CN104998590A - Surface-modified KIT-6 mesoporous material and synthesis method and application thereof - Google Patents
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 50
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 12
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 9
- 229920001400 block copolymer Polymers 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- -1 uranium ions Chemical class 0.000 abstract description 14
- VGIURMCNTDVGJM-UHFFFAOYSA-N 4-triethoxysilylbutanenitrile Chemical compound CCO[Si](OCC)(OCC)CCCC#N VGIURMCNTDVGJM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 2
- AAORDHMTTHGXCV-UHFFFAOYSA-N uranium(6+) Chemical compound [U+6] AAORDHMTTHGXCV-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
本发明公开了一种表面修饰的KIT-6介孔材料、合成方法及应用。本发明在酸性条件下，将嵌段共聚物EO20PO70EO20在水中溶解，与正丁醇混合均匀，加入正硅酸乙酯与3-氰丙基三乙氧基硅搅拌，100-110℃条件下水热反应，过滤、干燥得到表面带有氰基官能团的介孔材料；使用氯化羟胺对该介孔材料进行偕胺肟化，得到表面带有偕胺肟基团的介孔材料。该方法合成的材料具有良好的空间结构，大的比表面积和孔容，且表面带有的偕胺肟基团对铀离子具有选择吸附性，因此在吸附、分离领域具有极大的应用价值。
The invention discloses a surface-modified KIT-6 mesoporous material, a synthesis method and an application. In the present invention, under acidic conditions, the block copolymer EO 20 PO 70 EO 20 is dissolved in water, mixed evenly with n-butanol, added with tetraethyl orthosilicate and 3-cyanopropyl triethoxy silicon, stirred, 100- Hydrothermal reaction at 110°C, filtration, and drying to obtain mesoporous materials with cyano functional groups on the surface; use hydroxylamine chloride for amidoximation of the mesoporous materials to obtain mesoporous materials with amidoxime groups on the surface . The material synthesized by the method has good spatial structure, large specific surface area and pore volume, and the amidoxime group on the surface has selective adsorption for uranium ions, so it has great application value in the field of adsorption and separation.
Description
技术领域technical field
本发明涉及一种介孔材料、合成方法及其应用，特别是一种表面修饰的KIT-6介孔材料、合成方法及其应用，属于材料领域。The invention relates to a mesoporous material, a synthesis method and its application, in particular to a surface-modified KIT-6 mesoporous material, a synthesis method and its application, and belongs to the field of materials.
背景技术Background technique
近些年来，重金属对环境的污染日益严重，进而对人类及动植物造成了极大危害。其中铀(Ⅵ)不仅是重金属，也归属于放射性核素，环境中铀的存在，会严重地威胁环境及生物体的健康。In recent years, the pollution of heavy metals to the environment has become increasingly serious, which has caused great harm to humans, animals and plants. Among them, uranium (Ⅵ) is not only a heavy metal, but also a radionuclide. The existence of uranium in the environment will seriously threaten the health of the environment and organisms.
处理放射性废水的方法有多种，常用的方法有沉淀法、吸附法、离子交换法等。而其中吸附法操作最为方便，适合于大量废水的治理。吸附法中吸附剂的选择极为重要，通常选择比表面积大，物理及化学性质稳定的物质。如文献1(Xinghui Wang et al.Annalsof Nuclear Energy,2013,56,151-157)采用SBA-15吸附溶液中的铀(Ⅵ)。文献2(KleitzF,Choi S H,Ryoo R.Chemical Communications,2003(17):2136-2137.)报道了溶胶-凝胶法合成的KIT-6，其特点是具有Ia3d的空间结构，且有较大的比表面积和孔径。但对于重金属离子铀离子的吸附来说，其缺点是该材料缺少对离子的选择性。文献3(Nilchi A,Babalou AA,Rafiee R,et al.Reactive&Functional Polymers,2008,68(12):1665–1670.)使用树脂吸附水中铀酰离子，虽然树脂经表面改性后带有的官能团对铀酰离子具有选择性吸附，但是效果仍不理想，且吸附速率较慢，其主要原因是材料本身的结构不利于吸附。因此，选择有利于吸附且表面可进行修饰的材料对于溶液中铀离子的去处及其重要。There are many ways to treat radioactive wastewater, and the commonly used methods are precipitation, adsorption, ion exchange and so on. Among them, the adsorption method is the most convenient to operate and is suitable for the treatment of large amounts of wastewater. The choice of adsorbent in the adsorption method is extremely important, and usually a substance with a large specific surface area and stable physical and chemical properties is selected. For example, literature 1 (Xinghui Wang et al. Annals of Nuclear Energy, 2013, 56, 151-157) uses SBA-15 to adsorb uranium (VI) in the solution. Document 2 (KleitzF, Choi SH, Ryoo R.Chemical Communications, 2003 (17): 2136-2137.) reported KIT-6 synthesized by sol-gel method, which is characterized in having a spatial structure of Ia3d, and has relatively Large specific surface area and pore size. But for the adsorption of heavy metal ions uranium ions, the disadvantage is that the material lacks ion selectivity. Document 3 (Nilchi A, Babalou AA, Rafiee R, et al. Reactive & Functional Polymers, 2008, 68(12): 1665–1670.) uses resins to adsorb uranyl ions in water, although the functional groups carried by the resins after surface modification are Uranyl ions have selective adsorption, but the effect is still unsatisfactory, and the adsorption rate is slow. The main reason is that the structure of the material itself is not conducive to adsorption. Therefore, the selection of materials that are conducive to adsorption and can be modified on the surface is extremely important for the removal of uranium ions in solution.
发明内容Contents of the invention
本发明的目的在于提供一种表面修饰的KIT-6介孔材料、合成方法及所述介孔材料在铀离子上的吸附应用。The object of the present invention is to provide a surface-modified KIT-6 mesoporous material, a synthesis method and the adsorption application of the mesoporous material on uranium ions.
实现本发明目的的技术解决方案是：一种表面修饰的KIT-6介孔材料，所述的KIT-6介孔材料为空间立方相结构，且其表面均匀修饰偕胺肟基团。The technical solution to realize the object of the present invention is: a surface-modified KIT-6 mesoporous material, the KIT-6 mesoporous material has a cubic phase structure, and its surface is evenly modified with amidoxime groups.
所述的介孔材料的比表面积为484～824m2/g，孔容为0.50～1.13cm3/g，孔径为5.95～3.98nm。The specific surface area of the mesoporous material is 484-824m 2 /g, the pore volume is 0.50-1.13cm 3 /g, and the pore diameter is 5.95-3.98nm.
上述表面修饰的KIT-6介孔材料的合成方法，具体步骤如下：The synthetic method of the KIT-6 mesoporous material of above-mentioned surface modification, concrete steps are as follows:
(1)取嵌段共聚物EO20PO70EO20溶于水中，加入正丁醇，并混合均匀；(1) Dissolve block copolymer EO 20 PO 70 EO 20 in water, add n-butanol, and mix well;
(2)将正硅酸乙酯与3-氰丙基三乙氧基硅(CPTES)加入到步骤(1)的混合溶液中，并搅拌均匀，水热反应，冷却后将原液过滤、干燥、回流除去模板剂得到表面带有氰基官能团的KIT-6介孔材料；(2) Add tetraethyl orthosilicate and 3-cyanopropyl triethoxy silicon (CPTES) into the mixed solution of step (1), and stir evenly, undergo hydrothermal reaction, filter the stock solution after cooling, dry, Reflux to remove template agent to obtain KIT-6 mesoporous material with cyano functional groups on the surface;
(3)将步骤(2)中表面带有氰基官能团的KIT-6介孔材料进行偕胺肟化反应，调节反应溶液的pH值至6-7，反应结束后将溶液过滤、洗涤、真空干燥，即得表面带有偕胺肟基团的介孔材料。(3) Carry out amidoximation reaction to the KIT-6 mesoporous material with cyano functional groups on the surface in step (2), adjust the pH value of the reaction solution to 6-7, filter the solution after the reaction, wash, vacuum After drying, the mesoporous material with amidoxime groups on the surface is obtained.
步骤(1)中，嵌段共聚物EO20PO70EO20与正丁醇的质量比为1:1。In step (1), the mass ratio of block copolymer EO 20 PO 70 EO 20 to n-butanol is 1:1.
步骤(2)中，正硅酸乙酯与3-氰丙基三乙氧基硅的摩尔比为5:1～7:1，嵌段共聚物EO20PO70EO20与正硅酸乙酯的质量比为1:2.085，水热反应温度为100～110℃，反应时间24h。In step (2), the molar ratio of ethyl orthosilicate to 3-cyanopropyl triethoxy silicon is 5:1 to 7:1, and the block copolymer EO 20 PO 70 EO 20 and ethyl orthosilicate The mass ratio is 1:2.085, the hydrothermal reaction temperature is 100-110°C, and the reaction time is 24h.
步骤(3)中，偕胺肟化反应的试剂采用氯化羟胺，表面带有氰基官能团的KIT-6介孔材料与氯化羟胺质量比为1:8。In step (3), the reagent for amidoximation reaction is hydroxylamine chloride, and the mass ratio of the KIT-6 mesoporous material with cyano functional groups on the surface to hydroxylamine chloride is 1:8.
上述表面带有偕胺肟基团的介孔材料在铀离子吸附上的应用，所述的应用中pH为4-5，优选pH为4。The application of the above-mentioned mesoporous material with amidoxime groups on the surface in the adsorption of uranium ions has a pH of 4-5, preferably a pH of 4.
本发明与现有技术相比，其显著优点在于：Compared with the prior art, the present invention has significant advantages in that:
(1)本发明制备的表面带有偕胺肟基团的介孔材料成功的将偕胺肟基团均匀地分布在介孔材料二氧化硅材料表面，介孔材料二氧化硅材料具有大比表面积，可以容纳铀离子；(1) The mesoporous material with amidoxime group on the surface prepared by the present invention successfully distributes the amidoxime group on the surface of the mesoporous material silica material, and the mesoporous material silica material has a large specific Surface area, which can accommodate uranium ions;
(2)表面带有偕胺肟基团的介孔材料保留了介孔材料大的比表面积和孔容，因此可以广泛应用于吸附、分离、催化、信息存储和生物医药等领域。(2) Mesoporous materials with amidoxime groups on the surface retain the large specific surface area and pore volume of mesoporous materials, so they can be widely used in the fields of adsorption, separation, catalysis, information storage, and biomedicine.
附图说明Description of drawings
图1是本发明实施例1中所得表面修饰的KIT-6介孔材料CN-KIT-6-7:1的小角XRD谱图。Figure 1 is the small-angle XRD spectrum of the surface-modified KIT-6 mesoporous material CN-KIT-6-7:1 obtained in Example 1 of the present invention.
图2是本发明实施例1中所得表面修饰的KIT-6介孔材料CN-KIT-6-7:1的孔径分布曲线图(a)和氮气低温吸附-脱附等温线(b)。Fig. 2 is the pore size distribution curve (a) and the nitrogen low-temperature adsorption-desorption isotherm (b) of the surface-modified KIT-6 mesoporous material CN-KIT-6-7:1 obtained in Example 1 of the present invention.
图3是本发明实施例1中所得表面修饰的KIT-6介孔材料CN-KIT-6-7:1的TEM图像(标尺为100nm)。Fig. 3 is a TEM image of the surface-modified KIT-6 mesoporous material CN-KIT-6-7:1 obtained in Example 1 of the present invention (the scale bar is 100 nm).
图4是本发明实施例1中所得表面修饰的KIT-6介孔材料CN-KIT-6-7:1及表面带有偕胺肟基介孔材料AN-KIT-6-7:1的红外光谱图图像。Fig. 4 is the KIT-6 mesoporous material CN-KIT-6-7:1 of surface modification obtained in the embodiment of the present invention 1 and the surface has the infrared of amidoxime-based mesoporous material AN-KIT-6-7:1 Spectrogram image.
图5是本发明实施例2中所得表面修饰的KIT-6介孔材料CN-KIT-6-6:1的孔径分布曲线图(a)和氮气低温吸附-脱附等温线(b)。Fig. 5 is the pore size distribution curve (a) and the nitrogen low-temperature adsorption-desorption isotherm (b) of the KIT-6 mesoporous material CN-KIT-6-6:1 obtained in Example 2 of the present invention.
图6是本发明实施例3中所得表面修饰的KIT-6介孔材料CN-KIT-6-5:1的孔径分布曲线图(a)和氮气低温吸附-脱附等温线(b)。Fig. 6 is the pore size distribution curve (a) and the nitrogen low-temperature adsorption-desorption isotherm (b) of the surface-modified KIT-6 mesoporous material CN-KIT-6-5:1 obtained in Example 3 of the present invention.
图7是本发明实施例3中合成得到表面修饰的KIT-6介孔材料AN-KIT-6-5:1在不同反应时间条件下对铀酰离子的吸附量曲线。Fig. 7 is a graph showing the adsorption amount of uranyl ions of the surface-modified KIT-6 mesoporous material AN-KIT-6-5:1 synthesized in Example 3 of the present invention under different reaction time conditions.
具体实施方式Detailed ways
为了更好地理解本发明，下面通过具体的实施例来具体说明本发明的技术方案。In order to better understand the present invention, the technical solution of the present invention will be specifically described below through specific examples.
实施例1：表面修饰的KIT-6介孔材料的制备Embodiment 1: Preparation of surface-modified KIT-6 mesoporous material
(1)表面修饰的KIT-6介孔材料合成：称取1.00g嵌段共聚物EO20PO70EO20(P123)于烧杯中，量取2mL浓盐酸及36.6mL的去离子水，35℃条件下搅拌，将P123溶解在盐酸溶液中，使其自组装形成介孔结构。待P123完全溶解，溶液完全混合后加入1.00g正丁醇，搅拌1h后向溶液中加入正硅酸乙酯(TEOS)2.085g及有机硅烷化试剂-3-氰丙基三乙氧基硅(CPTES)0.3305g。混合物在35℃下搅拌24h，24h后对混合物质进行水热处理(100℃)24h。水热处理后将混合物过滤，烘干得到白色粉末。此时的白色粉末带有模板剂P123，采用回流的方法去除样品表面模板剂。去除模板剂后的样品烘干，得到表面修饰的KIT-6介孔材料CN-KIT-6-7:1。(1) Synthesis of surface-modified KIT-6 mesoporous material: Weigh 1.00g block copolymer EO 20 PO 70 EO 20 (P 123 ) in a beaker, measure 2mL concentrated hydrochloric acid and 36.6mL deionized water, 35 Stirring at ℃, dissolve P 123 in hydrochloric acid solution to make it self-assemble to form a mesoporous structure. After P123 is completely dissolved and the solution is completely mixed, add 1.00 g of n-butanol, stir for 1 hour, and then add 2.085 g of tetraethyl orthosilicate (TEOS) and organosilylating agent-3-cyanopropyltriethoxysilane ( CPTES) 0.3305g. The mixture was stirred at 35°C for 24h, after 24h the mixture was hydrothermally treated (100°C) for 24h. After hydrothermal treatment, the mixture was filtered and dried to obtain a white powder. At this time, the white powder contains template agent P 123 , and the template agent on the surface of the sample is removed by reflux. After removing the template, the sample was dried to obtain the surface-modified KIT-6 mesoporous material CN-KIT-6-7:1.
(2)材料偕胺肟化过程：偕胺肟化过程中，使用氯化羟胺对表面改性的介孔材料CN-KIT-6进行偕胺肟化，具体为：称量20mL蒸馏水，称量氯化羟胺4.0g，使用无水碳酸钠调节溶液pH值为6，70℃下反应3h。反应结束后将溶液过滤，并用蒸馏水将固体材料表面的无机盐洗涤干净，真空干燥箱60℃干燥12h，得到表面带有偕胺肟基团的介孔材料AN-KIT-6-7:1。(2) Material amidoximation process: In the amidoximation process, the surface-modified mesoporous material CN-KIT-6 is amidoximated using hydroxylamine chloride, specifically: weigh 20 mL of distilled water, weigh Hydroxylamine chloride was 4.0 g, the pH value of the solution was adjusted to 6 with anhydrous sodium carbonate, and the reaction was carried out at 70° C. for 3 h. After the reaction, the solution was filtered, and the inorganic salt on the surface of the solid material was washed with distilled water, and dried in a vacuum oven at 60°C for 12 hours to obtain the mesoporous material AN-KIT-6-7:1 with amidoxime groups on the surface.
图1所示是本实施例的XRD图谱，图中可以分辨出两个衍射峰，对比文献报道，它们可分别归属于具有Ia3d结构的KIT-6材料的(211)，(220)晶面的衍射峰。说明合成材料具有立方相的空间结构。Shown in Fig. 1 is the XRD collection of illustrative plates of the present embodiment, can distinguish two diffraction peaks among the figure, compare bibliographical reports, they can belong to (211) of the KIT-6 material with Ia3d structure respectively, (220) crystal plane Diffraction peaks. It shows that the synthetic material has a cubic phase structure.
图2所示是本实施例的氮气低温吸附-脱附等温线，图中曲线呈现典型的Ⅰ型吸附等温线。在P/P0为0.4～0.7时，有明显的滞后环，说明材料具有均一的介孔结构。其BET比表面积为706.526m2/g，孔容为0.85cm3/g，通过BJH计算得到的孔径分布曲线中最可几孔径为4.55nm。Figure 2 shows the low-temperature adsorption-desorption isotherm of nitrogen in this embodiment, and the curve in the figure presents a typical type I adsorption isotherm. When P/P 0 is 0.4-0.7, there are obvious hysteresis loops, indicating that the material has a uniform mesoporous structure. Its BET specific surface area is 706.526m 2 /g, pore volume is 0.85cm 3 /g, and the most probable pore diameter in the pore size distribution curve calculated by BJH is 4.55nm.
图3是本实施例的TEM图片，从图中可以清楚的看到材料的空间晶面结构，材料分布均匀。Fig. 3 is a TEM picture of this embodiment, from which the spatial crystal plane structure of the material can be clearly seen, and the material is evenly distributed.
图4是本实施例的红外光谱图，从红外光谱图中可以看出表面带有氰基官能团的材料(图中a)在2254cm-1(氰基官能团特征峰为2250～2260cm-1)处有特征峰出现，偕胺肟化后的材料(图中b)2254cm-1处的特征峰消失，且在1640cm-1以及1540cm-1左右的地方出现特征峰。Figure 4 is the infrared spectrogram of this embodiment, from which it can be seen that the material with cyano functional groups on the surface (a in the figure) is at 2254cm -1 (the characteristic peak of the cyano functional group is 2250～2260cm -1 ) A characteristic peak appears, and the characteristic peak at 2254cm -1 of the amidoximated material (b in the figure) disappears, and characteristic peaks appear at around 1640cm -1 and 1540cm -1 .
实施例2：本实施方式的具体实施步骤和实施例1的不同之处在于加入有机硅烷化试剂-3-氰丙基三乙氧基硅(CPTES)质量为0.3856g；其他与实施例1相同。Example 2: The difference between the specific implementation steps of this embodiment and Example 1 is that the quality of adding organosilylating agent-3-cyanopropyl triethoxy silicon (CPTES) is 0.3856g; others are the same as Example 1 .
图5所示是本实施例的氮气低温吸附-脱附等温线，图中曲线呈现典型的Ⅰ型吸附等温线。在P/P0为0.4～0.6时，有明显的滞后环，说明材料具有均一的介孔结构。其BET比表面积为603.163m2/g，孔容为0.60cm3/g，通过BJH计算得到的孔径分布曲线中最可几孔径为3.98nm。Fig. 5 shows the low-temperature adsorption-desorption isotherm of nitrogen in this embodiment, and the curve in the figure presents a typical type I adsorption isotherm. When P/P 0 is 0.4-0.6, there are obvious hysteresis loops, indicating that the material has a uniform mesoporous structure. Its BET specific surface area is 603.163m 2 /g, pore volume is 0.60cm 3 /g, and the most probable pore diameter in the pore size distribution curve calculated by BJH is 3.98nm.
实施例3：本实施方式的具体实施步骤和实施例1的不同之处在于加入有机硅烷化试剂-3-氰丙基三乙氧基硅(CPTES)质量为0.4627g；其他与实施例1相同。Example 3: The difference between the specific implementation steps of this embodiment and Example 1 is that the quality of adding organosilylating agent-3-cyanopropyl triethoxy silicon (CPTES) is 0.4627g; others are the same as Example 1 .
图6所示是本实施例的氮气低温吸附-脱附等温线，图中曲线呈现典型的Ⅰ型吸附等温线。在P/P0为0.4～0.6时，有明显的滞后环，说明材料具有均一的介孔结构。其BET比表面积为484.71m2/g，孔容为0.50cm3/g，通过BJH计算得到的孔径分布曲线中最可几孔径为4.15nm。Figure 6 shows the low-temperature adsorption-desorption isotherm of nitrogen in this embodiment, and the curve in the figure presents a typical type I adsorption isotherm. When P/P 0 is 0.4-0.6, there are obvious hysteresis loops, indicating that the material has a uniform mesoporous structure. Its BET specific surface area is 484.71m 2 /g, pore volume is 0.50cm 3 /g, and the most probable pore diameter in the pore size distribution curve calculated by BJH is 4.15nm.
实施例4：实施例3中合成得到的表面修饰的KIT-6介孔材料AN-KIT-6对铀离子的吸附应用。Example 4: The application of the surface-modified KIT-6 mesoporous material AN-KIT-6 synthesized in Example 3 for the adsorption of uranium ions.
(1)25℃，在250mL的锥形瓶中加入100mL铀离子的浓度为100mg/L的溶液，再向其中加入0.02g的表面修饰的介KIT-6孔材料AN-KIT-6，使用1M NaOH调节混合溶液的pH为4。(1) At 25°C, add 100mL of a uranium ion solution with a concentration of 100mg/L to a 250mL conical flask, and then add 0.02g of surface-modified KIT-6 pore material AN-KIT-6 to it, using 1M NaOH adjusted the pH of the mixed solution to 4.
(2)反应一段时间后过滤，使用UV1801紫外分光光度计测量滤液中铀离子的浓度，加入1mL的0.1％的偶氮胂III显色，使用q＝(C0-Ce)×V/m公式计算材料的吸附量。(2) Filter after reacting for a period of time, use UV1801 ultraviolet spectrophotometer to measure the concentration of uranium ions in the filtrate, add 1 mL of 0.1% arsenazo III to develop color, use q=(C 0 -C e )×V/m The formula calculates the adsorption capacity of the material.
图7是本实施例在不同反应时间条件下对铀离子的吸附量曲线。从图中观察到表面修饰的KIT-6材料AN-KIT-6对铀离子的吸附量随反应时间的增加而增大，其吸附容量为163.53mg/g。Fig. 7 is the curve of the adsorption capacity of uranium ions in this embodiment under different reaction time conditions. It is observed from the figure that the adsorption capacity of the surface-modified KIT-6 material AN-KIT-6 to uranium ions increases with the increase of the reaction time, and its adsorption capacity is 163.53 mg/g.
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