CN100486691C - Mesoporous titania with aminated pores and its preparation process - Google Patents
Mesoporous titania with aminated pores and its preparation process Download PDFInfo
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- CN100486691C CN100486691C CNB2006100982886A CN200610098288A CN100486691C CN 100486691 C CN100486691 C CN 100486691C CN B2006100982886 A CNB2006100982886 A CN B2006100982886A CN 200610098288 A CN200610098288 A CN 200610098288A CN 100486691 C CN100486691 C CN 100486691C
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011148 porous material Substances 0.000 title description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 8
- 229910003849 O-Si Inorganic materials 0.000 claims abstract description 6
- 229910003872 O—Si Inorganic materials 0.000 claims abstract description 6
- 229910003088 Ti−O−Ti Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 3
- 229910020489 SiO3 Inorganic materials 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000000193 wide-angle powder X-ray diffraction Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses one kind of amino radical functionated mesoporous titania and its preparation process. The amino radical functionated mesoporous titania is prepared through in-situ synthesis of amino radical hole wall inside a sol-gel system in a near neutral condition and low temperature, and implanting functionated mesoporous titania. It includes inorganic oxide skeleton Ti-O-Ti and Ti-O-Si and amino radical substituted alkyl radical -CnH2nNH2 connected with Si, and has the characteristic molecular expression of (TiO2)x(SiO3/2-CnH2nNH2)y, where x is 0-100 and y is 0-1. The preparation process is simple and environment friendly without acid solution exhaust. The synthesized mesoporous titania may be used as photocatalyst directly and as the substrate material for assembling organic molecule through chemical reaction. The present invention may find wide application in various fields.
Description
One, technical field
The present invention relates to a kind of medium pore of titania new material of chemical modification amino functional, meso-porous titanium oxide of amino functional and preparation method thereof in specifically a kind of hole.
Two, background technology
Titanium oxide is subjected to researcher's extensive concern always with its unique optical physics chemical property.As the representative of catalysis material, it has a wide range of applications at aspects such as catalysis organic synthesis, environmental poisonous substance degraded, drug loading, photoelectric devices.On appearance structure except the Powdered titanium oxide of coarsegrain, nano-titanium oxide synthetic also has a large amount of reports in recent years.And meso-porous titanium oxide is the non-silicon mesoporous material that becomes the research focus after the total silicon mesoporous material is successfully synthesized, its synthesis material is easy to get, but have orderly crystal structure, one dimension modulation duct and high specific area and photocatalytic activity, therefore receive much attention.
Because only producing ultraviolet light as photochemical catalyst, titanium oxide absorbs, in order to improve its efficiency of light absorption, increase is to the absorption of visible light, a large amount of research concentrates on metal or the nonmetal doping that titanium oxide is carried out body phase or surface, metal-doped mainly is the doping of transition metal, and nonmetalloid mainly comprises the doping of carbon, boron, phosphorus, sulphur, vanadium, nitrogen, and these means are by changing the band structure of titanium oxide, has increased absorption to visible light thereby reduce energy gap.Wherein phosphorus mixes the heat endurance that can increase titanium oxide, the absorption band edge generation red shift that nitrogen mixes and then obviously makes titanium oxide, thus improve photocatalysis efficiency.It mainly is by at NH that nitrogen mixes
3In the air-flow, 500 above heat treatment titanium dioxide powders, but also not too clear to the existence form of Doping Mechanism, nitrogen, in addition, the doping of nitrogen neither be controlled fully.
In the application of titanium oxide, below main branch the and aspect:
1, on Environmental Chemistry, as photochemical catalyst degrade organic poison such as aldehydes, dyestuff, organic agricultural chemicals, hormone and handle heavy metal-containing waste water.
2, come photochemical catalyzing, oxidizing alcohol and reduction CO as catalyst in the catalytic reaction
2
3, life science is as antiseptic kill bacteria and virus.Verified, TiO
2Particle can enter in the cancer cell, and itself is to utilize TiO to cancer cell and avirulence
2The strong oxidability of the active oxygen kind that the photosensitization photoactivation produces is killed cancer cell bacterium and virus.
4, at material science, as solar cell or electrode material.
Research for meso-porous titanium oxide concentrates on synthetic aspect relatively, and functionalization in the hole and application facet are not appeared in the newspapers.Can expect the high-specific surface area of meso-porous titanium oxide of hole wall functionalization, big one-dimensional tunnel structure will make it not only in photocatalysis field but also at aspects such as nano photoelectric device, drug delivery, biomolecule carrier wide application prospect be arranged.
Three, summary of the invention
The invention provides meso-porous titanium oxide of a kind of chemical modification amino functional and preparation method thereof.This method is the functional mesoporous titanium oxide of implanting near original position synthesizing amino hole wall under the neutrallty condition in collosol-gelatum system, and method is easy, no acid solution discharging, environmental friendliness.The amount of synthetic meso-porous titanium oxide surface amino groups is controlled, and specific area is big.Both can be used as photochemical catalyst and directly used, and also can be used as base material and in the hole, assemble specific organic molecule by chemical reaction and realize further functionalization.
The objective of the invention is to be achieved through the following technical solutions:
The meso-porous titanium oxide of amino functional in a kind of hole is characterized in that: it comprises organic surface group that inorganic oxide skeleton Ti-O-Ti links to each other with Ti-O-Si and with Si, and this organic surface group is the amino alkyl-C that replaces
nH
2nNH
2, wherein, the Ti/Si mol ratio is 1:1～100:1; Its feature molecular formula is: (TiO
2) x (SiO
3/2-C
nH
2nNH
2) y, in the formula, 0＜X≤100,0＜y≤1, n=1～4.
Among the present invention, the Ti among the described inorganic oxide skeleton Ti-O-Ti is generated by any one titanium in butyl titanate, isopropyl titanate, titanium tetrachloride, the titanyl sulfate.
Si among the described inorganic oxide skeleton Ti-O-Si is by silylating reagent NH
2C
nH
2n-Si (OC
mH
2m+1)
3Provide, wherein n is 1～4, m is 1～4.
The preparation method of the meso-porous titanium oxide of amino functional in a kind of hole is characterized in that: at non-ionic surface active agent macromolecule block polymer P123 (EO
20PO
70EO
20, molecular weight 5800) existence under, the presoma of titanium and aminopropyl-triethoxysilicane alkanisation reagent A PTES[(C
2H
5O)
3SiC
3H
6NH
2] copolyreaction, the evaporate to dryness product obtains with drying behind the ethanol cyclic washing product, may further comprise the steps:
A) under the room temperature non-ionic surface active agent P123 is dissolved in the absolute ethyl alcohol, stirring in water bath is to clarification; Can spend stirred in water bath 20～40 minutes 30～50.
B) at above-mentioned steps A) add butyl titanate and aminopropyl-triethoxysilicane alkanisation reagent A PTES in the gained solution, and under 30～50 degree Celsius, stir 15min, the organic surface group that obtains inorganic oxide skeleton Ti-O-Ti and Ti-O-Si and link to each other with Si.
C) in above-mentioned solution, dropwise add the ethanol-aqueous solution for preparing, stirring in water bath; And with the solution evaporate to dryness in water-bath that obtains; Wherein, ethanol: water=20:0.8 (V/V), 40 degree stirring in water bath 24 hours, the solution that obtains is evaporate to dryness in 80 degree water-baths.
D) add absolute ethyl alcohol to the above-mentioned light yellow gel that obtains, stir, filter;
Can add the 50mL absolute ethyl alcohol among the present invention, 40 degree stir 15min, filter; It is constant to keep pH=6～7 in the building-up process; Add the 30mL absolute ethyl alcohol in the precipitation again, 40 degree stir 30min, filter; Repeating to add twice 30mL absolute ethyl alcohol also filters.
E) solid that obtains is dried in drying box after, obtain product.Can in drying box, 100 degree oven dry obtain product after 24 hours.
Among the present invention, little angle powder X-ray diffraction spectrogram shows that (100) crystal face diffraction value of sample is between 0.63 °～2.0 °; Wide-angle powder X-ray diffraction spectrogram shows that the roasting structures of samples is the anatase crystalline substance.The specific area that nitrogen adsorption/desorption isotherm is measured is 100-197m
2/ g.
The meso-porous titanium oxide of the hole wall amino functional of the present invention's preparation has regular one-dimensional tunnel structure, specific area is big, has bigger aperture, hole surface evenly covers the end amino that individual layer disperses, these end amino have very strong reactivity, can be used as the further specific chromophoric group of coupling of reflecting point, thereby can realize self assembly in the hole of nano photoelectric device.Owing to be to utilize silylating reagent and titanate esters original position cocondensation to synthesize in the sol/gel system, the amino amount of hole surface is controlled.Simultaneously, building-up process is that the water yield by silylating reagent and the required stoichiometric proportion of titanate esters hydrolysis adds entry, makes to be reflected at neutrallty condition and to carry out, and does not relate to adding inorganic acid, and product is direct evaporate to dryness, has avoided a large amount of waste water that produce because of the product washing.
The present invention not only has wide application prospect in photocatalysis field but also at aspects such as nano photoelectric device, drug delivery, biomolecule carrier.
Four, the specific embodiment
Further specify the present invention by the following examples.
Embodiment 1
2g non-ionic surface active agent P123 is dissolved in the 30mL absolute ethyl alcohol, 30 fens kinds of 40 degree stirring in water bath are to clarification, add butyl titanate 3.40 grams and aminopropyl-triethoxysilicane alkanisation reagent 0.02 gram, 40 degree dropwise add ethanol-aqueous solution [ethanol: the water=20:0.8 (V/V) for preparing after stirring 15min down, contain 18.3 milliliters of absolute ethyl alcohols, 0.73 milliliter of deionized water], 40 degree stirring in water bath 24 hours, the solution that obtains is evaporate to dryness in 80 degree water-baths. and the light yellow gel that obtains adds the 50mL absolute ethyl alcohol, 40 degree stir 15min, filter.It is constant to keep pH=6-7 in the building-up process.Add the 30mL absolute ethyl alcohol in the precipitation again, 40 degree stir 30min, filter; Repeat to add twice 30mL absolute ethyl alcohol and also filter, the solid that obtains 100 degree oven dry in drying box obtained product after 24 hours.Little angle powder X-ray diffraction spectrogram shows that (100) crystal face diffraction value of sample is 0.63 °.The specific area that nitrogen adsorption/desorption isotherm is measured is 101.69m
2/ g.The Ti/Si=100:1 of product.Its feature molecular formula is: (TiO
2) x (SiO
3/2-C
nH
2nNH
2) y.X=100, y=1, n=3 in the formula.
Embodiment 2
2g non-ionic surface active agent P123 is dissolved in the 30mL absolute ethyl alcohol, 40 fens kinds of 30 degree stirring in water bath are to clarification, add butyl titanate 3.40 grams and aminopropyl-triethoxysilicane alkanisation reagent 0.04 gram, 30 degree Celsius dropwise add ethanol-aqueous solution [ethanol: the water=20:0.8 (V/V) for preparing after stirring 20min down, contain 18.3 milliliters of absolute ethyl alcohols, 0.73 milliliter of deionized water], 30 degree stirring in water bath 24 hours, the solution that obtains is evaporate to dryness in 80 degree water-baths. and the light yellow gel that obtains adds the 50mL absolute ethyl alcohol, 40 degree stir 15min, filter.It is constant to keep pH=6～7 in the building-up process.Add the 30mL absolute ethyl alcohol in the precipitation again, 40 degree stir 30min, filter; Repeat to add twice 30mL absolute ethyl alcohol and also filter, the solid that obtains 100 degree oven dry in drying box obtained product after 24 hours.Little angle powder X-ray diffraction spectrogram shows that (100) crystal face diffraction value of sample is 0.63 °; The specific area that nitrogen adsorption/desorption isotherm is measured is 189.49m
2/ g.The Ti/Si=50:1 of product.Its feature molecular formula is: (TiO
2) x (SiO
3/2-C
nH
2nNH
2) y.X=50, y=1, n=3 in the formula.
Embodiment 3
2g non-ionic surface active agent P123 is dissolved in the 30mL absolute ethyl alcohol, 20 fens kinds of 50 degree stirring in water bath are to clarification, add butyl titanate 3.40 grams and aminopropyl-triethoxysilicane alkanisation reagent 0.11 gram, 50 degree Celsius dropwise add ethanol-aqueous solution [ethanol: the water=20:0.8 (V/V) for preparing after stirring 10min down, contain 19.0 milliliters of absolute ethyl alcohols, 0.76 milliliter of deionized water], 50 degree stirring in water bath 24 hours, the solution that obtains is evaporate to dryness in 80 degree water-baths. and the light yellow gel that obtains adds the 50mL absolute ethyl alcohol, 50 degree stir 15min, filter.It is constant to keep pH=6～7 in the building-up process.Add the 30mL absolute ethyl alcohol in the precipitation again, 50 degree stir 30min, filter; Repeat to add twice 30mL absolute ethyl alcohol and also filter, the solid that obtains 100 degree oven dry in drying box obtained product after 24 hours.Little angle powder X-ray diffraction spectrogram shows that (100) crystal face diffraction value of sample is 0.63 °.The specific area that nitrogen adsorption/desorption isotherm is measured is 196.74m
2/ g.The Ti/Si=20:1 of product.Its feature molecular formula is: (TiO
2) x (SiO
3/2-C
nH
2nNH
2) y.X=20, y=1, n=3 in the formula.
Embodiment 4
2g non-ionic surface active agent P123 is dissolved among the anhydrous EtOH of 30mL, 30 fens kinds of 40 degree stirring in water bath are to clarification, add butyl titanate 3.40 grams and amino third-triethoxysilicane alkanisation reagent, 0.22 gram, 40 degree Celsius dropwise add ethanol-aqueous solution [ethanol: the water=20:0.8 (V/V) for preparing after stirring 15min down, contain 19.8 milliliters of absolute ethyl alcohols, 0.79 milliliter of deionized water], 40 degree stirring in water bath 4 hours, the solution that obtains is evaporate to dryness in 80 degree water-baths. and the light yellow gel that obtains adds the 50mL absolute ethyl alcohol, 40 degree stir 15min, filter.It is constant to keep pH=6-7 in the building-up process.Add the 30mL absolute ethyl alcohol in the precipitation again, 40 degree stir 30min, filter; Repeat to add twice 30mL absolute ethyl alcohol and also filter, the solid that obtains 100 degree oven dry in drying box obtained product after 24 hours.Little angle powder X-ray diffraction spectrogram shows that (100) crystal face diffraction value of roasting sample is 0.63 °.The Ti/Si=10:1 of product.Its feature molecular formula is: (TiO
2) x (SiO
3/2-C
nH
2nNH
2) y.X=10, y=1, n=3 in the formula.
The meso-porous titanium oxide of the hole wall amino functional of the present invention's preparation has regular one-dimensional tunnel structure, specific area is big, has bigger aperture, hole surface evenly covers the end amino that individual layer disperses, these end amino have very strong reactivity, can be used as the further specific chromophoric group of coupling of reflecting point, thereby can realize self assembly in the hole of nano photoelectric device.And the amino amount of hole surface is controlled.Simultaneously, building-up process is to carry out at neutrallty condition, does not relate to adding inorganic acid, and product is direct evaporate to dryness, has avoided a large amount of waste water that produce because of the product washing.
Claims (9)
1, the meso-porous titanium oxide of amino functional in a kind of hole, it is characterized in that: it comprises organic surface group that inorganic oxide skeleton Ti-O-Ti links to each other with Ti-O-Si and with Si, this organic surface group is the amino alkyl-C that replaces
nH
2nNH
2, wherein, the Ti/Si mol ratio is 1:1～100:1; Its feature molecular formula is: (TiO
2) x (SiO
3/2-C
nH
2nNH
2) y, in the formula, 0＜X≤100,0＜y≤1, n=1～4.
2, the meso-porous titanium oxide of amino functional in the hole according to claim 1 is characterized in that: the Ti among the described inorganic oxide skeleton Ti-O-Ti is generated by any one titanium in butyl titanate, isopropyl titanate, titanium tetrachloride, the titanyl sulfate.
3, the meso-porous titanium oxide of amino functional in the hole according to claim 1 is characterized in that: the Si among the described inorganic oxide skeleton Ti-O-Si is by silylating reagent NH
2C
nH
2n-Si (OC
mH
2m+1)
3Provide, wherein n is 1～4, m is 1～4.
4, the preparation method of the meso-porous titanium oxide of amino functional in the described hole of a kind of claim 1, it is characterized in that: in the presence of non-ionic surface active agent macromolecule block polymer P123, the presoma of titanium and aminopropyl-triethoxysilicane alkanisation reagent copolyreaction, the evaporate to dryness product, obtain with drying behind the ethanol cyclic washing product, may further comprise the steps:
A) under the room temperature non-ionic surface active agent P123 is dissolved in the absolute ethyl alcohol, stirring in water bath is to clarification;
B) at above-mentioned steps A) add butyl titanate and aminopropyl-triethoxysilicane alkanisation reagent in the gained solution;
C) in above-mentioned solution, dropwise add the ethanol-aqueous solution for preparing, stirring in water bath; And with the solution evaporate to dryness in water-bath that obtains;
D) add absolute ethyl alcohol to the above-mentioned light yellow gel that obtains, stir, filter;
E) solid that obtains is dried in drying box after, obtain product.
5, the preparation method of the meso-porous titanium oxide of amino functional in the hole according to claim 4, it is characterized in that: steps A), non-ionic surface active agent P123 is dissolved in the absolute ethyl alcohol, spends stirred in water bath 20～40 minutes 30～50.
6, the preparation method of the meso-porous titanium oxide of amino functional in the hole according to claim 4 is characterized in that: step B): surfactant and butyl titanate and aminopropyl-triethoxysilicane alkanisation reagent stirs 10～20min under 30～50 degree Celsius.
7, the preparation method of the meso-porous titanium oxide of amino functional in the hole according to claim 4, it is characterized in that: step C) dropwise add the ethanol-aqueous solution for preparing, wherein, ethanol: water=20:0.8 (V/V), 30～50 degree stirring in water bath 24 hours, the solution that obtains is evaporate to dryness in 80 degree water-baths.
8, the preparation method of the meso-porous titanium oxide of amino functional in the hole according to claim 4 is characterized in that: step D), add the 50mL absolute ethyl alcohol to the above-mentioned light yellow gel that obtains, 30～50 degree stir 10～20min down, filter; It is constant to keep pH=6～7 in the building-up process; Add the 30mL absolute ethyl alcohol in the precipitation again, 30～50 degree stir 20～40min, filter; Repeating to add twice 30mL absolute ethyl alcohol also filters.
9, the preparation method of the meso-porous titanium oxide of amino functional in the hole according to claim 4 is characterized in that: step e), 100 degree oven dry obtained product after 24 hours in drying box.
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|---|---|---|---|
| CNB2006100982886A CN100486691C (en) | 2006-12-08 | 2006-12-08 | Mesoporous titania with aminated pores and its preparation process |
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|---|---|---|---|
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| CN100486691C true CN100486691C (en) | 2009-05-13 |
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| CN101219908B (en) * | 2007-09-21 | 2012-12-05 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
| CN101380593B (en) * | 2008-10-23 | 2010-06-02 | 南京大学 | Interior sulfhydryl functional iron-containing meso-porous titanium oxide and preparation method thereof |
| CN105536692A (en) * | 2016-01-27 | 2016-05-04 | 北京理工大学 | Method for preparing novel mesoporous material for adsorbing rare earth metal ions |
| CN107626287A (en) * | 2017-10-19 | 2018-01-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of amidized nanometre titanium dioxide/silicon dioxide composite cellulosic membrane and products thereof and application |
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