CN100361900C - Porous manganese oxide nanosheet material and preparation method thereof - Google Patents
Porous manganese oxide nanosheet material and preparation method thereof Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002135 nanosheet Substances 0.000 title description 8
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract 4
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims abstract 3
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims abstract 3
- 235000010703 Modiola caroliniana Nutrition 0.000 claims abstract 3
- 244000038561 Modiola caroliniana Species 0.000 claims abstract 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 11
- 239000002060 nanoflake Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 abstract 4
- 239000000499 gel Substances 0.000 abstract 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
Description
一、技术领域：1. Technical field:
本发明是一种纳米薄片材料及其制备方法，尤其是一种多孔氧化锰纳米薄片材料及其制备方法。The invention relates to a nano-sheet material and a preparation method thereof, in particular to a porous manganese oxide nano-sheet material and a preparation method thereof.
二、背景技术2. Background technology
多孔氧化锰按孔径的大小分为微孔氧化锰(孔径≤2纳米)、介孔氧化锰(孔径在2～50纳米)和大孔氧化锰(孔径≥50纳米)。合成方法主要为模板法。按模板的种类分为：(1)离子模板，用于合成微孔氧化锰[Y.Chabre and J.Pannetier，Prog.Solid State Chem.，1995，23，1.]。即锰氧八面体围绕模板离子构筑成一定尺度大小的孔道，孔道的结构和大小依赖于模板离子。模板离子又成为微孔氧化锰的组分而保留在孔道中。产物的合成通过水热方法。(2)表面活性剂模板，用于合成介孔氧化锰[Z.Tian，W.Tong，J.Wang，N.Duan，V.V.Krishnan，S.L.Suib，Science，1997，276，926.；J.Luo，S.L.Suib，Chem.Commun.，1997，1031.]。锰的氧化物微粒按表面活性剂所形成的胶束形状构筑。当氧化锰颗粒所构筑的结构稳定以后，除去表面活性剂，得到介孔氧化锰。产物的合成通过水热方法或乙醇还原法。(3)胶体晶体模板，用于合成大孔氧化锰[H.Yan，C.F.Blanford，B.T.Holland，W.H.Smyrl，A.Stein，Chem.Mater.，2000，12，1134.]。可溶性锰盐溶液填充在胶体晶体的空隙中，蒸发溶剂使锰盐留在空隙中，适当温度处理使锰盐在胶体晶体模板中转变为氧化物。当氧化锰颗粒所构筑的结构稳定以后，除去胶体晶体，得到大孔氧化锰。产物的合成通过溶胶——凝胶方法。另一种合成介孔氧化锰的方法为水解法[A.D.Zarlaha，P.G.Routsoukos，C.Skordilis，P.J.Pomonis，J.Colloid Interface Sci.，1998，202，301；C.E.Salmas，V.N.Stathopoulos，P.J.Pomonis，G.P.Androutsopoulos，Langmuir，2002，18，423.]，即在一定条件下水解[Mn3(CH3COO)6(Pyr)3]ClO4化合物，形成由颗粒堆积而成的介孔氧化锰。Porous manganese oxide is divided into microporous manganese oxide (pore diameter ≤ 2 nanometers), mesoporous manganese oxide (pore diameter 2-50 nanometers) and macroporous manganese oxide (pore diameter ≥ 50 nanometers) according to the pore size. The synthesis method is mainly the template method. According to the type of template, it is divided into: (1) ion template, which is used to synthesize microporous manganese oxide [Y.Chabre and J.Pannetier, Prog.Solid State Chem., 1995, 23, 1.]. That is, the manganese-oxygen octahedron builds pores of a certain scale around the template ions, and the structure and size of the pores depend on the template ions. Template ions become components of microporous manganese oxide and remain in the pores. The synthesis of the product is via a hydrothermal method. (2) Surfactant template for the synthesis of mesoporous manganese oxide [Z.Tian, W.Tong, J.Wang, N.Duan, VVKrishnan, SLSuib, Science, 1997, 276, 926.; J.Luo, SLSuib , Chem. Commun., 1997, 1031.]. Manganese oxide particles are structured in the form of micelles formed by surfactants. After the structure constructed by manganese oxide particles is stable, the surfactant is removed to obtain mesoporous manganese oxide. The products were synthesized by hydrothermal method or ethanol reduction method. (3) Colloidal crystal template for the synthesis of macroporous manganese oxide [H. Yan, CF Blanford, BTHolland, WHSmyrl, A. Stein, Chem. Mater., 2000, 12, 1134.]. The soluble manganese salt solution is filled in the gaps of the colloidal crystals, the solvent is evaporated to leave the manganese salts in the gaps, and the manganese salts are converted into oxides in the colloidal crystal template by proper temperature treatment. When the structure constructed by manganese oxide particles is stable, the colloidal crystals are removed to obtain macroporous manganese oxide. The product was synthesized by a sol-gel method. Another method for synthesizing mesoporous manganese oxide is hydrolysis [ADZarlaha, PGRoutsoukos, C.Skordilis, PJPomonis, J.Colloid Interface Sci., 1998,202,301; CESalmas, VNSathopoulos, PJPomonis, GPAndroutsopoulos, Langmuir, 2002,18 , 423.], that is to hydrolyze [Mn 3 (CH 3 COO) 6 (Pyr) 3 ]ClO 4 compound under certain conditions to form mesoporous manganese oxide formed by particle accumulation.
其中，微孔氧化锰的孔道较小，在应用上受到一定的限制。介孔氧化锰的合成在技术上难度较大。胶体晶体模板的制备工艺过程复杂，技术难度较高，限制了大孔氧化锰的合成。对介孔和大孔氧化锰来说，需要在合成方法和手段上有所突破，才能获得可观量的样品。而且，所述介孔和大孔氧化锰分别为粉状和块状，难以进一步加工成纳米薄片材料，使其应用范围受到限制。Among them, the pores of microporous manganese oxide are small, which is limited in application. The synthesis of mesoporous manganese oxide is technically difficult. The preparation process of colloidal crystal template is complex and technically difficult, which limits the synthesis of macroporous manganese oxide. For mesoporous and macroporous manganese oxide, breakthroughs in synthesis methods and means are needed to obtain considerable samples. Moreover, the mesoporous and macroporous manganese oxides are in the form of powder and block respectively, and it is difficult to be further processed into nano-sheet materials, so that the scope of application is limited.
三、发明内容3. Contents of the invention
1、技术问题1. Technical issues
本发明的目的旨在提供一种制备方法简单、结晶程度高、孔道尺度大小可调的多孔氧化锰纳米薄片材料及其制备方法。The object of the present invention is to provide a porous manganese oxide nanosheet material with simple preparation method, high crystallization degree and adjustable pore size and its preparation method.
2、技术方案2. Technical solution
将等摩尔量的高锰酸钾KMnO4和季铵盐分别用溶液溶解，再将两溶液混合，生成紫红色的凝胶；过滤，洗涤，室温干燥，得到层状结构高锰酸季铵盐；将该物质进行热处理，得到纳米级薄片状的多孔氧化锰。其中，不同温度处理可以得到不同结构的纳米薄片多孔氧化锰。在300～400℃处理，得到厚度为13±2纳米、平均孔径4.0～7.0纳米的多孔氧化锰纳米薄片，相结构分别为Mn3O4(300℃处理)，Mn3O4和Mn5O8(400℃处理)。在处理温度为550～800℃时，得到厚度约为70±10纳米、平均孔径约为20～50纳米的多孔氧化锰纳米薄片，相结构均为Mn2O3。Dissolve equimolar amounts of potassium permanganate KMnO 4 and quaternary ammonium salt in solution respectively, and then mix the two solutions to form a purple-red gel; filter, wash, and dry at room temperature to obtain a layered structure of quaternary ammonium permanganate ; The substance is heat-treated to obtain nanoscale flake-like porous manganese oxide. Wherein, different temperature treatments can obtain nano-sheet porous manganese oxide with different structures. Treated at 300-400°C, porous manganese oxide nanoflakes with a thickness of 13±2 nm and an average pore diameter of 4.0-7.0 nm were obtained, and the phase structures were Mn 3 O 4 (treated at 300°C), Mn 3 O 4 and Mn 5 O 8 (400°C treatment). When the treatment temperature is 550-800° C., porous manganese oxide nanosheets with a thickness of about 70±10 nanometers and an average pore diameter of about 20-50 nanometers are obtained, and the phase structure is all Mn 2 O 3 .
其中，季铵盐可以使用八～十八烷基三甲基溴化铵，尤其是十六烷基三甲基溴化铵，其来源广、成本低；高锰酸钾和季铵盐的溶液可以是常用的水溶液，也可以是其它溶液(两者所使用的溶剂可为同一溶剂，或相互互溶溶剂，或部分互溶溶剂，这些溶剂只能溶解反应物，不能与反应物和产物发生反应)，浓度不限。室温干燥过程可以是在自然状态下风干，也可以是在真空条件下干燥。真空干燥的目的是加快干燥速度。热处理过程可以使用普通的加热炉(箱式炉，管式炉等)。Among them, the quaternary ammonium salt can use octadecyltrimethylammonium bromide, especially hexadecyltrimethylammonium bromide, which has wide sources and low cost; the solution of potassium permanganate and quaternary ammonium salt It can be a commonly used aqueous solution or other solutions (the solvent used for both can be the same solvent, or a mutual miscible solvent, or a partially miscible solvent, these solvents can only dissolve the reactants, and cannot react with the reactants and products) , the concentration is not limited. The room temperature drying process can be air-dried in a natural state, or dried under vacuum conditions. The purpose of vacuum drying is to speed up drying. Common heating furnaces (box furnaces, tube furnaces, etc.) can be used for the heat treatment process.
3、有益效果3. Beneficial effects
本发明的优点是(1)制备方法和手段上简单、可操作性强、易于推广。(2)所得材料为二维多孔纳米薄片材料。(3)结晶程度可调。(4)孔道尺度大小可调。The invention has the advantages of (1) simple preparation method and means, strong operability and easy popularization. (2) The obtained material is a two-dimensional porous nano sheet material. (3) The degree of crystallization is adjustable. (4) The size of the channel is adjustable.
四、附图说明4. Description of drawings
图1 300℃处理5小时的样品扫描电镜照片，薄片厚度为13纳米。Figure 1 Scanning electron micrograph of the sample treated at 300°C for 5 hours, the thickness of the flake is 13 nm.
图2 300℃处理5小时的样品透射电镜照片，平均孔径为4.0纳米。Fig. 2 Transmission electron micrographs of samples treated at 300°C for 5 hours, with an average pore size of 4.0 nm.
图3 400℃处理5小时的样品透射电镜照片，平均孔径为6.5纳米。Figure 3 TEM photograph of the sample treated at 400°C for 5 hours, with an average pore size of 6.5 nm.
图4 550℃处理5小时的样品扫描电镜照片，平均孔径为21.1纳米。Fig. 4 Scanning electron micrographs of samples treated at 550°C for 5 hours, with an average pore size of 21.1 nm.
图5 800℃处理5小时的样品扫描电镜照片，平均孔径为50.7纳米。Fig. 5 Scanning electron micrographs of samples treated at 800°C for 5 hours, with an average pore size of 50.7 nm.
图6 不同温度处理后样品的X-射线衍射图(图中数字对应处理温度)。Figure 6 X-ray diffraction patterns of samples after different temperature treatments (the numbers in the figure correspond to the treatment temperatures).
五、具体实施方式5. Specific implementation
实施例1Example 1
将等摩尔量的高锰酸钾与十六烷基三甲基溴化铵(季铵盐中的一种)分别配制成0.4摩尔/升的水溶液，再将两者混合使其反应，得到十六烷基三甲基高锰酸铵。该物质为层状结构，层间距为23.86纳米。元素分析其化学计量式为C19H41NMnO4，理论值为C19H42NMnO4。Potassium permanganate and hexadecyltrimethylammonium bromide (one of the quaternary ammonium salts) in equimolar amounts are prepared into 0.4 mol/liter aqueous solution respectively, and then the two are mixed and allowed to react to obtain ten Hexaalkyltrimethylammonium permanganate. The substance has a layered structure with a layer spacing of 23.86 nm. The stoichiometric formula of elemental analysis is C 19 H 41 NMnO 4 , and the theoretical value is C 19 H 42 NMnO 4 .
将所得十六烷基三甲基高锰酸铵在300℃处理5小时，使其自发反应发生膨化，得到平均孔径为4.0纳米，厚度为13±2纳米的多孔氧化锰薄片材料。比表面积为45.93m2/g。锰的平均氧化数为2.69。相结构为Mn3O4。Treat the obtained hexadecyltrimethylammonium permanganate at 300° C. for 5 hours to make it spontaneously react and expand to obtain a porous manganese oxide sheet material with an average pore diameter of 4.0 nanometers and a thickness of 13±2 nanometers. The specific surface area is 45.93m 2 /g. The average oxidation number of manganese is 2.69. The phase structure is Mn 3 O 4 .
实施例2Example 2
样品制备过程同实施例1。The sample preparation process is the same as in Example 1.
将所得十六烷基三甲基高锰酸铵在400℃处理5小时，使其自发反应发生膨化，得到平均孔径为6.5纳米，厚度为13±2纳米的多孔氧化锰薄片材料。比表面积为21.11m2/g。锰的平均氧化数为2.85。相结构为Mn3O4(主物相)和Mn5O8(次物相)。Treat the obtained hexadecyltrimethylammonium permanganate at 400° C. for 5 hours to make it spontaneously react and expand to obtain a porous manganese oxide sheet material with an average pore diameter of 6.5 nanometers and a thickness of 13±2 nanometers. The specific surface area is 21.11m 2 /g. The average oxidation number of manganese is 2.85. The phase structure is Mn 3 O 4 (main phase) and Mn 5 O 8 (secondary phase).
实施例3Example 3
样品制备过程同实施例1。The sample preparation process is the same as in Example 1.
将所得十六烷基三甲基高锰酸铵在550℃处理5小时，使其自发反应发生膨化，得到平均孔径为21.1纳米，厚度为70±10纳米的多孔氧化锰薄片材料。比表面积为8.31m2/g。锰的平均氧化数为3.00。相结构为Mn2O3。Treat the obtained hexadecyltrimethylammonium permanganate at 550° C. for 5 hours to make it spontaneously react and expand to obtain a porous manganese oxide sheet material with an average pore diameter of 21.1 nanometers and a thickness of 70±10 nanometers. The specific surface area is 8.31m 2 /g. The average oxidation number of manganese is 3.00. The phase structure is Mn 2 O 3 .
实施例4Example 4
样品制备过程同实施例1。The sample preparation process is the same as in Example 1.
将所得十六烷基三甲基高锰酸铵在800℃处理5小时，使其自发反应发生膨化，得到平均孔径为50.7纳米，厚度为70±10纳米的多孔氧化锰薄片材料。比表面积为4.56m2/g。锰的平均氧化数为3.00。相结构为Mn2O3。Treat the obtained hexadecyltrimethylammonium permanganate at 800° C. for 5 hours to make it spontaneously react and expand to obtain a porous manganese oxide sheet material with an average pore diameter of 50.7 nanometers and a thickness of 70±10 nanometers. The specific surface area is 4.56m 2 /g. The average oxidation number of manganese is 3.00. The phase structure is Mn 2 O 3 .
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| US3627694A (en) * | 1963-09-27 | 1971-12-14 | Gen Aniline & Film Corp | Production of aqueous suspension of manganese dioxide |
| FR2659075A1 (en) * | 1990-03-01 | 1991-09-06 | France Etat Armement | PROCESS FOR PREPARING MANGANESE OXIDES BY SOL-GEL ROUTE. |
| EP0710624A1 (en) * | 1994-11-07 | 1996-05-08 | Texaco Development Corporation | Sol-gel synthesis of manganese oxide material possessing octahedral structure |
| US6503476B1 (en) * | 1999-07-23 | 2003-01-07 | The University Of Connecticut | Manganese oxide helices, rings, strands, and films, and methods for their preparation |
-
2003
- 2003-05-01 CN CNB031133886A patent/CN100361900C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3627694A (en) * | 1963-09-27 | 1971-12-14 | Gen Aniline & Film Corp | Production of aqueous suspension of manganese dioxide |
| FR2659075A1 (en) * | 1990-03-01 | 1991-09-06 | France Etat Armement | PROCESS FOR PREPARING MANGANESE OXIDES BY SOL-GEL ROUTE. |
| EP0710624A1 (en) * | 1994-11-07 | 1996-05-08 | Texaco Development Corporation | Sol-gel synthesis of manganese oxide material possessing octahedral structure |
| US6503476B1 (en) * | 1999-07-23 | 2003-01-07 | The University Of Connecticut | Manganese oxide helices, rings, strands, and films, and methods for their preparation |
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