CN101723443A - Monodisperse macroporous titanium dioxide microsphere and preparing method thereof - Google Patents
Monodisperse macroporous titanium dioxide microsphere and preparing method thereof Download PDFInfo
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- CN101723443A CN101723443A CN200810202077A CN200810202077A CN101723443A CN 101723443 A CN101723443 A CN 101723443A CN 200810202077 A CN200810202077 A CN 200810202077A CN 200810202077 A CN200810202077 A CN 200810202077A CN 101723443 A CN101723443 A CN 101723443A
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Abstract
The invention relates to a titanium dioxide microsphere for high performance liquid chromatograph (HPLC) and a preparing method thereof. The titanium dioxide microsphere has a mesopore structure, the particle diameter (diameter) is 0.5-5 mum, and the specific surface area of the pore diameter is 100m<2>/g-130 m<2>/g. The titanium dioxide microsphere is prepared by an improved sol-gel and water thermal crystallisation method. The prepared titanium dioxide microsphere has the advantages of monodisperse property, mesopore structure, uniform particle size, conformance of the surface structure (large pore diameter and large specific surface area) to the chromatograph requirements, no need of grading treatment, and the like. In addition, in the process of the preparation method, the particle diameter of the object (titanium dioxide microspheres) can be controlled (i.e. the microspheres with different particle diameters can be easily obtained through adjusting different titanate concentrations), and the whole preparation process is simple and easy.
Description
Technical field
The present invention relates to a kind of high performance liquid chromatography (HPLC) with monodisperse mesoporous titania microsphere and preparation method thereof.
Background technology
Silica gel has been widely used in the chromatogram stationary phase of (comprising HPLC).Right owing to be that the chromatograph packing material of matrix is only comparatively stable in the pH value is 2～8 scope with silica gel, therefore, when some strongly alkaline compounds are analyzed, comparatively serious conditions of streaking (even the irreversible adsorption phenomenon takes place) can appear, thus the impact analysis result.
Titanium oxide (TiO
2), because it has higher physical strength, thermostability and chemical stability characteristics such as (suitable in pH value is 1～14 scope), be used as the stationary phase of normal-phase chromatography, ion-exchange chromatography, reverse-phase chromatography.But service condition unsatisfactory (may be relevant) with the structure of prepared titania microsphere.
Existing preparation is used for the method for the titania microsphere of chromatogram (comprising HPLC) stationary phase, mainly contains three kinds: (1) sol-gel method (Tani, K.; Suzuki, Y.Chromatographia, 1994,38,291-294.); (2) oily emulsion process (Tr ü dinger, U.; M ü ller, G.; Unger, K.K.J.Chromatogr, A 1990,535,111-125); (3) polymerisation induced coacervation of colloid method (Jiang Zitao, " design, preparation and the sign thereof of titanium gel matrix high performance liquid chromatography the stationary phase, " master of Nankai University Diplomarbeit).
Adopt the titania microsphere of existing sol-gel method and oily emulsion process preparation, existing the aperture of the size distribution broad (size distribution is about ± 3 μ m) of gained titania microsphere and gained titania microsphere and specific surface area, less (sol-gel method: the aperture is about
The oil emulsion process: specific surface area is about 78m
2/ problem such as g), and during used as chromatogram (comprising HPLC) stationary phase, can cause resolution lower, the impact analysis accuracy.Existing polymerisation induced colloid method because its complex steps can cause prepared titania microsphere cost to rise (being unfavorable for commercial applications), and adopts that the specific surface area of the existing prepared titania microsphere of polymerisation induced colloid method is less (to be about 36.7m
2/ g).
Given this, need improve the method that existing preparation is used for the titania microsphere of chromatogram (comprising HPLC) stationary phase, thereby obtain narrow diameter distribution, aperture and the bigger titania microsphere that is used for chromatogram (comprising HPLC) stationary phase of pore volume.
Summary of the invention
One of purpose of the present invention is, provides a kind of narrow diameter distribution, aperture and pore volume the bigger titania microsphere as chromatogram (comprising HPLC) stationary phase;
Two of purpose of the present invention is, a kind of method for preparing above-mentioned titania microsphere is provided.
The said titania microsphere that is used for chromatogram (comprising HPLC) stationary phase of the present invention is characterized in that said titania microsphere has meso-hole structure, and its particle diameter (diameter) is 0.5 μ m～5 μ m, and the aperture is
Specific surface area is 100m
2/ g～130m
2/ g.
Description of drawings
Fig. 1 is for using scanning electron microscope (SEM) figure of the prepared titania microsphere of embodiment 1;
Fig. 2 is for using scanning electron microscope (SEM) figure of the prepared titania microsphere of embodiment 2;
Fig. 3 is for using scanning electron microscope (SEM) figure of the prepared titania microsphere of embodiment 3;
Fig. 4 is for using the N of the prepared titania microsphere of embodiment 1
2The adsorption/desorption graphic representation;
Wherein: ■---adsorption curve, ●---the desorption curve;
Fig. 5 is for using the N of the prepared titania microsphere of embodiment 2
2The adsorption/desorption graphic representation;
Wherein: ■---adsorption curve, ●---the desorption curve;
Fig. 6 is for being HPLC column packed material with embodiment 1 prepared titania microsphere, to the HPLC analysis chart of uridylic, guanosine, VITAMIN B4 and cytosine(Cyt) mixture;
Wherein: peak sequence is followed successively by: uridylic, guanosine, VITAMIN B4 and cytosine(Cyt).
Fig. 7 is for being HPLC column packed material with embodiment 2 prepared titania microspheres, to the HPLC analysis chart of NN-xylidine, Ortho Toluidine, pyridine, aniline and para-totuidine mixture;
Wherein: peak sequence is followed successively by: NN-xylidine, Ortho Toluidine, pyridine, aniline and para-totuidine.
Embodiment
A kind of method for preparing titania microsphere of the present invention, it comprises the steps:
(1) template, sequestrant and titanium ester are joined in the dehydrated alcohol, under 20 ℃～40 ℃ conditions, stir mixed solution; Add deionized water in this mixed solution, stir, when throw out to be had is separated out, stop to stir and leaving standstill 30 minutes～120 minutes, filter, throw out gets the titanium gel micro-ball after with absolute ethanol washing and drying;
(2) will place autoclave by titanium gel micro-ball, urea, dehydrated alcohol and the deionized water that step (1) makes, after being uniformly dispersed, kept 8 hours～36 hours down in 70 ℃～130 ℃ states, after cooling, filtration and washing, get pressed powder, the pressed powder of gained is first through vacuum-drying 6 hours～12 hours, under 300 ℃～500 ℃ conditions, sintering 3 hours～6 hours gets target compound then;
Wherein: said titanium ester is tetrabutyl titanate or isopropyl titanate; Said template is primary amine (RNH
2, R is C
12～C
20Alkyl); Said sequestrant is a methyl ethyl diketone;
The mol ratio of titanium ester, template, sequestrant, dehydrated alcohol and deionized water is 1: (0.2～1): (0.5～2): (100～500): (25～50);
The mass ratio of titanium gel micro-ball and urea is 1: (0.05～0.2), the volume ratio of the volume of titanium gel micro-ball, dehydrated alcohol and deionized water are 1: (40～150): (0.5～80).
The titania microsphere that the present invention is prepared, it has monodispersity and meso-hole structure and particle diameter, and evenly (particle size distribution range be ± 0.2 μ m), surface tissue (aperture is big, specific surface area is big) meet the stratographic requirement and reach advantages such as not needing stage treatment.In addition, in adopting preparation method's process provided by the present invention, the particle diameter of target compound (titania microsphere) controlled (by regulating the be easy to get microballoon of different-grain diameter of different titanium ester concentrations), whole process of preparation is simple.
Below by embodiment this outbreak is further set forth, its purpose only is better to understand content of the present invention.Therefore, protection of the present invention is not limited by the cases cited.
Embodiment 1
Step (1) adds the 0.0024mol amino dodecane in the 200ml round-bottomed flask, the 100ml dehydrated alcohol, 0.006mol methyl ethyl diketone, 0.012mol tetrabutyl titanate after stirring under 20 ℃, adds the 0.3mol deionized water, stop after the solution muddiness stirring, leave standstill 45 minutes after-filtration, behind the absolute ethanol washing 2～4 times, room temperature (25 ℃～30 ℃) dry solid.
Step (2) will be by the solid 1g of step (1) gained, urea 0.2g, add the 16ml dehydrated alcohol, the 4ml deionized water places in the autoclave of the poly-tetrafluoro of liner, leave standstill 8h under 130 ℃, cooled and filtered, wash 2～3 times successively with acetone and methyl alcohol after, the dry 6h of high-temperature vacuum, place 300 ℃ of sintering 6h of retort furnace, get target compound.
Utilize scanning electron microscope analysis, recording the particle diameter mean size is 1.8 μ m, referring to Fig. 1;
Utilize N
2The adsorption/desorption instrument is analyzed its aperture row, and recording the aperture is 9.8nm, referring to Fig. 4;
The titania microsphere of preparation is loaded into 2.1 * 150i.d.mm stainless steel chromatogram post with the homogenate method, the mixture of uridylic, guanosine, VITAMIN B4, cytosine(Cyt) is carried out liquid-phase chromatographic analysis, the results are shown in Figure 6.The liquid-phase chromatographic analysis condition is as follows:
Under hydrophilic pattern, with acetonitrile: the 50mM phosphate buffered aqueous solution (the pH value is 3)=70: 30 (v/v) is moving phase, and flow velocity is 0.2ml/min, and VWD is 254nm.
Step (1) adds 0.1mol 20 amine in the 2000ml round-bottomed flask, the 1000ml dehydrated alcohol, 0.2mol methyl ethyl diketone, 0.10mol isopropyl titanate after stirring under 40 ℃, adds the 5mol deionized water, treat to stop to stir after the solution muddiness, leave standstill 60 minutes after-filtration, behind the absolute ethanol washing 2～4, the dry solid that gets of room temperature (25 ℃～30 ℃).
Step (2) will be by the solid 4g of step (1) gained, urea 0.35g, add the 54ml dehydrated alcohol, the 36ml deionized water places in the autoclave of the poly-tetrafluoro of liner, leave standstill 36h under 70 ℃, cooled and filtered, after acetone and methanol wash 2～3 times, the dry 10h of high-temperature vacuum, place 400 ℃ of sintering 4h of retort furnace, obtain target compound.
Utilize scanning electron microscope analysis, recording the particle diameter mean size is 2.8 μ m, referring to Fig. 2;
Utilize N
2The adsorption/desorption instrument is analyzed its hole, and recording the aperture is 10.5nm, referring to Fig. 5;
The titania microsphere of preparation is loaded into 2.1 * 150i.d.mm stainless steel chromatogram post with the homogenate method, NN-xylidine, Ortho Toluidine, pyridine, aniline and para-totuidine mixture are carried out liquid-phase chromatographic analysis, the results are shown in Figure 7.The liquid-phase chromatographic analysis condition is as follows:
Under positive mode, with normal hexane: Virahol/0.1% triethylamine=95: 5 (v/v) is moving phase, and flow velocity is 0.2ml/min, and VWD is 254nm.
In the step in embodiment 1 (1), the 0.012mol tetrabutyl titanate is replaced with the 0.006mol tetrabutyl titanate, 0.3mol deionized water replaces with the 0.2mol deionized water, other step also can obtain being similar to single titania microsphere that disperses among the embodiment 1 all by embodiment 1 operation.Utilize scanning electron microscope analysis, recording the particle diameter mean size is 3.4 μ m.
In the step in embodiment 1 (1), the 0.006mol methyl ethyl diketone is replaced with the 0.02mol methyl ethyl diketone, the 0.3mol deionized water replaces with the 0.7mol deionized water, and other step also can obtain single titania microsphere that disperses among the embodiment 1 all by embodiment 1 operation.Utilize scanning electron microscope analysis, record among the particle diameter ratio embodiment 3 big slightly.
In the step in embodiment 1 (2), the 16ml dehydrated alcohol is replaced with the 12ml dehydrated alcohol, the 4ml deionized water replaces with the 8ml deionized water, and other step also can obtain single titania microsphere that disperses among the embodiment 1 all by embodiment 1 operation.Utilize N
2The adsorption/desorption instrument is analyzed its hole, and its aperture is about 10nm.
Embodiment 6
In the step in embodiment 2 (1), 0.1mol 20 amine are replaced with the 0.045mol amino dodecane, the 0.2mol methyl ethyl diketone is replaced with 0.065mol or 0.060mol methyl ethyl diketone, 0.1mol isopropyl titanate replace with the 0.12mol tetrabutyl titanate, the 5mol deionized water replaces with the 2mol deionized water, other steps all by embodiment 2 operations, also can obtain monodispersed titania microsphere among the embodiment 2.The product of gained is slightly little among the particle diameter ratio embodiment 2.
Embodiment 7
In the step in embodiment 1～6 (2), autoclave is placed 100 ℃, left standstill 12 hours, other step also can obtain single titania microsphere that disperses among the embodiment 1 all by embodiment 1 operation.Slightly little among the aperture ratio embodiment 1.
Embodiment 8
In the step in embodiment 1～7 (2), temperature replaces with 300 ℃ or 600 ℃ in retort furnace, and sintering time prolongs 6 hours or shortens 3 hours, and other steps all by each embodiment operation, also can obtain monodispersed titania microsphere.
Scanning electron microscope (SEM) figure of scanning electron microscope (SEM) figure of the titania microsphere that the present invention is prepared and the titania microsphere of commodity " Sachtopore " by name (referring to Winkler, J.; Marme, S., Titania as a sorbent in normal-phaseliquid chromatography.Journal of Chromatography A, 2000,888, (1-2), 51-62.) contrast, the size distribution of the prepared titania microsphere of the present invention is narrower as can be known.
Claims (5)
1. a titania microsphere that is used for high performance liquid chromatography is characterized in that, said titania microsphere has meso-hole structure, and its particle diameter is 0.5 μ m～5 μ m, and the aperture is
Specific surface area is 100m
2/ g～130m
2/ g.
2. one kind prepares the method for titania microsphere according to claim 1, it is characterized in that said preparation method comprises the steps:
(1) template, sequestrant and titanium ester are joined in the dehydrated alcohol, under 20 ℃～40 ℃ conditions, stir mixed solution; Add deionized water in this mixed solution, stir, when throw out to be had is separated out, stop to stir and leaving standstill 30 minutes～120 minutes, filter, throw out gets the titanium gel micro-ball after with absolute ethanol washing and drying;
(2) will place autoclave by titanium gel micro-ball, urea, dehydrated alcohol and the deionized water that step (1) makes, after being uniformly dispersed, kept 8 hours～36 hours down in 70 ℃～130 ℃ states, after cooling, filtration and washing, get pressed powder, the pressed powder of gained is first through vacuum-drying 6 hours～12 hours, under 300 ℃～500 ℃ conditions, sintering 3 hours～6 hours gets target compound then;
Wherein: the mol ratio of titanium ester, template, sequestrant, dehydrated alcohol and deionized water is 1: (0.2～1): (0.5～2): (100～500): (25～50);
The mass ratio of titanium gel micro-ball and urea is 1: (0.05～0.2), the volume ratio of the volume of titanium gel micro-ball, dehydrated alcohol and deionized water are 1: (40～150): (0.5～80).
3. preparation method as claimed in claim 2 is characterized in that, wherein said titanium ester is tetrabutyl titanate or isopropyl titanate.
4. preparation method as claimed in claim 2 is characterized in that, wherein said template is RNH
2, R is C
12～C
20Alkyl.
5. preparation method as claimed in claim 2 is characterized in that, wherein said sequestrant is a methyl ethyl diketone.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159257A (en) * | 2013-03-22 | 2013-06-19 | 中国石油天然气集团公司 | Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel |
| CN106140123A (en) * | 2015-03-16 | 2016-11-23 | 中智环保新材料江苏有限公司 | A kind of preparation method and applications of mesopore titania photocatalyst |
| CN106601484A (en) * | 2016-12-10 | 2017-04-26 | 三峡大学 | Iodine-doping titanium dioxide microsphere electrode and manufacturing method thereof |
| CN107021522A (en) * | 2017-05-05 | 2017-08-08 | 常州大学 | A kind of single dispersing TiO based on microemulsion2The synthetic method of microballoon |
| CN109970100A (en) * | 2019-05-13 | 2019-07-05 | 沈阳工业大学 | A kind of titanium dioxide powder and preparation method thereof of nanocrystalline overlap joint open structure |
-
2008
- 2008-10-31 CN CN2008102020771A patent/CN101723443B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159257A (en) * | 2013-03-22 | 2013-06-19 | 中国石油天然气集团公司 | Biomimetic preparation method of hollow titanium dioxide nanospheres in sepharose gel |
| CN106140123A (en) * | 2015-03-16 | 2016-11-23 | 中智环保新材料江苏有限公司 | A kind of preparation method and applications of mesopore titania photocatalyst |
| CN106601484A (en) * | 2016-12-10 | 2017-04-26 | 三峡大学 | Iodine-doping titanium dioxide microsphere electrode and manufacturing method thereof |
| CN106601484B (en) * | 2016-12-10 | 2018-06-19 | 三峡大学 | I2 doping titanium dioxide microballoon sphere electrode and preparation method thereof |
| CN107021522A (en) * | 2017-05-05 | 2017-08-08 | 常州大学 | A kind of single dispersing TiO based on microemulsion2The synthetic method of microballoon |
| CN109970100A (en) * | 2019-05-13 | 2019-07-05 | 沈阳工业大学 | A kind of titanium dioxide powder and preparation method thereof of nanocrystalline overlap joint open structure |
| CN109970100B (en) * | 2019-05-13 | 2021-07-06 | 沈阳工业大学 | Titanium dioxide powder with nanocrystalline lap joint loose structure and preparation method thereof |
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