二维层状材料麦羟硅钠石的研究进展
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摘要
二维层状材料硅酸盐是硅、氧与其他化学元素等结合而成的化合物的总称。其以硅氧四面体为基本结构,根据不同的配合形成了各类的硅酸盐,其种类繁多、熔点高、比表面积大、抗蠕变性良好以及可插层,且具有优异的耐腐蚀性、热稳定性和化学稳定性,被广泛应用于化工、建材、耐火材料、陶瓷、造纸、橡胶、塑料、医药、农药、纺织、化妆品、国防和环保等领域。麦羟硅钠石是一种水合硅钠石,它属于层状硅酸盐,结构式为Na_2Si_(14)O_(29)·n H_2O,作为一种新型的层状硅酸盐材料,相比于蒙脱石等其他层状硅酸盐,它的活性Si-OH位于层间的表面上,有利于其功能化改性,且显著提高了层间电荷密度,从而提高了其离子交换能力。麦羟硅钠石具有规整的层板结构和可调控的层间距,可以在层间引入不同功能的分子,作为组装多功能复合材料的基础材料。麦羟硅钠石是纯硅体系,具有很好的生物相容性,单个片层较厚(1.12 nm),结构稳定性好,可以人工合成,通过控制合成工艺,可以得到高纯度的产物,且价格低廉,具有市场竞争优势。到目前为止,麦羟硅钠石的制备主要是通过水热法人工合成,硅源可以为硅藻土、水玻璃、沉淀白炭黑浆料(PPS)、SiO_2-NaOH-Na_2CO_3-H_2O体系、硅胶、正硅酸甲酯、正硅酸乙酯等。随着研究的不断深入,制备方法越来越简单,晶型也越来越完善。麦羟硅钠石的改性研究包括有机插层改性、酸化处理和无机改性。此外,由于聚合物/层状硅酸盐复合材料具有常规聚合物复合材料所没有的结构、形态,以及较常规聚合物复合材料更优异的力学性能、耐热性和气体液体阻隔性能等,麦羟硅钠石/聚合物复合材料也得到了广泛的研究。在应用方面,麦羟硅钠石由于具有较高的离子交换量和较大的比表面积,可以作为吸附材料吸附重金属离子和有机染料等。因其层状结构和较大的比表面积,麦羟硅钠石可以作为硅源合成沸石分子筛,其具有较高的水热稳定性和一定的耐酸性。麦羟硅钠石由于化学稳定性及较强的负载能力,可以有效负载催化材料,并使催化材料获得很好的分散效果,增强其催化性能。为反映当今国内外麦羟硅钠石的研究成果,本文介绍了麦羟硅钠石的结构与性质、制备、改性以及应用等内容。但是目前对于麦羟硅钠石的研究还不够成熟,存在一定的局限性。若将来麦羟硅钠石能够在生产实践中得到应用,其前景将十分广阔。
The two-dimensional layered silicate is a general name of a compound in which silicon,oxygen and other chemical elements are combined.Based on the basic structure of silicon-oxy tetrahedron,diverse silicates are formed according to various combinations. Silicate shows a wide variety,high melting point,large specific surface area,favorable creep resistance,easy for intercalation,and excellent corrosion resistance,thermal stability,chemical stability,which enable its wide application in chemical,building materials,refractories,ceramics,paper,rubber,polymer,plastics,pharmaceuticals,pesticides,textiles,cosmetics,defense and environmental protection industry.Magadiite is a kind of sodium silicate hydrate,which belongs to layered silicate with the structural formula of Na_2Si_(14)O_(29)·n H_2O. As a novel layered silicate material,magadiite features its active Si-OH located on the interlayers surface,which is more conducive to the functional modification compared with other layered silicate like montmorillonite. In addition,it will significantly increase the interlayer charge density,thus contribute to its ion exchange capacity. Thanks to its regular laminar structure and adjustable interlayer spacing,magadiite can be used as a basic material for the assembly of multifunctional composites by introducing various functional molecules. Magadiite exhibits competitive advantages in market,owing to its favorable biocompatibility,stable structure,thicker monolayer( 1.12 nm),moderate price,and the capability for artificial synthesis and generating high purity products with a controlled process.Up to now,the primary preparation method of magadiite is hydro-thermal synthesis,the possible silicon source include diatomaceous earth,water glass,precipitated silica slurry( PPS),SiO_2-NaOH-Na_2CO_3-H_2O system,silica gel,methyl orthosilicate,tetraethylorthosilicate and so forth. The continuous progress of research has brought about more simplified preparation methods and more perfect crystal structure of products.The modification of magadiite includes organic intercalation,acidification treatment and inorganic modification. Besides,magadiite/polymer composites have also received extensively studied because of the unique structure and morphology of polymer/layered silicate composites differed from conventional polymer composites,and superior mechanical properties,heat resistance,gas-liquid barrier. With regard to the application of magadiite,it can be employed as adsorption material to adsorb heavy metal ions and organic dyes because of its higher ion exchange capacity and large specific surface area. Moreover,due to its layered structure and large specific surface area,magadiite can be used as a silicon source for the synthesis of zeolite molecular sieves,which show high hydrothermal stability and acid resistance. In addition,magadiite possesses excellent chemical stability and strong load capacity,which enable it support catalyst effectively and make the catalyst well dispersed so as to increase the catalytic performance.In order to present the current research of magadiite at home and abroad,this article introduces the structure and properties,preparation,modification and application of magadiite. While,the current researches on magadiite are not mature enough and exist certain limitations. It is believed that the magadiite own a broad prospect,if it can be applied in production practice in the future.
The two-dimensional layered silicate is a general name of a compound in which silicon,oxygen and other chemical elements are combined.Based on the basic structure of silicon-oxy tetrahedron,diverse silicates are formed according to various combinations. Silicate shows a wide variety,high melting point,large specific surface area,favorable creep resistance,easy for intercalation,and excellent corrosion resistance,thermal stability,chemical stability,which enable its wide application in chemical,building materials,refractories,ceramics,paper,rubber,polymer,plastics,pharmaceuticals,pesticides,textiles,cosmetics,defense and environmental protection industry.Magadiite is a kind of sodium silicate hydrate,which belongs to layered silicate with the structural formula of Na_2Si_(14)O_(29)·n H_2O. As a novel layered silicate material,magadiite features its active Si-OH located on the interlayers surface,which is more conducive to the functional modification compared with other layered silicate like montmorillonite. In addition,it will significantly increase the interlayer charge density,thus contribute to its ion exchange capacity. Thanks to its regular laminar structure and adjustable interlayer spacing,magadiite can be used as a basic material for the assembly of multifunctional composites by introducing various functional molecules. Magadiite exhibits competitive advantages in market,owing to its favorable biocompatibility,stable structure,thicker monolayer( 1.12 nm),moderate price,and the capability for artificial synthesis and generating high purity products with a controlled process.Up to now,the primary preparation method of magadiite is hydro-thermal synthesis,the possible silicon source include diatomaceous earth,water glass,precipitated silica slurry( PPS),SiO_2-NaOH-Na_2CO_3-H_2O system,silica gel,methyl orthosilicate,tetraethylorthosilicate and so forth. The continuous progress of research has brought about more simplified preparation methods and more perfect crystal structure of products.The modification of magadiite includes organic intercalation,acidification treatment and inorganic modification. Besides,magadiite/polymer composites have also received extensively studied because of the unique structure and morphology of polymer/layered silicate composites differed from conventional polymer composites,and superior mechanical properties,heat resistance,gas-liquid barrier. With regard to the application of magadiite,it can be employed as adsorption material to adsorb heavy metal ions and organic dyes because of its higher ion exchange capacity and large specific surface area. Moreover,due to its layered structure and large specific surface area,magadiite can be used as a silicon source for the synthesis of zeolite molecular sieves,which show high hydrothermal stability and acid resistance. In addition,magadiite possesses excellent chemical stability and strong load capacity,which enable it support catalyst effectively and make the catalyst well dispersed so as to increase the catalytic performance.In order to present the current research of magadiite at home and abroad,this article introduces the structure and properties,preparation,modification and application of magadiite. While,the current researches on magadiite are not mature enough and exist certain limitations. It is believed that the magadiite own a broad prospect,if it can be applied in production practice in the future.
引文
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20 Ozawa K, Iso F, NakaoY, et al. Journal of the European Ceramic Society,2007,27,2665.
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37 Sun X, King J, Anthony L J. Chemical Engineering Journal,2009,147,2.
38 Cui M, Zhang Y, Liu X. Microporous and Mesoporous Materials,2014,200,86.
39 Wang Y, Lyu T, Ma Y. Microporous and Mesoporous Materials,2016,228,86
40 Shi Z, Wang Y, Meng C. Microporous and Mesoporous Materials,2013,176,155.
41 Wang Y, Lyu T, Wang H. Microporous and Mesoporous Materials,2015,208,66.
42 Takahashi N, Kuroda K. Chemistry of Materials,2011,21,14336.
43 Kim S J, Lee G, Ryu Y K. Research on Chemical Intermediates,2012,38,1191.
44 Chen Y, Yu G. Clays and Clay Minerals,2013,48,739.
45 Chen Y, Yu G, Li F. Applied Clay Science,2014,88,163.
46 Chen Y, Yu G, Li F. Clays and Clay Minerals,2013.61,26.
47 Lagaly G, Beneke K. American Mineralogist,1975,60,642.
48 Wang Y, Shang Y S, Zhu J, et al. Journal of Chemical Technology and Biotechnology,2009,84,1894.
49 Wang Y R, Wang S F, Chang L C. Applied Clay Science,2006,33(1),73.
50 Kwon O Y, Park K W. Bulletin of the Korean Chemical Society,2004,25(1),25.
51 Kwon O Y, Jeong S Y, Suh J K, et al. Bulletin of the Korean Chemical Society,1995,16(8),737.
52 Kosuge K, Yamazaki A, Tsunashima A, et al. Bulletin of the Chemical Society of Japan,1992,100,326.
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55 Macedo T R, Airoldi C. Microporous and Mesoporous Materials,2006,94,81.
56 Kooli F, Liu Y. Physical Chemistry Chemical Physics,2009,113,1947.
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