CN104998590A - Surface-modified KIT-6 mesoporous material and synthesis method and application thereof - Google Patents
Surface-modified KIT-6 mesoporous material and synthesis method and application thereof Download PDFInfo
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- CN104998590A CN104998590A CN201510439287.2A CN201510439287A CN104998590A CN 104998590 A CN104998590 A CN 104998590A CN 201510439287 A CN201510439287 A CN 201510439287A CN 104998590 A CN104998590 A CN 104998590A
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Abstract
The invention discloses a surface-modified KIT-6 mesoporous material and a synthesis method and application thereof. A segmented copolymer EO20PO70EO20 is dissolved in water under the acidic condition and evenly mixed with n-butyl alcohol, ethyl orthosilicate and (3-cyanopropyl)triethoxy-silane are added and stirred, hydrothermal reaction is performed under 100 DEG C-110 DEG C, filtration and drying are performed to obtain a mesoporous material with an cyano functional group on the surface, and amidoximation is performed on the mesoporous material through hydroxylammonium chloride to obtain the mesoporous material with an amidoxime group on the surface. The material synthesized through the method has a good spatial structure, a large specific area and a large pore volume, the amidoxime group on the surface of the material has selective adsorption on uranium ions, and therefore the material has great application value in the adsorption or separation field.
Description
Technical field
The present invention relates to a kind of mesoporous material, synthetic method and application thereof, the KIT-6 mesoporous material of particularly a kind of finishing, synthetic method and application thereof, belong to Material Field.
Background technology
In the last few years, heavy metal was day by day serious to the pollution of environment, and then caused high risks to the mankind and animals and plants.Wherein uranium (VI) is not only heavy metal, also belongs to radionuclide, the existence of uranium in environment, understands the health of seriously threatening environment and organism.
The method of process radioactive wastewater has multiple, and conventional method has the precipitation method, absorption method, ion-exchange etc.And wherein absorption method operation is the most convenient, be suitable for the improvement of a large amount of waste water.In absorption method, the selection of adsorbent is very important, and usual Selection radio surface area is large, the material of physics and stable chemical nature.The uranium (VI) in SBA-15 adsorbent solution is adopted as document 1 (Xinghui Wang et al.Annalsof Nuclear Energy, 2013,56,151-157).Document 2 (KleitzF, Choi S H, Ryoo R.Chemical Communications, 2003 (17): 2136-2137.) KIT-6 of sol-gel process synthesis is reported, be characterized in the space structure with Ia3d, and have larger specific area and aperture.But for the absorption of heavy metal ion uranium ion, it is selective that its shortcoming is that this material lacks ion.Document 3 (Nilchi A, Babalou AA, Rafiee R, et al.Reactive & Functional Polymers, 2008,68 (12): 1665 – 1670.) use uranyl ion in resin adsorption water, although resin after surface modification with functional group to uranyl ion, there is selective absorption, but effect is still undesirable, and the rate of adsorption is comparatively slow, and its main cause is that the structure of material itself is unfavorable for absorption.Therefore, select to be conducive to adsorbing and the material modified can be carried out for the place to go of uranium ion in solution and important in surface.
Summary of the invention
The object of the present invention is to provide a kind of KIT-6 mesoporous material of finishing, synthetic method and the adsorption applications of described mesoporous material on uranium ion.
The technical solution realizing the object of the invention is: a kind of KIT-6 mesoporous material of finishing, and described KIT-6 mesoporous material is space Emission in Cubic structure, and its surface uniform modifies amidoxime group.
The specific area of described mesoporous material is 484 ~ 824m
2/ g, pore volume is 0.50 ~ 1.13cm
3/ g, aperture is 5.95 ~ 3.98nm.
The synthetic method of the KIT-6 mesoporous material of above-mentioned finishing, concrete steps are as follows:
(1) block copolymer EO is got
20pO
70eO
20soluble in water, add n-butanol, and mix;
(2) ethyl orthosilicate and 3-cyanogen propyl-triethoxysilicane (CPTES) are joined in the mixed solution of step (1), and stir, hydro-thermal reaction, obtains the KIT-6 mesoporous material of surface with cyano functional group by stoste filtration, drying, backflow removing template after cooling;
(3) the KIT-6 mesoporous material with cyano functional group surperficial in step (2) is carried out amidoximation, regulate the pH value of reaction solution to 6-7, by solution filtration, washing, vacuum drying after reaction terminates, obtain the surperficial mesoporous material with amidoxime group.
In step (1), block copolymer EO
20pO
70eO
20be 1:1 with the mass ratio of n-butanol.
In step (2), the mol ratio of ethyl orthosilicate and 3-cyanogen propyl-triethoxysilicane is 5:1 ~ 7:1, block copolymer EO
20pO
70eO
20be 1:2.085 with the mass ratio of ethyl orthosilicate, hydrothermal temperature is 100 ~ 110 DEG C, reaction time 24h.
In step (3), the reagent of amidoximation adopts hydroxylamine chloride, and the surperficial KIT-6 mesoporous material with cyano functional group and hydroxylamine chloride mass ratio are 1:8.
Above-mentioned surface is with the application of mesoporous material in uranium ion absorption of amidoxime group, and in described application, pH is 4-5, and preferred pH is 4.
Compared with prior art, its remarkable advantage is in the present invention:
(1) amidoxime group is successfully evenly distributed in mesoporous material earth silicon material surface with the mesoporous material of amidoxime group by the present invention surface of preparing, and mesoporous material earth silicon material has bigger serface, can hold uranium ion;
(2) surface remains the large specific area of mesoporous material and pore volume with the mesoporous material of amidoxime group, therefore can be widely used in the fields such as absorption, separation, catalysis, information storage and biological medicine.
Accompanying drawing explanation
Fig. 1 is the little angle XRD spectra of the KIT-6 mesoporous material CN-KIT-6-7:1 of gained finishing in the embodiment of the present invention 1.
Fig. 2 is pore size distribution curve figure (a) and the nitrogen cryogenic absorption-desorption isotherm (b) of the KIT-6 mesoporous material CN-KIT-6-7:1 of gained finishing in the embodiment of the present invention 1.
Fig. 3 is the TEM image (scale is 100nm) of the KIT-6 mesoporous material CN-KIT-6-7:1 of gained finishing in the embodiment of the present invention 1.
Fig. 4 is the KIT-6 mesoporous material CN-KIT-6-7:1 of gained finishing in the embodiment of the present invention 1 and the surface infrared spectrogram image with amidoxime group mesoporous material AN-KIT-6-7:1.
Fig. 5 is pore size distribution curve figure (a) and the nitrogen cryogenic absorption-desorption isotherm (b) of the KIT-6 mesoporous material CN-KIT-6-6:1 of gained finishing in the embodiment of the present invention 2.
Fig. 6 is pore size distribution curve figure (a) and the nitrogen cryogenic absorption-desorption isotherm (b) of the KIT-6 mesoporous material CN-KIT-6-5:1 of gained finishing in the embodiment of the present invention 3.
Fig. 7 be KIT-6 mesoporous material AN-KIT-6-5:1 that in the embodiment of the present invention 3, synthesis obtains finishing under differential responses time conditions to the adsorbance curve of uranyl ion.
Detailed description of the invention
In order to understand the present invention better, illustrate technical scheme of the present invention below by specific embodiment.
Embodiment 1: the preparation of the KIT-6 mesoporous material of finishing
(1) the KIT-6 mesoporous material synthesis of finishing: take 1.00g block copolymer EO
20pO
70eO
20(P
123) in beaker, measure the deionized water of 2mL concentrated hydrochloric acid and 36.6mL, stir, by P under 35 DEG C of conditions
123be dissolved in hydrochloric acid solution, make its self assembly form meso-hole structure.Treat that P123 dissolves completely, after solution mixes completely, add 1.00g n-butanol, after stirring 1h, in solution, add ethyl orthosilicate (TEOS) 2.085g and organic-silylation reagent-3-cyanogen propyl-triethoxysilicane (CPTES) 0.3305g.Mixture stirs 24h at 35 DEG C, carries out hydrothermal treatment consists (100 DEG C) 24h after 24h to compounding substances.After hydrothermal treatment consists, mixture is filtered, dry and obtain white powder.White powder is now with template P
123, adopt the method for backflow to remove sample surfaces template.Remove the sample after template to dry, obtain the KIT-6 mesoporous material CN-KIT-6-7:1 of finishing.
(2) material amidoxim process: in amidoxim process, use the mesoporous material CN-KIT-6 of hydroxylamine chloride effects on surface modification to carry out amidoxim, be specially: weigh 20mL distilled water, weigh hydroxylamine chloride 4.0g, natrium carbonicum calcinatum is used to regulate solution ph to be react 3h at 6,70 DEG C.After reaction terminates, solution is filtered, and by the inorganic salts washes clean of distilled water by solid material surface, vacuum drying chamber 60 DEG C of dry 12h, obtain the mesoporous material AN-KIT-6-7:1 of surface with amidoxime group.
Be the XRD collection of illustrative plates of the present embodiment shown in Fig. 1, can tell two diffraction maximums in figure, documents is reported, they can belong to (211) of the KIT-6 material with Ia3d structure respectively, the diffraction maximum of (220) crystal face.Illustrate that synthetic material has the space structure of Emission in Cubic.
Be the nitrogen cryogenic absorption-desorption isotherm of the present embodiment shown in Fig. 2, in figure, curve presents typical I type adsorption isotherm.At P/P
0when being 0.4 ~ 0.7, have obvious hysteresis loop, illustrative material has homogeneous meso-hole structure.Its BET specific surface area is 706.526m
2/ g, pore volume is 0.85cm
3/ g, in the pore size distribution curve calculated by BJH, most probable pore size is 4.55nm.
Fig. 3 is the TEM picture of the present embodiment, and from figure, can be clearly seen that the space crystal plane structure of material, distribution of material is even.
Fig. 4 is the infrared spectrogram of the present embodiment, can find out that the material of surface with cyano functional group is (a) at 2254cm in figure from infrared spectrogram
-1(cyano functional group characteristic peak is 2250 ~ 2260cm
-1) place has characteristic peak to occur, material after amidoxim (b) 2254cm in figure
-1the characteristic peak at place disappears, and at 1640cm
-1and 1540cm
-1there is characteristic peak in the place of left and right.
Embodiment 2: the concrete implementation step of present embodiment and the difference of embodiment 1 are that adding organic-silylation reagent-3-cyanogen propyl-triethoxysilicane (CPTES) quality is 0.3856g; Other are identical with embodiment 1.
Be the nitrogen cryogenic absorption-desorption isotherm of the present embodiment shown in Fig. 5, in figure, curve presents typical I type adsorption isotherm.At P/P
0when being 0.4 ~ 0.6, have obvious hysteresis loop, illustrative material has homogeneous meso-hole structure.Its BET specific surface area is 603.163m
2/ g, pore volume is 0.60cm
3/ g, in the pore size distribution curve calculated by BJH, most probable pore size is 3.98nm.
Embodiment 3: the concrete implementation step of present embodiment and the difference of embodiment 1 are that adding organic-silylation reagent-3-cyanogen propyl-triethoxysilicane (CPTES) quality is 0.4627g; Other are identical with embodiment 1.
Be the nitrogen cryogenic absorption-desorption isotherm of the present embodiment shown in Fig. 6, in figure, curve presents typical I type adsorption isotherm.At P/P
0when being 0.4 ~ 0.6, have obvious hysteresis loop, illustrative material has homogeneous meso-hole structure.Its BET specific surface area is 484.71m
2/ g, pore volume is 0.50cm
3/ g, in the pore size distribution curve calculated by BJH, most probable pore size is 4.15nm.
Embodiment 4: synthesize the KIT-6 mesoporous material AN-KIT-6 of the finishing obtained in embodiment 3 to the adsorption applications of uranium ion.
(1) 25 DEG C, the concentration adding 100mL uranium ion in the conical flask of 250mL is the solution of 100mg/L, then adds Jie KIT-6 Porous materials AN-KIT-6 of finishing of 0.02g wherein, uses 1M NaOH to regulate the pH of mixed solution to be 4.
(2) filter after reacting a period of time, use UV1801 ultraviolet specrophotometer to measure the concentration of uranium ion in filtrate, add the arsenazo III colour developing of 0.1% of 1mL, use q=(C
0-C
ethe adsorbance of) × V/m formulae discovery material.
Fig. 7 is the present embodiment adsorbance curve to uranium ion under differential responses time conditions.The adsorbance of KIT-6 materials A N-KIT-6 to uranium ion observing finishing from figure increases with the increase in reaction time, and its adsorption capacity is 163.53mg/g.
Claims (8)
1. a KIT-6 mesoporous material for finishing, is characterized in that, described KIT-6 mesoporous material is space Emission in Cubic structure, and its surface uniform modifies amidoxime group.
2. the KIT-6 mesoporous material of finishing as claimed in claim 1, it is characterized in that, the specific area of described mesoporous material is 484 ~ 824m
2/ g, pore volume is 0.50 ~ 1.13cm
3/ g, aperture is 5.95 ~ 3.98nm.
3. the synthetic method of the KIT-6 mesoporous material of finishing as claimed in claim 1, it is characterized in that, concrete steps are as follows:
(1) block copolymer EO is got
20pO
70eO
20soluble in water, add n-butanol, and mix;
(2) ethyl orthosilicate and 3-cyanogen propyl-triethoxysilicane are joined in the mixed solution of step (1), and stir, hydro-thermal reaction, obtains the KIT-6 mesoporous material of surface with cyano functional group by stoste filtration, drying, backflow removing template after cooling;
(3) the KIT-6 mesoporous material with cyano functional group surperficial in step (2) is carried out amidoximation, regulate the pH value of reaction solution to 6-7, by solution filtration, washing, vacuum drying after reaction terminates, obtain the surperficial mesoporous material with amidoxime group.
4. the synthetic method of the KIT-6 mesoporous material of finishing as claimed in claim 3, is characterized in that, in step (1), and block copolymer EO
20pO
70eO
20be 1:1 with the mass ratio of n-butanol.
5. the synthetic method of the KIT-6 mesoporous material of finishing as claimed in claim 3, it is characterized in that, in step (2), the mol ratio of ethyl orthosilicate and 3-cyanogen propyl-triethoxysilicane is 5:1 ~ 7:1, block copolymer EO
20pO
70eO
20be 1:2.085 with the mass ratio of ethyl orthosilicate, hydrothermal temperature is 100 ~ 110 DEG C, reaction time 24h.
6. the synthetic method of the KIT-6 mesoporous material of finishing as claimed in claim 3, it is characterized in that, in step (3), the reagent of amidoximation adopts hydroxylamine chloride, and the surperficial KIT-6 mesoporous material with cyano functional group and hydroxylamine chloride mass ratio are 1:8.
7. the application of KIT-6 mesoporous material in uranium ion absorption of the finishing as described in as arbitrary in claim 1-6.
8. apply as claimed in claim 7, it is characterized in that, the pH value of adsorption process is 4-5.
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| CN106179271A (en) * | 2016-08-05 | 2016-12-07 | 四川大学 | Hyperbranched Nano diamond of polyamidoxime functionalization and preparation method and application |
| CN106824101A (en) * | 2017-03-14 | 2017-06-13 | 浙江大学 | A kind of method of the adsorption uranium from seawater |
| CN112076734A (en) * | 2020-08-25 | 2020-12-15 | 辽宁大学 | Preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery |
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| CN112076734A (en) * | 2020-08-25 | 2020-12-15 | 辽宁大学 | Preparation method of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material and application of salicylaldoxime/polydopamine/three-dimensional mesoporous silica composite material in gallium recovery |
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