CN103588219B

CN103588219B - Method for enlarging aperture of mesoporous material SBA-15 and effectively removing template agent, and mesoporous material

Info

Publication number: CN103588219B
Application number: CN201310557518.0A
Authority: CN
Inventors: 李永生; 李楠; 张兴棣; 施剑林
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2013-11-11
Filing date: 2013-11-11
Publication date: 2015-07-01
Anticipated expiration: 2033-11-11
Also published as: CN103588219A

Abstract

The invention relates to a method for enlarging the aperture of a mesoporous material SBA-15 and effectively removing a template agent. The method comprises the following steps: S1, preparing SBA-15-AS containing the template agent; S2, preparing a mixed solvent by using sodium sulfate, deionized water, ethylene glycol, n-butyl alcohol and polyethylene glycol at the molar ratio of (0.5-2):(420-840):531:(48-96):0.19; S3, mixing 0.6-1 g of SBA-15-AS and 85-95 ml of mixed solvent to obtain the mixture, placing the mixture into a hot water kettle to be subjected to solvothermal aftertreatment at 100-120 DEG C for 12-72 h to obtain the product SBA-15-ST. The invention further provides the mesoporous material, namely the SBA-15-ST obtained through the method. The method provided by the invention has the advantage that the aperture of the mesoporous material is enlarged and the template agent is removed through the mixed solvothermal aftertreatment at one step.

Description

A kind of method and mesoporous material thereof making mesoporous material SBA-15 borehole enlargement and template effective elimination

Technical field

The present invention relates to nanometer and technical field of biological material, particularly a kind of method and mesoporous material thereof making mesoporous material SBA-15 borehole enlargement and template effective elimination.

Background technology

Owing to having the simplicity of good duct order, aperture adjustability and preparation method, ordered mesoporous material has attracted the concern of more and more investigator since appearance, and shows wide application prospect in the field such as loading release of catalysis, albumen sepn, drug molecule.People (the D.Y.Zhao such as Zhao in 1998, J.L.Feng, Q.S.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka, G.D.Stucky.Science279,548 (1998)) first with nonionic triblock multipolymer---polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer P123 (EO ₂₀pO ₇₀eO ₂₀) be template, prepare and there is two-dimentional hexagonal hole road structure and the good mesoporous SBA-15 material of order, and by changing the condition such as temperature or acid concentration in building-up process, achieve the physical property of SBA-15 as the controllable adjustment such as shape characteristic, pore size.In order to expand the range of application of SBA-15, the modification experiment of a lot of SBA-15 also obtain pleasurable achievement, and the material of the gained that adulterates as the transition metal such as titanium and palladium and SBA-15 carried out can give play to good catalytic performance; The grafting of surface-functionalized or even further organic molecule group is carried out to SBA-15 and can give the good medicine loading of SBA-15 and release characteristics.

Though the application potential of SBA-15 is very large, in order to produce orderly vesicular structure, must by the template removal in synthetic product.Current use comparatively widely template removal method is high-temperature calcination and solvent extration respectively.But the structure influence of calcination processing process to product is larger, side effect the most common is the contraction of inorganic skeleton network.Given this, the people such as He (J.He, X.B.Yang, D.G.Evans, X.Duan.Mater.Chem.Phys.77,270 (2002)) use two steps annealing method to SBA-15 process, be namely first fired to the decomposition temperature of template, continue to be heated to 550 DEG C after being suitably incubated, the structure and properties of resulting materials like this improves compared with dinectly bruning; The template that the people such as Yang (C.M.Yang, B.Zibrowius, W.Schmidt, F.Schuth.Chem.Mater.16,2918 (2004)) propose progressively removal method also has good treatment effect.For solvent extration, although the surface impact of this method on meso-hole structure and hole wall is less, and extraction gained template recoverable, the liquid solvent that this process need consumption is a large amount of, and post-processing step is comparatively loaded down with trivial details.

In order to make the template in SBA-15 better be removed, the people such as He (J.He, X.B.Yang, D.G.Evans, X.Duan.Mater.Chem.Phys.77,270 (2002)) and people (B.Z.Tian, the X.Y.Liu such as Tian, C.Z.Yu, F.Gao, Q.Luo, S.H.Xie, B.Tu, D.Y.Zhao.Chem.Commun.1186 (2002)) all have and utilize microwave treatment to remove the correlative study of template in SBA-15.Compared with Conventional calcination method removed template method, microwave treatment method is consuming time short, and removal efficiency is high, and products therefrom structure both shrinks rate is little, leaves surface hydroxyl more.Utilize supercritical fluid extraction method also can carry out removing of template in SBA-15, the people such as Grieken (R.V.Grieken, G.Calleja, G.D.Stucky, J.A.Melero, R.A.Garcia, J.Iglesias.Langmuir.19,3966 (2003)) at supercritical conditions with CO ₂to SBA-15 process, while reaching template removal effect, products obtained therefrom only creates very micro-structure both shrinks, maintains homogeneous pore size distribution characteristics specified and high specific surface area.It should be noted that a large amount of silanol groups can appear in product surface after this method process.In addition, the people such as Xiao (L.P.Xiao, J.Y.Li, H.X.Jin, R.R.Xu.Micropor.Mesopor.Mater.96,413 (2006)) ultraviolet/deionized water facture is utilized to carry out removing of template in SBA-15, this method just can be carried out at normal temperatures, simply effectively.

Now, ordered mesoporous material has been applied to the every field of material science and technology, and SBA-15 also plays vital effect as one of member.With regard to the removal methods of template in SBA-15, although existing a large amount of relevant report, but still there is a lot of defect:

(1) although calcination is easy, larger meso-hole structure can be caused to shrink, inhibit the physicochemical characteristic of material to a certain extent; Though two steps annealing method effect is better than calcination, but effect promoting not obvious;

(2) solvent extration is compared with calcination method, although it can not cause the contraction of meso-hole structure, but also can not realize the expansion of meso-hole structure, the impact caused meso-hole structure is less, but extraction process is loaded down with trivial details, usually will extract two to three template just can remove completely, and this problem is present in as in the methods such as ultraviolet/deionized water facture equally;

(3) template progressively removal method combine the advantage of solvent extration and calcination method, be conducive to removing completely of template, structure both shrinks dropped to very low simultaneously, but more loaded down with trivial details on treatment step;

(4) microwave treatment method and supercritical liq method for template remove completely and the protection of structure has good effect, but have certain operation easier and consumables cost.

Summary of the invention

The present invention aims to provide a kind of method making SBA-15 borehole enlargement and template effective elimination, thus while making the organic formwork agent P123 in SBA-15 obtain good removal effect, expands its aperture, makes product obtain good physicochemical characteristic.

The method making SBA-15 borehole enlargement and template effective elimination of the present invention, comprises the steps: S1, the SBA-15-AS of preparation containing template; S2 is (0.5-2) by sodium sulfate, deionized water, ethylene glycol, propyl carbinol and polyoxyethylene glycol according to mol ratio: (420-840): 531:(48-96): 0.19 is mixed with mixed solvent; S3, after being mixed mutually by mixed solvent described in SBA-15-AS and 85-95ml described in 0.6-1g, is placed in water heating kettle with 100-120 DEG C of solvent thermal aftertreatment 12-72h, obtains product SBA-15-ST.

Preferably, described step S1 comprises template P123, deionized water, hydrochloric acid according to after the ratio mixing of mol ratio 1:9667:937, stir 4-8h at 38-42 DEG C after, add 59.2mol tetraethoxy, and vigorous stirring 5min, after standing 20h, suction filtration, washing, drying treatment obtain described SBA-15-AS.

Preferably, the mol ratio of sodium sulfate, deionized water, ethylene glycol, propyl carbinol and polyoxyethylene glycol in described step S2 is 1:789:531:90:0.19.

Preferably, the temperature of the solvent thermal aftertreatment in described step S3 is 110 DEG C.

Preferably, the time of the solvent thermal aftertreatment in described step S3 is 48h.

Preferably, described SBA-15-AS is without hydrothermal treatment consists.

Preferably, described SBA-15-AS calcines and obtains SBA-15 after hydrothermal treatment consists.

Preferably, described hydrothermal treatment consists comprises described SBA-15-AS at 100 DEG C of hydrothermal treatment consists 24h.

A kind of mesoporous material, described mesoporous material is the SBA-15-ST obtained according to aforesaid method.

Principle of the present invention is: because the silicon extent of polymerization of SBA-15-AS is lower, it has very high polycondensation potentiality again.During high temperature, hydrophilic radical polyethylene oxide (PEO) the hydratability step-down of template, simultaneously the hydrophobicity grow of poly(propylene oxide) (PPO), PEO part is recovered to micella inside, thus makes the hydrophobic part of whole micella become large; Meanwhile, it is inner that long-chain alcohol is added to template micella, issues and be conigenous group rearrangement, in the process increasing micellar hydrophobic partial volume, duct is expanded at high-temperature and high-pressure conditions.On the other hand, due to the existence of micropore in SBA-15-AS, sodium ion can be packed into due to hydrophilic radical PEO shrink and in left micropore, its by with a certain amount of H on hole wall ⁺replace, thus make silanol groups that further condensation occur, and then cause hole wall to shrink (part under high temperature or even duct is caved in), namely duct expands effect.After mesopore orbit expanded, alcoholic solvent has enough spaces by template micella parcel, stripping, final generation template removal effect.

Method provided by the present invention is new and original, aftertreatment is carried out to containing template SBA-15-AS by the concept introducing mixed solvent heat treatment, the borehole enlargement of mesoporous material SBA-15 and template removal one step are completed, optimizes high-temperature calcination common at present and solvent extration etc.Procedure simple and effective provided by the present invention, reproducible.Expanded further through the aperture of the mesoporous material of mixed solvent heat treatment, order is good, is expected to the advantage playing mesoporous material in medicine controlled releasing field (particularly in the controlled release of protein molecular).

Accompanying drawing explanation

Fig. 1 is the process flow sheet making the method for mesoporous material SBA-15 borehole enlargement and template effective elimination provided by the present invention;

Fig. 2 is that the Fourier of the SBA-15-ST of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1 resonates infrared spectra comparison diagram;

Fig. 3 is the thermogravimetric analysis collection of illustrative plates comparison diagram of the SBA-15-ST of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1;

Fig. 4 is the comparison diagram that the small angle X-ray diffraction of the SBA-15-ST of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1 analyzes collection of illustrative plates;

The scanning electron microscope image (Fig. 5 a:SBA-15-ST-100, Fig. 5 b:SBA-15-ST-110, Fig. 5 c:SBA-15-ST-120) of the SBA-15-ST of the borehole enlargement that Fig. 5 is prepared according to the technique of Fig. 1 and template effective elimination;

Fig. 6 is the images of transmissive electron microscope (Fig. 6 a:SBA-15-ST-100, Fig. 6 b:SBA-15-ST-110, Fig. 6 c:SBA-15-ST-120) of the SBA-15-ST of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1;

Fig. 7 be the nitrogen adsorption-desorption image of the SBA-15-ST of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1 (Fig. 7 a) and graph of pore diameter distribution (Fig. 7 b);

Fig. 8 is the technique according to Fig. 1, SBA-15-ST-110 and the SBA-15-AS under optimization solvent thermal post-treatment condition prepared by (specific solvent composition, 110 DEG C, 48h) and the nmr spectrum comparison diagram of SBA-15-HT-Cal;

Fig. 9 is that the Fourier of the SBA-15-EP of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1 resonates infrared spectra spectrogram;

Figure 10 is that (Figure 10 a) and graph of pore diameter distribution (Figure 10 b) for the nitrogen adsorption-desorption image of the SBA-15-EP of borehole enlargement and the template effective elimination prepared according to the technique of Fig. 1.

Embodiment

Below in conjunction with accompanying drawing, provide preferred embodiment of the present invention, and be described in detail.

Embodiment 1

At ambient temperature, by template P123, deionized water, hydrochloric acid according to after the ratio mixing of mol ratio 1:9667:937, stir 6h at 40 DEG C after, add 59.2mol tetraethoxy, and vigorous stirring 5min, after standing 20h, suction filtration, washing, drying treatment are carried out to gained g., jelly-like liquid, both obtained pretreatment sample SBA-15-AS(SBA-15-As Synthesized).Above-mentioned steps can with reference to J.AM.CHEM.SOC.2004,126,14348-14349.

With the heat-up rate of 1.5 DEG C/min, at 550 DEG C, be incubated 6h, both obtained product SBA-15-AS-Cal(SBA-15-Calcination).Pass through heating and heat preservation step herein by the template removal in SBA-15-AS, obtain contrast sample SBA-15-AS-Cal).

After above-mentioned for 0.8g pretreatment sample SBA-15-AS is mixed mutually with 88ml mixed solvent (sodium sulfate, deionized water, ethylene glycol, propyl carbinol and polyoxyethylene glycol are that 1:789:531:90:0.19 prepares according to mol ratio), be placed in water heating kettle with 110 DEG C of solvent thermal 48h, after suction filtration, washing, drying treatment, obtain the finished product SBA-15-ST-110(SBA-15-Solvent Thermal Treatment).

Embodiment 2

Implementation method and basic recipe identical with embodiment 1, the treatment temp only changing solvent thermal post-processing step is 100 DEG C, obtains the finished product SBA-15-ST-100.

Embodiment 3

Implementation method and basic recipe identical with embodiment 1, the treatment temp only changing solvent thermal post-processing step is 120 DEG C, obtains the finished product SBA-15-ST-120.

Fig. 2 is the Fourier transform infrared spectroscopy figure of each sample in embodiment 1-3, and for the ease of observing, respectively each curve has been carried out vertically moving in various degree, therefore transmittance is not as a reference.Compared to SBA-15-AS sample, other each sample are at 1200-1500cm ^-1and 2850-3000cm ^-1to indicate template removal effect remarkable in the disappearance of place's vibration peak.In Fig. 3 Mass be changed to mass loss, SBA-15-AS-Cal is through the sample of calcining, wherein not containing template, without the need to carrying out thermogravimetric analysis.For other samples, Mass change is less, and template removal effect is better.Template removal effect is followed successively by 120 DEG C of >110 DEG C of >100 DEG C.

Embodiment 4

By template P123, deionized water, hydrochloric acid is according to after the ratio mixing of 1:9667:937, stir 6-10h at 40 DEG C after, add 59.2mol tetraethoxy, and vigorous stirring 5min, after standing 20h, carry out 100 DEG C of hydrothermal treatment consists 24h, suction filtration is carried out to gained liquid, carrying out washing treatment, the SBA-15-HT(SBA-15-Hydrothermal Treatment obtained after drying) be placed in retort furnace, with the heat-up rate of 1.5 DEG C/min, 6h is incubated at 550 DEG C, both product SBA-15-HT-Cal(SBA-15-Hydrothermal Treatment-Calcination was obtained), be common SBA-15.

Fig. 4 is the small angle X-ray diffraction spectrogram comparison diagram of each sample in embodiment 1-4, can find, compared with SBA-15-AS-Cal sample, the order through each SBA-15-ST sample of solvent thermal aftertreatment is good, just can not reach the order not second to SBA-15-HT-Cal by calcining step.In addition, the main peak (100) of each SBA-15-ST sample shows and significantly moves to left, and means the borehole enlargement of SBA-15 after solvent thermal post-processing step, and the data of its concrete borehole enlargement are characterized by nitrogen adsorption desorption.

Fig. 5 and Fig. 6 is through the scanning electron microscope of each SBA-15-ST sample of solvent thermal aftertreatment and transmission electron microscope photo in embodiment 1-3, can find, comparatively high temps process (120 DEG C), although be conducive to the lifting of template removal effect, can cause the part in sample duct to cave in.

Fig. 7 a is the nitrogen adsorption-desorption spectrogram through each SBA-15-ST sample of solvent thermal aftertreatment in embodiment 1-4, and each spectrogram all presents IV type adsorption equilibrium thermoisopleth, illustrates that each SBA-15-ST sample maintains meso-hole structure after solvent thermal aftertreatment; All from then on the parameters such as specific surface area, pore volume, pore size distribution obtain in spectrogram.Fig. 7 b is the graph of pore diameter distribution through each SBA-15-ST sample of solvent thermal aftertreatment in embodiment 1-4, can find, the aperture of each SBA-15-ST sample is all at about 10nm, close with the aperture of SBA-15-HT-Cal after being stripped of template, and is obviously greater than the aperture of SBA-15-AS-Cal.In addition, the graph of pore diameter distribution of 120 DEG C shows swarming, this and the channel section shown in scanning electron microscope and transmission electron microscope photo phenomenon of caving in is consistent.

Give the pore structure parameter of each SBA-15-ST sample in following table 1, its specific surface area is at 320-360m ²within the scope of/g.

Table 1

Fig. 8 is the nmr spectrum comparison diagram of sample SBA-15-ST-110 and SBA-15-AS and SBA-15-HT-Cal, can find, pretreatment sample SBA-15-AS is after solvent thermal aftertreatment, and its silicon Skeleton Table reveals certain contraction, but still remains more silanol groups.

Embodiment 5

Implementation method and basic recipe identical with embodiment 1, the mixed solvent mol ratio only changing solvent thermal post-processing step is 0.5:789:531:90:0.19, obtains the finished product SBA-15-EP-1(SBA-15-Exterme Point).

Embodiment 6

Implementation method and basic recipe identical with embodiment 1, the mixed solvent mol ratio only changing solvent thermal post-processing step is 2:789:531:90:0.19, obtains the finished product SBA-15-EP-2.

Embodiment 7

Implementation method and basic recipe identical with embodiment 1, the mixed solvent mol ratio only changing solvent thermal post-processing step is 1:420:531:90:0.19, obtains the finished product SBA-15-EP-3.

Embodiment 8

Implementation method and basic recipe identical with embodiment 1, the mixed solvent mol ratio only changing solvent thermal post-processing step is 1:840:531:90:0.19, obtains the finished product SBA-15-EP-4.

Embodiment 9

Implementation method and basic recipe identical with embodiment 1, the mixed solvent mol ratio only changing solvent thermal post-processing step is 1:789:531:48:0.19, obtains the finished product SBA-15-EP-5.

Embodiment 10

Implementation method and basic recipe identical with embodiment 1, the mixed solvent mol ratio only changing solvent thermal post-processing step is 1:789:531:96:0.19, obtains the finished product SBA-15-EP-6.

Fig. 9 is the Fourier transform infrared spectroscopy figure of each sample in embodiment 5-10, and for the ease of observing, respectively each curve has been carried out vertically moving in various degree, therefore transmittance is not as a reference.Can find, compared to SBA-15-AS sample, other each sample are at 1200-1500cm ^-1and 2850-3000cm ^-1place's vibration peak all shows disappearance in various degree, shows that template is removed.

Figure 10 a is the nitrogen adsorption-desorption spectrogram through each SBA-15-EP sample of solvent thermal aftertreatment in embodiment 5-10, and each spectrogram all presents IV type adsorption equilibrium thermoisopleth, illustrates that each SBA-15-EP sample maintains meso-hole structure after solvent thermal aftertreatment; All from then on the parameters such as specific surface area, pore volume, pore size distribution obtain in spectrogram.Figure 10 b is the graph of pore diameter distribution through each SBA-15-EP sample of solvent thermal aftertreatment in embodiment 5-10, can find, compared to SBA-15-AS-Cal sample, each SBA-15-EP sample all shows borehole enlargement in various degree.

The pore structure parameter of each SBA-15-EP sample is given in following table 2.

Table 2

The present invention, according to suitable formula, makes mesoporous SBA-15 material borehole enlargement by the method for solvent thermal aftertreatment, and template effective elimination.Wherein, under optimization solvent thermal post-treatment condition the borehole enlargement of gained and the SBA-15-ST-110 sample of template effective elimination not only similar to the order of common SBA-15, and while guarantee structural integrity, surface remains a large amount of silanol groups, can give play to larger advantage in actual applications.

In like manner, after mixed solvent described in 0.6g SBA-15-AS and 85ml mixes by applicant mutually, be placed in water heating kettle with 100 DEG C of solvent thermal aftertreatment 72h, obtain product SBA-15-ST.After mixed solvent described in 1gSBA-15-AS and 95ml is mixed mutually, be placed in water heating kettle with 120 DEG C of solvent thermal aftertreatment 12h, obtain product SBA-15-ST.By template P123, deionized water, hydrochloric acid according to after the ratio mixing of mol ratio 1:9667:937, stir 8h at 38 DEG C after, obtain described SBA-15-AS.By template P123, deionized water, hydrochloric acid according to after the ratio mixing of mol ratio 1:9667:937, stir 4h at 42 DEG C after, obtain described SBA-15-AS.Above-described embodiment can realize content of the present invention equally.

Above-described, be only preferred embodiment of the present invention, and be not used to limit scope of the present invention, the above embodiment of the present invention can also make a variety of changes.Namely every claims according to the present patent application and description are done simple, equivalence change and modify, and all fall into the claims of patent of the present invention.The not detailed description of the present invention be routine techniques content.

Claims

1. make a method for mesoporous material SBA-15 borehole enlargement and template effective elimination, it is characterized in that, the method comprises the steps:

S1, the SBA-15-AS of preparation containing template;

S2 is (0.5-2) by sodium sulfate, deionized water, ethylene glycol, propyl carbinol and polyoxyethylene glycol according to mol ratio: (420-840): 531:(48-96): 0.19 is mixed with mixed solvent;

S3, after being mixed mutually by mixed solvent described in SBA-15-AS and 85-95ml described in 0.6-1g, is placed in water heating kettle with 100-120 DEG C of solvent thermal aftertreatment 12-72h, obtains product SBA-15-ST;

Wherein, described step S1 comprises template P123, deionized water, hydrochloric acid according to after the ratio mixing of mol ratio 1:9667:937, stir 4-8h at 38-42 DEG C after, add 59.2mol tetraethoxy, and vigorous stirring 5min, after standing 20h, suction filtration, washing, drying treatment obtain described SBA-15-AS.

2. method according to claim 1, is characterized in that, the mol ratio of the sodium sulfate in described step S2, deionized water, ethylene glycol, propyl carbinol and polyoxyethylene glycol is 1:789:531:90:0.19.

3. method according to claim 1, is characterized in that, the temperature of the solvent thermal aftertreatment in described step S3 is 110 DEG C.

4. method according to claim 1, is characterized in that, the time of the solvent thermal aftertreatment in described step S3 is 48h.

5. method according to claim 1, is characterized in that, described SBA-15-AS is without hydrothermal treatment consists.

6. a mesoporous material, is characterized in that, described mesoporous material is the SBA-15-ST that the method according to any one of the claims 1-5 obtains.