CN105944705A - Preparation method of TiO2-SiO2 porous material - Google Patents
Preparation method of TiO2-SiO2 porous material Download PDFInfo
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- CN105944705A CN105944705A CN201610292812.7A CN201610292812A CN105944705A CN 105944705 A CN105944705 A CN 105944705A CN 201610292812 A CN201610292812 A CN 201610292812A CN 105944705 A CN105944705 A CN 105944705A
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- porous material
- sio
- tio
- citric acid
- preparation
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- 239000011148 porous material Substances 0.000 title claims abstract description 30
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 99
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001879 gelation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000005056 compaction Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction 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
- 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
-
- B01J35/39—
-
- B01J35/60—
-
- B01J35/651—
Abstract
The invention discloses a preparation method of a TiO2-SiO2 porous material. The method comprises the following steps: uniformly dispersing ions in xerogel powder by using a dispersant through using butyl titanate and ethyl orthosilicate as raw materials and anhydrous ethanol and deionized water as a solvent, carrying out direct compaction molding on the xerogel, and carrying out heat treatment to obtain the TiO2-SiO2 porous material. The method has the advantages of short preparation period, simple technology device, and low cost, and a proper dispersant formula makes the dimension and the distribution of apertures of the obtained porous material be uniform.
Description
Technical field
The invention belongs to field of material technology, particularly to a kind of TiO2-SiO2The preparation side of porous material
Method.
Background technology
Nano-TiO2-SiO2Composite is a kind of efficient photocatalyst, and it has bigger specific surface
Long-pending, photo absorption performance is strong, and therefore it has excellent photocatalytic, can be widely used in air cleaning, have
The fields such as the degraded of machine thing.Nano-TiO2-SiO2The microscopic appearance of composite powder material, particle diameter, crystalline phase
Composition and specific surface area are relatively big, along with TiO on the impact of its photocatalysis performance2-SiO2Composite powder material grain
The reduction in footpath, its surface activity is the biggest, and photocatalytic activity is the biggest.But, the increase of specific surface area is easily made
Become TiO2-SiO2The agglomeration of composite nano powder, this will be unfavorable for TiO2-SiO2The light of composite granule
Catalytic effect.Synthesis TiO2-SiO2Porous material, when the hole of porous material is perforate, hole little and
When distribution of sizes is more uniform, can effectively solve agglomeration traits, higher surface activity can be kept, thus
There is higher photocatalytic activity.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of TiO2-SiO2
The preparation method of porous material, has the advantages that production technology is simple, equipment requirements is simple, the cycle is short.
To achieve these goals, the technical solution used in the present invention is:
A kind of TiO2-SiO2The preparation method of porous material, comprises the steps:
(1) citric acid is dissolved in ammonia obtains citric acid solution, measure the citric acid solution of 1/5, will
It is standby that tetraethyl orthosilicate is dissolved in wherein formation solution A；Butyl titanate is dissolved in shape in residue citric acid solution
Become solution B；
(2) dispersant is added in solution B, add absolute ethyl alcohol and stirring and dissolve, regulate pH afterwards
It is worth to 6～8 acquisition sol B；
(3) by sol B water-bath 15～30min at 80～85 DEG C, lower solution A is added being stirred continuously
Enter wherein, continue in this water bath condition down to gelation, then at 140～160 DEG C, be dried formation xerogel,
Naturally carry out ground sieve after drying under room temperature and obtain xerogel powder body；
(4) the dry powder block blank of material of direct dry-pressing formed formation after sieving, finally by bulk base substrate
Material carries out being thermally treated resulting in TiO2-SiO2Porous material.
In described step (1), the amount of ammonia is as the criterion can dissolve citric acid.
In described step (1), the mol ratio of Si Yu Ti is 1:(3～10), and Si ion and Ti
Ion sum is 1:(1～2 with the mol ratio of citric acid total amount in step 1).
In described step (2), described dispersant is by ethylenediaminetetraacetic acid, citric acid, diethylenetriamine five
Carboxylic acid, tartaric acid, ethylene glycol and Polyethylene Glycol composition.
After described dispersant adds in solution B, the concentration range of dispersant each component is 0～0.5mol/L.
In described step (2), the volume of dehydrated alcohol is the 1/2～1 of ammonia cumulative volume.
Described heat treatment is to carry out burying burning in ZnO powder body, and temperature is 600～800 DEG C.
Compared with prior art, the invention has the beneficial effects as follows: the TiO that the present invention provides2-SiO2Porous
In the preparation method of material, with ethylenediaminetetraacetic acid, citric acid, diethylenetriamine pentacarboxylic acid, tartaric acid,
Ethylene glycol, PEG400, Macrogol 4000, polyethylene glycol 6000 etc. directly enter as dispersant
The gelation process of row complexation foaming, by controlling the concentration of each material, the consumption of the most each dispersant,
Making the xerogel of applicable straight forming, this is possible not only to reduce pelletize, old process, also can make
Crystallization process completes with sintering one step.In conjunction with burying the heat treatment process of burning, utilize organic foaming and point
Solve combustion process and form TiO2-SiO2Porous material.This method processing step is few, manufacturing cycle is short,
Equipment is simple, low cost, and gained TiO2-SiO2Pore-size and the distribution controllability of porous material are good.
Detailed description of the invention
Embodiments of the present invention are described in detail below in conjunction with embodiment.
Embodiment 1
A kind of TiO2-SiO2The preparation method of porous material, comprises the steps:
(1) being dissolved in ammonia by citric acid, the amount of ammonia is as the criterion can dissolve citric acid, measures 1/5
Citric acid solution, is dissolved in wherein formation solution A standby by tetraethyl orthosilicate；Butyl titanate is dissolved in residue
Citric acid solution is formed solution B, wherein, Si:Ti (mol ratio)=1:3, ion: citric acid (rubs
That ratio)=1:1.
(2) a certain amount of dispersant is weighed (by ethylenediaminetetraacetic acid, citric acid, diethylenetriamine five carboxylic
Acid, tartaric acid, ethylene glycol, Polyethylene Glycol composition, wherein Polyethylene Glycol include again PEG400,
Macrogol 4000 and polyethylene glycol 6000) add in solution B, the concentration of dispersant each component controls
At 0.5mol/L.(volume of dehydrated alcohol is step 1 ammonia volume to add absolute ethyl alcohol and stirring dissolving
1/2), regulation pH value i.e. obtains sol B to 6～8 afterwards.
(3) by sol B water-bath 15～30min at 85 DEG C, lower by solution A addition being stirred continuously
Wherein, continue in this water bath condition down to gelation.It is dried at 140 DEG C again and forms xerogel, room temperature
Lower naturally dry after be ground sieving by powder body.
(4) the direct dry pressing of dry powder after sieving forms block blank of material, finally by bulk base substrate
Material carries out burying burning in ZnO powder body and i.e. obtains TiO2-SiO2Porous material, heat treatment temperature is
600℃.Gained TiO2-SiO2In porous material, particle size is about 100nm～500nm, gap size
For 50nm～150nm.
Embodiment 2
A kind of TiO2-SiO2The preparation method of porous material, comprises the steps:
(1) being dissolved in ammonia by citric acid, the amount of ammonia is as the criterion can dissolve citric acid, measures 1/5
Citric acid solution, is dissolved in wherein formation solution A standby by tetraethyl orthosilicate；Butyl titanate is dissolved in residue
Citric acid solution is formed solution B, wherein, Si:Ti (mol ratio)=1:10, ion: citric acid
(mol ratio)=1:2.
(2) a certain amount of dispersant is weighed (by ethylenediaminetetraacetic acid, citric acid, diethylenetriamine five carboxylic
Acid, tartaric acid, ethylene glycol, Polyethylene Glycol composition) add in solution B, the concentration of dispersant each component
Control at 0.4mol/L.Add absolute ethyl alcohol and stirring and dissolve (volume of dehydrated alcohol and step 1 ammonia body
Long-pending identical), regulation pH value i.e. obtains sol B to 6～8 afterwards.
(3) by sol B water-bath 15～30min at 80 DEG C, lower solution A is added it being stirred continuously
In, continue in this water bath condition down to gelation.It is dried at 150 DEG C again and forms xerogel, under room temperature
Naturally it is ground sieving by powder body after drying.
(4) the direct dry pressing of dry powder after sieving forms block blank of material, finally by bulk base substrate
Material carries out burying burning in ZnO powder body and i.e. obtains TiO2-SiO2Porous material, heat treatment temperature is
800℃.Gained TiO2-SiO2In porous material, particle size is about 100nm～500nm, gap size
For 50nm～150nm.
Embodiment 3
A kind of TiO2-SiO2The preparation method of porous material, comprises the steps:
(1) being dissolved in ammonia by citric acid, the amount of ammonia is as the criterion can dissolve citric acid, measures 1/5
Citric acid solution, is dissolved in wherein formation solution A standby by tetraethyl orthosilicate；Butyl titanate is dissolved in residue
Citric acid solution is formed solution B, wherein, Si:Ti (mol ratio)=1:5, ion: citric acid (rubs
That ratio)=1:1.5.
(2) a certain amount of dispersant is weighed (by ethylenediaminetetraacetic acid, citric acid, diethylenetriamine five carboxylic
Acid, tartaric acid, ethylene glycol, Polyethylene Glycol composition) add in solution B, the concentration of dispersant each component
Control 0.01,0.1,0.1,0.2,0.2,0.5mol/L.Add absolute ethyl alcohol and stirring and dissolve (anhydrous
The volume of ethanol is the 3/4 of ammonia volume), regulation pH value i.e. obtains sol B to 6～8 afterwards.
(3) by sol B water-bath 15～30min at 80 DEG C DEG C, lower by solution A addition being stirred continuously
Wherein, continue in this water bath condition down to gelation.It is dried at 160 DEG C again and forms xerogel, room temperature
Lower naturally dry after be ground sieving by powder body.
(4) the direct dry pressing of dry powder after sieving forms block blank of material, finally by bulk base substrate
Material carries out burying burning in ZnO powder body and i.e. obtains TiO2-SiO2Porous material, heat treatment temperature is
700℃.Gained TiO2-SiO2In porous material, particle size is about 100nm～500nm, gap size
For 50nm～150nm.
Claims (7)
1. a TiO2-SiO2The preparation method of porous material, it is characterised in that comprise the steps:
(1) citric acid is dissolved in ammonia obtains citric acid solution, measure the citric acid solution of 1/5, will
It is standby that tetraethyl orthosilicate is dissolved in wherein formation solution A；Butyl titanate is dissolved in shape in residue citric acid solution
Become solution B；
(2) dispersant is added in solution B, add absolute ethyl alcohol and stirring and dissolve, regulate pH afterwards
It is worth to 6～8 acquisition sol B；
(3) by sol B water-bath 15～30min at 80～85 DEG C, lower solution A is added being stirred continuously
Enter wherein, continue in this water bath condition down to gelation, then at 140～160 DEG C, be dried formation xerogel,
Naturally carry out ground sieve after drying under room temperature and obtain xerogel powder body；
(4) the dry powder block blank of material of direct dry-pressing formed formation after sieving, finally by bulk base substrate
Material carries out being thermally treated resulting in TiO2-SiO2Porous material.
TiO the most according to claim 12-SiO2The preparation method of porous material, it is characterised in that
In described step (1), the amount of ammonia is as the criterion can dissolve citric acid.
TiO the most according to claim 12-SiO2The preparation method of porous material, it is characterised in that
In described step (1), the mol ratio of Si Yu Ti is 1:(3～10), and Si ion and Ti ion
Sum is 1:(1～2 with the mol ratio of citric acid total amount in step 1).
TiO the most according to claim 12-SiO2The preparation method of porous material, it is characterised in that
In described step (2), described dispersant by ethylenediaminetetraacetic acid, citric acid, diethylenetriamine pentacarboxylic acid,
Tartaric acid, ethylene glycol and Polyethylene Glycol composition.
TiO the most according to claim 42-SiO2The preparation method of porous material, it is characterised in that
After described dispersant adds in solution B, the concentration range of dispersant each component is 0～0.5mol/L.
TiO the most according to claim 12-SiO2The preparation method of porous material, it is characterised in that
In described step (2), the volume of dehydrated alcohol is the 1/2～1 of ammonia cumulative volume.
TiO the most according to claim 12-SiO2The preparation method of porous material, it is characterised in that
Described heat treatment is to carry out burying burning in ZnO powder body, and temperature is 600～800 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891206A (en) * | 2010-07-21 | 2010-11-24 | 陕西科技大学 | Preparation method of SiO2/TiO2 composite microspheres |
| CN101890326A (en) * | 2010-07-21 | 2010-11-24 | 陕西科技大学 | Method for preparing TiO2/SiO2 composite microspheres |
| CN101891974A (en) * | 2010-07-21 | 2010-11-24 | 陕西科技大学 | Method for preparing TiO2/SiO2 composite powder |
| CN104003411A (en) * | 2014-05-16 | 2014-08-27 | 北京科技大学 | Preparation method of lithium silicate porous material used for absorption of high temperature CO2 |
-
2016
- 2016-05-05 CN CN201610292812.7A patent/CN105944705B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891206A (en) * | 2010-07-21 | 2010-11-24 | 陕西科技大学 | Preparation method of SiO2/TiO2 composite microspheres |
| CN101890326A (en) * | 2010-07-21 | 2010-11-24 | 陕西科技大学 | Method for preparing TiO2/SiO2 composite microspheres |
| CN101891974A (en) * | 2010-07-21 | 2010-11-24 | 陕西科技大学 | Method for preparing TiO2/SiO2 composite powder |
| CN104003411A (en) * | 2014-05-16 | 2014-08-27 | 北京科技大学 | Preparation method of lithium silicate porous material used for absorption of high temperature CO2 |
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