of silicon tetrachloride and water glass solution is 1:(4~10).
In a wherein example, SiO in water glass solution2Mass fraction be 1%~10%.
With the evolution of hydrone in silica dioxide gel drying process, since surface tension will lead to tunnel collapse, do
Gel can shorten a small group into after dry, so that partial size is larger, specific surface area is reduced.In a wherein example, using supercritical drying
Dry mode avoids gel from collapsing and reunite caused by the period of the day from 11 p.m. to 1 a.m that dries out is due to surface tension, the product after making drying
Fluffy form is kept, obtains that partial size is small, titania/silica photochemical catalyst of large specific surface area.
The supercritical fluid of use can be methanol, ethyl alcohol or carbon dioxide etc..In a wherein example, using ethyl alcohol
As supercritical fluid, supercritical drying includes the following steps:
The mixture of TiO 2 sol and silica dioxide gel is carried out solvent with ethyl alcohol to replace to obtain alcogel, by alcohol
Gel and ethyl alcohol are added in autoclave, and after being passed through inert gas discharge air, the overcritical value of increasing temperature and pressure to ethyl alcohol, heat preservation is protected
Press 0.5h~2h；Temperature is maintained, pressure release to normal pressure is passed through 0.5~2h of inert gas purge, cools down, discharging.
Wherein, when carrying out solvent displacement, first gel can be smashed, filtered after absolute ethyl alcohol and stirring washing is added.Wash number
After secondary, absolute ethyl alcohol and stirring 20min~40min be added, then filter after standing 30min~60min, repeatedly, obtaining alcohol
Gel.
Before supercritical drying, first the mixture of TiO 2 sol and silica dioxide gel can be put into baking oven
A period of time is evaporated at 70 DEG C~100 DEG C, removes the partial moisture in TiO 2 sol.Such as make liquid evaporation to liquid level with
When the position that gel flushes, then supercritical drying step is carried out, can so reduce to the greatest extent and lose two when carrying out solvent displacement
Titanium oxide, while the moisture state of silica dioxide gel can be kept, it avoids reuniting.
The preparation method of above-mentioned titania/silica photochemical catalyst is first passed through to titanate esters, ethyl alcohol and glacial acetic acid body
Water is added dropwise in system, controls the hydrolysis rate of titanate esters, obtains the lesser unformed TiO 2 particles of partial size, then Strong oxdiative is added dropwise
Property acid reacted to obtain TiO 2 sol, so that unformed titanium dioxide is changed into the titanium dioxide of anatase, prepare
Obtained titanium dioxide granule partial size is small, and Anatase purity is high, no Rutile Type generates, and is conducive to improve photocatalytic activity.
It disperses the TiO 2 sol particle ultrasonic agitation of preparation in silica dioxide gel, dry obtained photochemical catalyst, titanium dioxide
Titanium particulate load is on silica dioxide granule, and since silica dioxide granule has biggish specific surface area, and silica can
The phase transformation for inhibiting titanium dioxide, is conducive to further increasing for photocatalytic activity.Above method preparation condition is mild, without carrying out
Calcination processing saves the energy, while obtaining good photocatalytic activity.
Further, the present invention also provides a kind of titanium dioxide/bis- obtained according to any of the above-described exemplary preparation method
Silica photochemical catalyst.
Make below in conjunction with preparation method of the specific embodiment to titania/silica photochemical catalyst of the invention into one
Walk explanation.
Embodiment 1
(1) preparation of TiO 2 sol
It takes a certain amount of dehydrated alcohol to be added in flask, a certain amount of glacial acetic acid is added, stir 20min.Take a certain amount of metatitanic acid
Four butyl esters are added in above-mentioned mixed liquor, after stirring 20min, a certain amount of deionized water are slowly added dropwise while stirring, time for adding is
20min obtains white opacity hydrolyzate.Deionized water drips rear heating water bath and persistently stirs 20min to 50 DEG C.Wherein, ice
Acetic acid, butyl titanate, dehydrated alcohol and deionized water volume ratio be 1:10:100:200.
The nitric acid solution of a certain amount of 0.2mol/L is taken, is added dropwise under stirring in above-mentioned hydrolyzate, 5min~10min is dripped off,
Nitric acid solution and the volume ratio of above-mentioned reaction solution are 1:1.5.Condenser pipe is added after dripping on flask, bath temperature is risen to
75 DEG C, constant temperature persistently stirs 5h and obtains translucent stable TiO 2 sol.
(2) prepared by silica dioxide gel
It takes containing SiO2Mass concentration be 3% water glass solution reacted with silicon tetrachloride, silicon tetrachloride is molten with waterglass
The volume ratio of liquid is 1:10, and reaction temperature is 80 DEG C, and after reaction carries out a period of time, when system pH is 12-13, solution becomes
Gel, stops stirring, and aging after sixty minutes, obtains silica dioxide gel.
(3) prepared by titania/silica gel
Above-mentioned TiO 2 sol is added in above-mentioned silica dioxide gel, gel is smashed, 3h is stirred by ultrasonic.It is put into again
80 DEG C of evaporation a period of times, the position for flushing liquid evaporation with gel to liquid level in baking oven.
(4) supercritical drying
The gel that upper step obtains is smashed, is washed three times with absolute ethyl alcohol and stirring, is filtered after stirring 30min every time.It uses again
Ethyl alcohol carries out solvent displacement, and gel is placed in dehydrated alcohol, 30min is first stirred, then is filtered after standing 40min, is set in two times
It changes, obtains alcogel.
Alcogel is added in autoclave, dehydrated alcohol is added, reaches the 1/2 of autoclave volume.Autoclave is sealed
It purges autoclave 5 minutes well and with nitrogen, starts to warm up.When temperature and pressure reaches the critical value (250 DEG C, 7.1Mpa) of ethyl alcohol
Afterwards, heat-insulation pressure keeping 1 hour.
It maintains critical-temperature pressure release to normal pressure, is purged one hour with nitrogen, cooling.Etc. temperature be cooled to room temperature, open kettle and go out
Material obtains titania/silica photochemical catalyst.
Fig. 1 is the electron microscope of above-mentioned titania/silica photochemical catalyst, it can be seen that duct is more, particle compared with
Carefully, it is fluff structure, is conducive to increase specific surface area, increases catalytic activity.
Fig. 2 is the XRD test chart of above-mentioned titania/silica photochemical catalyst, it can be seen that there is apparent dioxy
The characteristic peak and silica undefined structure for changing titanium, illustrate that titanium dioxide has loaded on silica, and to mutual
Crystalline structure do not influence.
Above-mentioned titania/silica photochemical catalyst is used to formaldehyde degradation by photocatalytic oxidation process to test, after testing experiment 4h
Degradation rate is 93%.
Embodiment 2
(1) preparation of TiO 2 sol
It takes a certain amount of dehydrated alcohol to be added in flask, a certain amount of glacial acetic acid is added, stir 5min.Take a certain amount of metatitanic acid four
Butyl ester is added in above-mentioned mixed liquor, after stirring 30min, a certain amount of deionized water is slowly added dropwise while stirring, time for adding is
15min obtains white opacity hydrolyzate.Deionized water drips rear heating water bath and persistently stirs 10min to 65 DEG C.Wherein, ice
Acetic acid, butyl titanate, dehydrated alcohol and deionized water volume ratio be 1:8:80:150.
The nitric acid solution of a certain amount of 0.2mol/L is taken, is added dropwise under stirring in above-mentioned hydrolyzate, 10min is dripped off, and nitric acid is molten
The volume ratio of liquid and above-mentioned reaction solution is 1:1.2.Condenser pipe is added after dripping on flask, bath temperature is risen to 60 DEG C,
Constant temperature persistently stirs 6h and obtains translucent stable TiO 2 sol.
(2) prepared by silica dioxide gel
It takes containing SiO2Mass concentration be 10% water glass solution reacted with silicon tetrachloride, silicon tetrachloride is molten with waterglass
The volume ratio of liquid is 1:4, and reaction temperature is 100 DEG C, and after reaction carries out a period of time, when system pH is 12-13, solution becomes
Gel stops stirring, after aging 30 minutes, obtains silica dioxide gel.
(3) prepared by titania/silica gel
Above-mentioned TiO 2 sol is added in above-mentioned silica dioxide gel, gel is smashed, 2h is stirred by ultrasonic.It is put into again
70 DEG C of evaporation a period of times, the position for flushing liquid evaporation with gel to liquid level in baking oven.
(4) supercritical drying
The gel that upper step obtains is smashed, is washed three times with absolute ethyl alcohol and stirring, is filtered after stirring 40min every time.It uses again
Ethyl alcohol carries out solvent displacement, and gel is placed in dehydrated alcohol, 40min is first stirred, then is filtered after standing 30min, is set in two times
It changes, obtains alcogel.
Alcogel is added in autoclave, dehydrated alcohol is added, reaches the 1/2 of autoclave volume.Autoclave is sealed
It purges autoclave 5 minutes well and with nitrogen, starts to warm up.When temperature and pressure reaches the critical value (250 DEG C, 7.1Mpa) of ethyl alcohol
Afterwards, heat-insulation pressure keeping 1 hour.
It maintains critical-temperature pressure release to normal pressure, is purged one hour with nitrogen, cooling.Etc. temperature be cooled to room temperature, open kettle and go out
Material obtains titania/silica photochemical catalyst.
Above-mentioned titania/silica photochemical catalyst is used to formaldehyde degradation by photocatalytic oxidation process to test, after testing experiment 4h
Degradation rate is 85%.
Embodiment 3
(1) preparation of TiO 2 sol
It takes a certain amount of dehydrated alcohol to be added in flask, a certain amount of glacial acetic acid is added, stir 30min.Take a certain amount of metatitanic acid
Four butyl esters are added in above-mentioned mixed liquor, after stirring 5min, a certain amount of deionized water are slowly added dropwise while stirring, time for adding is
30min obtains white opacity hydrolyzate.Deionized water drips rear heating water bath and persistently stirs 40min to 40 DEG C.Wherein, ice
Acetic acid, butyl titanate, dehydrated alcohol and deionized water volume ratio be 1:15:150:250.
The nitric acid solution of a certain amount of 0.1mol/L is taken, is added dropwise under stirring in above-mentioned hydrolyzate, 5min~10min is dripped off,
Nitric acid solution and the volume ratio of above-mentioned reaction solution are 1:2.Condenser pipe is added after dripping on flask, bath temperature is risen to 85
DEG C, constant temperature persistently stirs 3h and obtains translucent stable TiO 2 sol.
(2) prepared by silica dioxide gel
It takes containing SiO2Mass concentration be 1% water glass solution reacted with silicon tetrachloride, silicon tetrachloride is molten with waterglass
The volume ratio of liquid is 1:7, and reaction temperature is 60 DEG C, and after reaction carries out a period of time, when system pH is 12-13, solution becomes
Gel, stops stirring, and aging after forty minutes, obtains silica dioxide gel.
(3) prepared by titania/silica gel
Above-mentioned TiO 2 sol is added in above-mentioned silica dioxide gel, gel is smashed, 1h is stirred by ultrasonic.It is put into again
100 DEG C of evaporation a period of times, the position for flushing liquid evaporation with gel to liquid level in baking oven.
(4) supercritical drying
The gel that upper step obtains is smashed, is washed three times with absolute ethyl alcohol and stirring, is filtered after stirring 20min every time.It uses again
Ethyl alcohol carries out solvent displacement, and gel is placed in dehydrated alcohol, 20min is first stirred, then is filtered after standing 60min, is set in two times
It changes, obtains alcogel.
Alcogel is added in autoclave, dehydrated alcohol is added, reaches the 1/2 of autoclave volume.Autoclave is sealed
It purges autoclave 5 minutes well and with nitrogen, starts to warm up.When temperature and pressure reaches the critical value (250 DEG C, 7.1Mpa) of ethyl alcohol
Afterwards, heat-insulation pressure keeping 1 hour.
It maintains critical-temperature pressure release to normal pressure, is purged one hour with nitrogen, cooling.Etc. temperature be cooled to room temperature, open kettle and go out
Material obtains titania/silica photochemical catalyst.
Above-mentioned titania/silica photochemical catalyst is used to formaldehyde degradation by photocatalytic oxidation process to test, after testing experiment 4h
Degradation rate is 76%.
Embodiment 4
The step of this comparative example, is substantially the same manner as Example 1, and difference is, in step (1), glacial acetic acid, butyl titanate,
The volume ratio of dehydrated alcohol and deionized water is 1:6:100:200.
Above-mentioned titania/silica photochemical catalyst is used to formaldehyde degradation by photocatalytic oxidation process to test, after testing experiment 4h
Degradation rate is 67%.
Comparative example 1
The step of this comparative example, is substantially the same manner as Example 1, and difference is, in step (1), after nitric acid dropping, and water
Bath temperature is 100 DEG C, is stirred to react 12h and obtains titania gel.By the titania gel and silica dioxide gel ultrasound
Stirring is mixed.
Above-mentioned titania/silica photochemical catalyst is used to formaldehyde degradation by photocatalytic oxidation process to test, after testing experiment 4h
Degradation rate is 51%.
Comparative example 2
The step of this comparative example, is substantially the same manner as Example 1, and difference is, in step (1), after nitric acid dropping, and water
Bath temperature is 100 DEG C, is stirred to react 12h and obtains titania gel.The titania gel is directly subjected to supercritical drying
Obtain titanium dioxide optical catalyst.
Above-mentioned titanium dioxide optical catalyst is used for formaldehyde degradation by photocatalytic oxidation process experiment, the degradation rate after testing experiment 4h is
54%.
Comparative example 3
The step of this comparative example, is substantially the same manner as Example 1, and difference is, in step (1), by glacial acetic acid, four fourth of metatitanic acid
Ester, dehydrated alcohol and deionized water are stirred to react after directly mixing.
Above-mentioned titania/silica photochemical catalyst is used to formaldehyde degradation by photocatalytic oxidation process to test, after testing experiment 4h
Degradation rate is 23%.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of titania/silica photochemical catalyst, which comprises the following steps:
It takes titanate esters to be added in the mixed liquor of ethyl alcohol and glacial acetic acid, water is added dropwise while stirring, at 40 DEG C~65 DEG C after being added dropwise
Under be stirred to react, obtain hydrolyzate；
Acid with strong oxidizing property is added dropwise into the hydrolyzate, continues to be stirred to react at 60 DEG C~85 DEG C after being added dropwise, obtains dioxy
Change titanium colloidal sol；
The TiO 2 sol is added in silica dioxide gel, ultrasonic agitation, it is dry to get.
2. preparation method as described in claim 1, which is characterized in that glacial acetic acid, titanate esters, the volume ratio of second alcohol and water are 1:
(8~15): (80~150): (150~250).
3. preparation method as described in claim 1, which is characterized in that the time for adding of water is 15min~30min, and water droplet adds
After time for being stirred to react be 5min~30min；And/or
The time for adding of the acid with strong oxidizing property is 5min~10min, what the acid with strong oxidizing property was stirred to react after being added dropwise
Time is 3h~6h.
4. preparation method as described in claim 1, which is characterized in that the concentration of the acid with strong oxidizing property be 0.1mol/L~
The volume ratio of 0.2mol/L, the acid with strong oxidizing property and the hydrolyzate is 1:(1.2~2).
5. preparation method as described in claim 1, which is characterized in that the time of the ultrasonic agitation is 1h~3h.
6. preparation method as described in claim 1, which is characterized in that the silica dioxide gel is by the side that includes the following steps
Method is prepared:
Take volume ratio be 1:(4~10) silicon tetrachloride and water glass solution be stirred to react at 60 DEG C~100 DEG C, as system pH
When value is 12~13, stop stirring, aging 30min~60min to get.
7. preparation method as described in claim 1, which is characterized in that the drying is dry under the conditions of postcritical.
8. preparation method as claimed in claim 7, which is characterized in that drying under the conditions of postcritical includes:
The mixture of the TiO 2 sol and the silica dioxide gel is carried out solvent with ethyl alcohol to replace to obtain alcogel,
The alcogel and ethyl alcohol are added in autoclave, after being passed through inert gas discharge air, increasing temperature and pressure to ethyl alcohol it is overcritical
Value, heat-insulation pressure keeping 0.5h~2h；Temperature is maintained, pressure release to normal pressure is passed through inert gas purge 0.5h~2h, cools down, discharging.
9. preparation method as described in any one of claims 1 to 8, which is characterized in that the titanate esters are selected from butyl titanate, titanium
At least one of propyl propionate and tetraethyl titanate；And/or
The acid with strong oxidizing property is selected from least one of nitric acid, sulfuric acid.
10. a kind of titania/silica light being prepared by preparation method as described in any one of claims 1 to 9
Catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811484282.1A CN109499562A (en) | 2018-12-06 | 2018-12-06 | Titania/silica photochemical catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811484282.1A CN109499562A (en) | 2018-12-06 | 2018-12-06 | Titania/silica photochemical catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109499562A true CN109499562A (en) | 2019-03-22 |
Family
ID=65753105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811484282.1A Pending CN109499562A (en) | 2018-12-06 | 2018-12-06 | Titania/silica photochemical catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109499562A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659368A (en) * | 2020-07-08 | 2020-09-15 | 西安文理学院 | Preparation method of formaldehyde-removing photocatalyst preparation |
| CN111662441A (en) * | 2020-07-22 | 2020-09-15 | 华东理工大学 | Preparation method of environment-friendly polyester catalyst |
| CN113786825A (en) * | 2021-09-10 | 2021-12-14 | 蚌埠学院 | Nano nickel ferrite/zinc titanate modified microporous silicon oxide, preparation method and application thereof |
| CN114767915A (en) * | 2022-05-11 | 2022-07-22 | 深圳誉迪芯创科技有限公司 | Light emitting assembly and manufacturing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110020200A1 (en) * | 2005-05-04 | 2011-01-27 | Jurgen Schimanski | Process for Producing a Thermostable Ti02/Si02 Mixed Oxide and Mixed Oxide Produced Therefrom |
| CN103170333A (en) * | 2013-04-09 | 2013-06-26 | 沈阳化工大学 | Method for preparing recyclable magnetic titanium dioxide nanometer photocatalyst |
| CN103706348A (en) * | 2013-12-30 | 2014-04-09 | 南京工业大学 | Composite TiO2-SiO2 aerogel and application thereof |
| CN104014286A (en) * | 2014-05-16 | 2014-09-03 | 厦门大学 | Preparation method for TiO2-SiO2 composite aerogel |
| CN104072188A (en) * | 2014-07-04 | 2014-10-01 | 中节能六合天融环保科技有限公司 | Preparation method of TiO2/SiO2 composite aerogel material |
| JP2014188417A (en) * | 2013-03-26 | 2014-10-06 | Panahome Corp | Method for manufacturing a photocatalyst composition and method for manufacturing a photocatalyst body |
-
2018
- 2018-12-06 CN CN201811484282.1A patent/CN109499562A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110020200A1 (en) * | 2005-05-04 | 2011-01-27 | Jurgen Schimanski | Process for Producing a Thermostable Ti02/Si02 Mixed Oxide and Mixed Oxide Produced Therefrom |
| JP2014188417A (en) * | 2013-03-26 | 2014-10-06 | Panahome Corp | Method for manufacturing a photocatalyst composition and method for manufacturing a photocatalyst body |
| CN103170333A (en) * | 2013-04-09 | 2013-06-26 | 沈阳化工大学 | Method for preparing recyclable magnetic titanium dioxide nanometer photocatalyst |
| CN103706348A (en) * | 2013-12-30 | 2014-04-09 | 南京工业大学 | Composite TiO2-SiO2 aerogel and application thereof |
| CN104014286A (en) * | 2014-05-16 | 2014-09-03 | 厦门大学 | Preparation method for TiO2-SiO2 composite aerogel |
| CN104072188A (en) * | 2014-07-04 | 2014-10-01 | 中节能六合天融环保科技有限公司 | Preparation method of TiO2/SiO2 composite aerogel material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659368A (en) * | 2020-07-08 | 2020-09-15 | 西安文理学院 | Preparation method of formaldehyde-removing photocatalyst preparation |
| CN111662441A (en) * | 2020-07-22 | 2020-09-15 | 华东理工大学 | Preparation method of environment-friendly polyester catalyst |
| CN113786825A (en) * | 2021-09-10 | 2021-12-14 | 蚌埠学院 | Nano nickel ferrite/zinc titanate modified microporous silicon oxide, preparation method and application thereof |
| CN114767915A (en) * | 2022-05-11 | 2022-07-22 | 深圳誉迪芯创科技有限公司 | Light emitting assembly and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109499562A (en) | Titania/silica photochemical catalyst and preparation method thereof | |
| US10717066B2 (en) | Titania particles and a process for their production | |
| CN106268734B (en) | A kind of preparation method of water dispersible ternary mixed crystal nano titanium dioxide photocatalyst | |
| CN102600881B (en) | Preparation method for nitrogen and carbon co-doped nanometer titanium dioxide visible-light photocatalyst | |
| CN102380385B (en) | Supported metal doped mesoporous titanium dioxide photocatalyst and application thereof | |
| CN103531363B (en) | The preparation method of dye sensibilization solar cell nanometer TiO2 film light anode slurries | |
| CN101318128A (en) | Method of preparing anatase structured highlight catalytic active nano-TiO2 | |
| CN108786822A (en) | A kind of methane reforming multinuclear shell hollow type nickel-nisiloy hydrochlorate-CeO2Preparation method | |
| CN101318694A (en) | Method for preparing titanium dioxide nanocrystalline with highlight catalytic activity in low-temperature | |
| CN107792863A (en) | Catalyzing hydrogen peroxide oxidation reaction HTS TS 1 synthetic method | |
| CN102895964A (en) | Preparation method for blue sheet-like titanium dioxide nanomaterial | |
| CN101015793A (en) | Process for preparing nano-TiO2 photocatalysis material | |
| CN103276475A (en) | Preparation method of heteropoly acid/metal oxide composite nano fiber | |
| CN109482241A (en) | TiO2/ MOF-5 photochemical catalyst and preparation method thereof | |
| CN110354895A (en) | A kind of oxide porous photochemical catalyst of molecular screen base Ce-Mn and its preparation method and application | |
| CN105271400B (en) | A kind of preparation method of mixed crystal nano-titanium dioxide | |
| CN108837827A (en) | A kind of bilayer core-shell structure platinum catalyst and its preparation method and application | |
| CN104891566B (en) | The method that pulse electromagnetic field prepares anatase-type nanometer titanium dioxide | |
| CN104495868B (en) | A kind of preparation method of big particle diameter HTS | |
| CN108355654A (en) | A kind of graphene-based Cu/Cu2O/TiO2Composite visible light catalyst and preparation method thereof | |
| CN110743522B (en) | High-index crystal face titanium dioxide nano catalyst and preparation method thereof | |
| CN105506736A (en) | Nano TiO2 single-crystal material, preparation method and application of material | |
| JP4631013B2 (en) | Acicular titanium oxide fine particles, production method thereof and use thereof | |
| DE10394356T5 (en) | Synthesis of ultrafine titania particles in rutile phase at low temperature | |
| CN109775756A (en) | A kind of synthetic method of high thermal stability rutile titania phase nano-titanium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190322 |
|
| RJ01 | Rejection of invention patent application after publication |