CN108298551A - 一种核-壳-核结构介孔分子筛纳米复合材料的制备方法 - Google Patents
一种核-壳-核结构介孔分子筛纳米复合材料的制备方法 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011258 core-shell material Substances 0.000 title claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
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- 238000007789 sealing Methods 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 16
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- 239000013335 mesoporous material Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 239000002086 nanomaterial Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009416 shuttering Methods 0.000 description 1
- -1 silicic acid radical ion Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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Abstract
本发明公开了一种核‑壳‑核结构介孔分子筛纳米复合材料的制备方法，是通过化学共沉淀法制备锑掺杂二氧化锡(ATO)纳米粒子，以锑掺杂二氧化锡(ATO)纳米粒子为核，采用自组装法通过加入复合模板剂CTMAB和TBAB，在ATO核表面引入一层MCM‑41包覆层制备了ATO/MCM‑41，结合溶胶凝胶法将纳米TiO2再组装入MCM‑41孔道中，合成了ATO/TiO2‑MCM‑41分子筛纳米复合材料，该材料可一体化实现纳米ATO及纳米TiO2的功能，可广泛应用于涂料、光催化、光电等领域，具有较强的应用前景。
Description
技术领域
本发明涉及纳米材料领域，特别涉及一种核-壳-核结构介孔分子筛纳米复合材料的制备方法。
背景技术
自上世纪90年代初介孔材料的成功发现以来，人们一直致力于在此基础上研发新的结构、新型复合材料和具有特殊功能的新材料的尝试与创新，并且在介孔材料主－客体装载复合物的合成方面取得了显著的进步，人们已找到了一些把客体纳米颗粒引入介孔材料中的方法。MCM-41介孔分子筛是在1992年由美国Mobil公司的Beck等人首次报道的，其孔径在1.5-10nm范围内变化，成为分子筛发展的一个重要里程碑。由于MCM-41介孔材料的孔径大且孔分布均匀，具有良好的热稳定性，突破了沸石分子筛孔径长期限于微孔范畴(<1.5nm)的局面。因为MCM-41具有大的孔径以及极性的羟基，为分子筛内表面的修饰及大客体分子组装提供了必备的条件，也为组装化学提供了优良的主体材料。
近年来，由于核壳型异质纳米结构材料具有不同于任何单一物质的性质，在材料化学和纳米技术领域引起了广泛的关注。核壳型异质纳米结构材料可由不同组成功能的材料构成，通过材料复合、互补和优化可以构建更优质的复合功能材料与器件，满足发展的需求。在颗粒表面包覆壳层物质形成核壳结构材料，可以很好地控制粒子之间的相互作用，通过改变包覆物的尺寸、结构以及粒子的组成能够赋予颗粒特殊的功能特性，从而具有更加广泛的潜在应用前景。
纳米锑掺杂二氧化锡(Antimony doped Tin Oxide，ATO)，是一种n型半导体材料，具有优良的导电性、浅色透明性、良好的耐候性、耐高温性、化学稳定性以及低的红外发射率，广泛应用于隔热涂料、建筑用低辐射率玻璃、红外吸收隔热材料、抗静电塑料、防辐射抗静电涂层材料、纤维、电极材料、气敏元件等领域。纳米TiO2是一种白色宽禁带的n型半导体纳米材料，具有较高的光催化氧化能力、特殊的光电性能、化学稳定性、紫外屏蔽能力等优势，广泛应用于光催化、染料敏化太阳能电池、卫生用品杀菌及涂料等领域。以分子筛为壳，形成核-壳-核的纳米双核结构材料在文献中鲜有报道，若将纳米ATO、纳米TiO2与MCM-41相复合将在隔热涂料、光催化、光电等领域具有很强的工业化能力与应用前景。
发明内容
本发明的目的在于克服现有技术中存在的缺点，提供一种核-壳-核结构介孔分子筛纳米复合材料的制备方法，具体是ATO/TiO2-MCM-41分子筛纳米复合材料。该材料可以保持ATO与TiO2两种材料的特性，又使各组分间协同作用，制作工艺简单，成本低，在涂料、光催化、光电等领域具有很强的应用前景。
本发明的目的通过下述技术方案实现：
一种核-壳-核结构介孔分子筛纳米复合材料的制备方法，是采用化学共沉淀法制备纳米锑掺杂二氧化锡(ATO)前驱物；然后以锑掺杂二氧化锡(ATO)纳米粒子为核，加入复合模板剂(CTAB+TBAB)，采用自组装法在ATO核表面引入一层MCM-41包覆层，得到ATO/MCM-41；再采用溶胶凝胶法，将纳米TiO2再组装入MCM-41孔道中，合成了核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料。
具体包括下述步骤：
(1)采用化学共沉淀法制备纳米ATO前驱物：按锑掺杂摩尔浓度为2～10％称取SnCl4·5H2O和SbCl3溶于盐酸溶液中，加入体积浓度为5～30％的氨水至pH＝3～4；将溶液50～80℃恒温水热15～120min，生成浅黄色沉淀；抽滤，用乙醇和去离子水清洗，获得纳米ATO前驱物；
(2)制备ATO/MCM-41粉体：将质量比为(1～5):(50～300)的纳米ATO前驱物加入无水乙醇中，超声分散10～60min；加入10～25wt％的氨水和质量比为(0.5～2):(2～10):(50～300)的四丁基溴化铵(TBAB)、十六烷基三甲基溴化铵(CTMAB)、水，搅拌10-60min；滴加正硅酸乙酯反应3～4h；抽滤，用乙醇和去离子水清洗，烘干，程序升温到450～750℃恒温煅烧2～8h，获得ATO/MCM-41粉体；
(3)配制TiO2溶胶：在无水乙醇中加入二乙醇胺，加入钛酸四丁酯，常温下封口搅拌1～12h；再缓慢滴加去离子水，搅拌1～12h，获得TiO2溶胶；
(4)将ATO/MCM-41粉体加入到TiO2溶胶中，超声分散15～30min；磁力搅拌反应1～12h，静止吸附1～12h；乙醇洗涤，抽滤，烘干；450～750℃煅烧2～8h，得到核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料。
步骤(1)中，所述SnCl4·5H2O和SbCl3的质量比为(30～40):2；所述盐酸溶液浓度为2～3mol/L。
步骤(2)中，所述程序升温的升温速率为1℃/min。
步骤(3)中，无水乙醇、二乙醇胺、钛酸四丁酯、去离子水按体积配比为(100-300):(5-30):5:(1-10)。
步骤(4)中，ATO/MCM-41粉体和TiO2溶胶的配比为1:(30～60)g/ml。
所述核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料，是以纳米ATO为内核，MCM-41为包覆层，在MCM-41孔道中组装有纳米TiO2的核壳结构。
本发明与现有技术相比具有如下优点和效果：
(1)本发明的核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料，实验设备及工艺方法简单，经济成本低。
(2)通过MCM-41分子筛为壳层，将纳米ATO和纳米TiO2两种纳米粒子共组装，可一体化实现纳米ATO及纳米TiO2的功能，发挥其协同作用，在隔热涂料、光催化、光电等领域具有应用前景。
附图说明
图1是核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的透射电子显微镜图。
图2是核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的XRD图谱。
图3是核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的XRD小角-射线衍射图。
图4是核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的EDS图谱。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
实施例1
称量33g SnCl4·5H2O及2g SbCl3溶于2mol/L盐酸溶液中，加入体积浓度为10％的氨水至pH＝3；将溶液60℃恒温水热30min，至生成浅黄色沉淀；抽滤，用乙醇和去离子水清洗10次，得到黄色沉淀的纳米ATO前驱物。
将1g纳米ATO前驱物加入100mL无水乙醇，超声分散30min；加入9mL的氨水(25wt％)，将0.6125g TBAB溶解于10mL去离子水中，2.7698g CTMAB溶解于50mL去离子水中加入溶液搅拌30min；滴加11mL正硅酸乙酯，反应3h；反应物摩尔比为CTMAB：TEOS：NH3：H2O：TBAB＝0.152：1：2.8：141.2：0.038；抽滤，用乙醇和去离子水清洗，烘干，程序升温(升温速率为1℃/min)到550℃恒温煅烧4h，获得ATO/MCM-41粉体。
在75mL无水乙醇中加入5mL二乙醇胺，滴加2.5mL钛酸四丁酯，常温下封口搅拌1小时；再缓慢滴加1mL去离子水，搅拌1h获得TiO2溶胶。将制得的ATO/MCM-41粉体加入到上述TiO2溶胶中，超声分散15～30min；磁力搅拌反应1h，静止吸附6h；乙醇洗涤3次，抽滤，80℃烘干12h，取出放入马弗炉550℃煅烧4h，得到核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料。
图1是核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的透射电子显微镜图。从图1中可以看出，样品均为球型核壳结构，核内为晶相的ATO纳米粒子，MCM-41包覆层可以直观的观测到有序介孔孔道的存在，厚度约为20nm。图中观察不到孔道表面出现TiO2粒子析出或富集的区域，说明经过浸渍吸附及后续热处理的工艺，纳米TiO2可以均匀分散在有序介孔氧化硅的孔道中。
图2为核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的XRD图。如图2所示，出现了SnO2的(110)，(101)，(200)，(211)，(220)，(310)，(301)等晶面的多重衍射峰,，其衍射数据与JCPDS(21～1250)标准卡片相符,为金红石结构结构的SnO2。未见氧化锑的衍射峰出现，表明锑已完全掺杂进入到SnO2晶格中；且在2θ≈26.5o处出现金红石TiO2(101)晶面特征衍射峰，与SnO2的(110)晶面的特征衍射峰叠加。
图3是ATO/TiO2-MCM-41的XRD小角-射线衍射图。从图3中可以看出，在2.35°有一个较强的衍射峰，为MCM-41结构(100)晶面特征峰，是具有六方结构介孔相材料的最主要特征峰。该特征峰的存在，表明了无机硅酸根离子与表面活性剂离子通过自组装方式生成了呈周期性排列的液晶织态结构，证实所合成样品壳层中的无机骨架形成了具有MCM-41特征的六方介孔结构。
图4为核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料的EDS图谱。从图4中我们可以清楚的看出Sn、Sb、Si、O和Ti元素存在，进一步证明了ATO、SiO2及TiO2层的存在。
Claims (6)
1.一种核-壳-核结构介孔分子筛纳米复合材料的制备方法，其特征在于：
(1)采用化学共沉淀法制备纳米ATO前驱物：按锑掺杂摩尔浓度为2～10％称取SnCl4·5H2O和SbCl3溶于盐酸溶液中，加入体积浓度为5～30％的氨水至pH＝3～4；将溶液50～80℃恒温水热15～120min，生成浅黄色沉淀；抽滤，用乙醇和去离子水清洗，获得纳米ATO前驱物；
(2)制备ATO/MCM-41粉体：将质量比为(1～5):(50～300)的纳米ATO前驱物加入无水乙醇中，超声分散10～60min；加入10～25wt％的氨水和质量比为(0.5～2):(2～10):(50～300)的四丁基溴化铵(TBAB)、十六烷基三甲基溴化铵(CTMAB)、水，搅拌10-60min；滴加正硅酸乙酯反应3～4h；抽滤，用乙醇和去离子水清洗，烘干，程序升温到450～750℃恒温煅烧2～8h，获得ATO/MCM-41粉体；
(3)配制TiO2溶胶：在无水乙醇中加入二乙醇胺，加入钛酸四丁酯，常温下封口搅拌1～12h；再缓慢滴加去离子水，搅拌1～12h，获得TiO2溶胶；
(4)将ATO/MCM-41粉体加入到TiO2溶胶中，超声分散15～30min；磁力搅拌反应1～12h，静止吸附1～12h；乙醇洗涤，抽滤，烘干；450～750℃煅烧2～8h，得到核-壳-核结构介孔分子筛纳米复合材料，即核壳结构ATO/TiO2-MCM-41分子筛纳米复合材料。
2.根据权利要求1所述的核-壳-核结构介孔分子筛纳米复合材料的制备方法，其特征在于：步骤(1)中，所述SnCl4·5H2O和SbCl3的质量比为(30～40):2；所述盐酸溶液浓度为2～3mol/L。
3.根据权利要求1所述的核-壳-核结构介孔分子筛纳米复合材料的制备方法，其特征在于：步骤(2)中，所述程序升温的升温速率为1℃/min。
4.根据权利要求1所述的核-壳-核结构介孔分子筛纳米复合材料的制备方法，其特征在于：步骤(3)中，无水乙醇、二乙醇胺、钛酸四丁酯、去离子水按体积配比为(100-300):(5-30):5:(1-10)。
5.根据权利要求1所述的核-壳-核结构介孔分子筛纳米复合材料的制备方法，其特征在于：步骤(4)中，ATO/MCM-41粉体和TiO2溶胶的配比为1:(30～60)g/ml。
6.一种核-壳-核结构介孔分子筛纳米复合材料，其特征在于：采用权利要求1～5中任一项所述的方法制备得到，是以纳米ATO为内核，MCM-41为包覆层，在MCM-41孔道中组装有纳米TiO2的核壳结构。
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