以K_4Nb_6O_（17）为前驱体合成插层化合物的研究
|
摘要
本文主要研究的内容是：以分析纯Nb205和K2C03为原料,经过仔细研磨,将其放入铂坩埚中,采用高温固相反应制备K4Nb6O17,制备出的K4Nb6O17具有层状结构。向K4Nb6O17层间插入一些过渡金属氢氧化物、氧化物,制备出具有一定功能性的层状化合物,旨在研究以K4Nb6O17为前躯体插层化合物的合成方法,以及合成插层化合物的最佳反应条件。
系统研究了原料K4Nb6O17的合成、质子交换反应、胺剥层反应以及过渡金属的插层反应,并得出各步反应的最佳反应条件。
以铌酸钾为前驱体,通过水热合成的方法合成了镍铌氧插层化合物,其化学式为[Ni(OH)0.68]1.55K1.95Nb6O17·5.82H20,此化合物为单晶格化合物,正交晶系,晶胞参数为a=0.3442 nm,b=1.0943 nm,c=0.4341 nm,α=β=γ=90°。
以铌酸钾为前驱体,通过水热合成的方法合成了铜铌氧插层化合物,其化学式为[Cu(OH)0.66]1.53K1.95Nb6O17·8.31H2O,此化合物为单晶格化合物,正交晶系,晶胞参数为a=0.5251 nm,b=1.0707 nm,c=0.6302 nml,α=β=γ=90°。
所得的插层化合物采用一系列的测试手段,并对这些测试的数据进行分析,最后得出插层化合物的结构特点及其性质。
Nowadays, growing attention has been paid to the issue of energy. People are exploiting plenty of energies such as coal mining, oil, natural gas, etc. These energy sources will be exhausted in the near future. Thus finding new energy sources is the important task now. It can produce much energy when hydrogen is burned, and the water which is no hurt to the environment is the final product. So hydrogen is considered as the green energy source and become the best energy source. However, how to produce hydrogen conveniently is still a great challenge at present. Many scientists are trying to explore a variety of highly efficient catalysts. They hope to split the water into hydrogen and oxygen with solar energy by using these catalysts. The layered compounds caused more attentions of the scientists due to the interesting structures. Some compositions can be intercalated into the interlayered spaces of the layered compounds with some special methods, by which the width of the forbidden band is changed to nearly 1.23 ev, and these compounds can be used as the catalysts in the water spitting with visible light.
In the layered compounds, niobium oxides and titanium oxides are paid more attentions by many researchers. K4Nb6O17 is a two-dimensional layered material built with NbO6 octahedrons. The lattice parameters of K4Nb5O17 are:a=0.783 nm, b= 3.321 nm, c=0.646 nm. In this thesis, by using K4Nb6O17 as the precursor, through ion-exchange, exfoliation, intercalation, etc, some intercalation compounds have been synthesized. The synthesis conditions of the compounds have been investigated, and the characterization of the compounds have been produced.
The layered compound NiNbO has been hydrothermally synthesized with K4Nb6O17 as a precursor. Its chemical formula is [Ni(OH)o.68]1.55K1.95Nb6O17·5.82H2O. This compound is orthogonal, and the lattice parameters are:a=0.3442 nm, b= 1.0943 nm,c.0.4341 nm,α=β=γ=90°.
The layered compound CuNbO has been hydrothermally synthesized with K4Nb6017 as a precursor.Its chemical formula is [Cu(OH)0.66]1.53K1.95Nb6017·8.31H2O. This compound is orthogonal,and the lattice parameters are:a=0.5251 nm,b= 1.0707 nm,c=0.6302 nm,α=β=γ=90°。
系统研究了原料K4Nb6O17的合成、质子交换反应、胺剥层反应以及过渡金属的插层反应,并得出各步反应的最佳反应条件。
以铌酸钾为前驱体,通过水热合成的方法合成了镍铌氧插层化合物,其化学式为[Ni(OH)0.68]1.55K1.95Nb6O17·5.82H20,此化合物为单晶格化合物,正交晶系,晶胞参数为a=0.3442 nm,b=1.0943 nm,c=0.4341 nm,α=β=γ=90°。
以铌酸钾为前驱体,通过水热合成的方法合成了铜铌氧插层化合物,其化学式为[Cu(OH)0.66]1.53K1.95Nb6O17·8.31H2O,此化合物为单晶格化合物,正交晶系,晶胞参数为a=0.5251 nm,b=1.0707 nm,c=0.6302 nml,α=β=γ=90°。
所得的插层化合物采用一系列的测试手段,并对这些测试的数据进行分析,最后得出插层化合物的结构特点及其性质。
Nowadays, growing attention has been paid to the issue of energy. People are exploiting plenty of energies such as coal mining, oil, natural gas, etc. These energy sources will be exhausted in the near future. Thus finding new energy sources is the important task now. It can produce much energy when hydrogen is burned, and the water which is no hurt to the environment is the final product. So hydrogen is considered as the green energy source and become the best energy source. However, how to produce hydrogen conveniently is still a great challenge at present. Many scientists are trying to explore a variety of highly efficient catalysts. They hope to split the water into hydrogen and oxygen with solar energy by using these catalysts. The layered compounds caused more attentions of the scientists due to the interesting structures. Some compositions can be intercalated into the interlayered spaces of the layered compounds with some special methods, by which the width of the forbidden band is changed to nearly 1.23 ev, and these compounds can be used as the catalysts in the water spitting with visible light.
In the layered compounds, niobium oxides and titanium oxides are paid more attentions by many researchers. K4Nb6O17 is a two-dimensional layered material built with NbO6 octahedrons. The lattice parameters of K4Nb5O17 are:a=0.783 nm, b= 3.321 nm, c=0.646 nm. In this thesis, by using K4Nb6O17 as the precursor, through ion-exchange, exfoliation, intercalation, etc, some intercalation compounds have been synthesized. The synthesis conditions of the compounds have been investigated, and the characterization of the compounds have been produced.
The layered compound NiNbO has been hydrothermally synthesized with K4Nb6O17 as a precursor. Its chemical formula is [Ni(OH)o.68]1.55K1.95Nb6O17·5.82H2O. This compound is orthogonal, and the lattice parameters are:a=0.3442 nm, b= 1.0943 nm,c.0.4341 nm,α=β=γ=90°.
The layered compound CuNbO has been hydrothermally synthesized with K4Nb6017 as a precursor.Its chemical formula is [Cu(OH)0.66]1.53K1.95Nb6017·8.31H2O. This compound is orthogonal,and the lattice parameters are:a=0.5251 nm,b= 1.0707 nm,c=0.6302 nm,α=β=γ=90°。
引文
[1]侯文艳,刘宗怀,张国春.无机层状化合物的剥离技术及应用研究.[J].材料导报,2007,21：110～113
[2]段雪,张法智等.插层组装与功能材料.北京：化学工业出版社,2007
[3]Holger Borchert,Manfred Baerns. [J].J Cata,1997,168:315-320
[4]Tsuneo Matsuda. [J].J Cata,1997,168:26-34
[5]Lago R,Bini G, et al. [J].J Cata,1997,167:198-209
[6]Hyun G Kim,et al. [J]. Chem Commun,1999,1077-1078
[7]Tsungio Sato,Yositaka Yamamoto, Yshinobu Fujishiro, et al. [J].Chem Soc Faraday Trans,1996,92 : 5089-5092
[8]Tsungio Sato, Katsuhiko Masaki, Kenrichi Sato, et al. [J].J Chem Tech Biotechnol,1996,67:339-344
[9]Tsungio Sato, Katsuhiko Masaki, Kenrichi Sato, et al. [J].J Chem Tech Biotechnol,1996,67:345-349
[10]Jihuai Wu,Jianming Lin,Shu Yin,et al. [J].J Mater Chem.,2001,11:3343-3347
[11]Dan li, Juan Yang, Lili Zhang, et al. [J].J Mater Chem,2002,12,1796-1799
[12]Juan yang, Dan Li, Xin Wang, et al. [J].J Mater Sci,2003,38,2907-2911
[13]Juan yang, Dan Li, Henzhi Wang, et al. [J].Mater Lett,2001,50:230-234
[14]Saupe, G. B., Waraksa, C. C.,Kim, H.N.,Han, Y. J.,Kaschak, D.M.,Skinner, D. M.,Mallouk, T. E. Chem. Mater,2000,12,1556-1562.
[15]Nalwa H S. Handbook of nanostructured materal and nanotechnology. Chap. 1.Academic Press. San Diego,1999
[16]何白天,胡汉杰.[M].功能高分子与技术.北京：化学工业出版社,2001
[17]张玉清,彭淑鸽等.插层复合材料.北京：科学出版社,2008
[18]Jin-Ho Choy, Hyum Cheol Lee, Hyum Jung, et al. [J].J Mater Chem,2001,11:2232-2234
[19]Yanagisawa M,et al.[J].Chem Mater,2001 (13):174-178
[20]Ogawa M., Takizawa Y. [J]. Chem Mater,1999,11:30-32
[21]Zhang Z.W., Michael M., J.Chem.Mater.,1996,8,257.
[22]Z. P Xu, H. C. Zeng. Interconversion of brucite-like and hydrotalcite-like phases in cobalt hydroxide compounds. Chem. Mater.,2002 (12):5185-5185.
[23]Zhaoping Liu, Renzhi Ma, Minoru Osada, Nobuo Iyi, Yasuo Ebina,Kazunori Takada, Takayoshi Sasaki., J. Am. Chem. Soc.,2006,128,4872.
[24]F. Basile, G. Fornasari, V. Rosetti, et al. Effect of the Mg/Al ratio of the hydrotalcite-type precursor on the dispersion and activity of Rh and Rucatalysts for the partial oxidation of methane. Catal Today,2004 (91-92):293-297.
[25]ZhongSheng Wang, Takayoshi Sasaki, Masaru Muramatsu, Yasuo Ebina,Tomohiro Tanaka,Lianzhou Wang,Mamoru Watanabe.Chem.Mater.,2003,15,807
[26]Tawkaew S, Fujishiro Y, Shu Y, et al. [J]. Colloids and Surfaces, A:2001, 179:139-144.
[27]Furube A, Shiozawa T, Ishikawa A, et al. [J]. J.Phy. Chem.,B:2002,106: 3065-3072
[28]Prasad G K, Takei T, Yonesaki Y, Kumada N, Kinomura N(2006) Mater Lett,2006,60:3727
[29]张莉莉,陆路德.无机层状化合物及其应用述评[J].化工新型材料,2004,32：1
[30]Gateshki M, Hwang SJ, Park D H, et al. Structure of exfoliated titanate nanosheets determined by atomic pair distribution function analysis [J]. Chem Mater,2004,16:5153
[31]Alberti G, Cavalaglio S, Dionigi C, et al. Formation of aqueous colloidal dispersions of exfoliated γ-zirconium phosphate by intercalation of short alkylamines[J]. Langmuir,2000,16:7663
[32]Ebina Y, Sasaki T, Watanabe M. Study on exfoliation of layered perovskite-type niobates[J]. Solid State Ionics,2002,151:177
[33]Liu Z H, Ooi K, Kanoh H,et al.Swelling and delamination behaviors of birnessite-type manganese oxide by intercalation of tetraalky lammonium ions[J]. Langmuir,2000,16:4154
[34]Adachi-Pagano M,Forano C, Besse J P. Delamination of layered double hydroxides by use of surfactants [J]. Chem Commun,2000:91
[35]Hibino T. Delamination of layered double hydroxides containing amino acids [J]. Chem Mater,2004,16:5482
[36]Liu Z H, Wang Z M, Yang X J, et al. Intercalation of organic ammonium ions into layered graphite oxide[J]. Langmuir,2002,18:4926
[37]Benavente E, Santa Am M A, Mendizdbal F, et al. Intercalation chemistry of molybdenum disulfide. Coordination [J]. Chem Rev,2002,224:87
[38]沈家骢等.超分子层状结构-组装与功能.北京：科学出版社,2004
[39]张希,沈家骢.超分子科学：认识物质世界的新界面.科学通报,2003,14：1477
[40]王家俊,益小苏.高聚物/无机物插层型纳米复合材料[J].材料导报,1999,13(13)：54-56.
[41]Sayama K, Tanaka A, Domen K, Maruya K, Onishi T, J. Phys. Chem.,1991,95,1345
[42]Ebina Y, Sasaki T, Watanabe M.Study on exfoliation of layered perovskite-type niobates[J]. Solid State Ionics,2002,151:177
[43]Du,G.,Chen, Q.,Yu, Y., Zhang, S.,Zhou, W.,Peng,L.M. J. Mater.Chem.,2004, 14,1437-1442
[44]Zhang G K, Zou X, Gong J, et al. Characterization and Photocatalytic Activity of Cu-doped K2Nb4O11[J]. Journal of Molecular Catalysis A: Chemical,2006,255(1-2):109116.
[45]Zou Z G, Ye J H, Arakawa H. Structural Properties of InNbO4 and In TaO4-Co relation with Photocatalytic and Photophysical Properties[J]. Chemical Physics Letts,2000,332(3):271-277
[46]Li X K, Ye J H. Photocatalytic Degradation of Rhodamine Over Pb3Nb4O13/ Fumed SiO2 Composite Under Visible Light Irradiation[J]. J Physics Chem, 2007. 111:13109-13116.
[47]Garzatovar L L, Torrmartinez L M, Rodreguez D B, et al. Photocatalytic Degradation of Methylene Blue on Bi2MNbo7(M=AI, Fe, In, Sm)Solgel Catalysts [J]. Journal of Molecular Catalysis A:Chemical,2006,247(1-2):283-290
[48]Okazaki S, Kuroha H, Okuyama T. Effect of Nb2O5Addition on the Catalytic Activity of FeO for Reduction of NO with NH3 and O2[J]. Chemical Letters, 1985, (1):45.
[49]Parvulescu V, Ruwet M, Grange P, et al. Preparation, Characterization and Catalytic Behaviour of Cobaltniobia Catalysts[J]. Journal of Molecular Catalysis A:Chemical,1998,135(1):75-88.
[50]Ross J R H, Smits R H H, Scshan K. Preparation Physicochemical Properties and Catalytic Activities of Niobium M aterials International Symposium on Niobium Compounds[J]. Catal Today,1993,16(3-4):503-511.
[51]上官文锋.[J].无机化学学报,2001.17：619～626
[52]郭宪吉,侯文华等.[J].科学通报,2002.47：1681～1689
[53]Holger Borchert. Manfred Baerns. [J] J. Cata,1997.168:315-320
[54]Tsuneo Matsuda. [J].J.Cata,1997.168:26-34
[55]LagoR. Bini G,et al. [J].J.Cata,1997,167:198-209
[56]Hyun G Kim,et al. [J].C C.,1999.1077-1078
[57]TsungiSato,YositakaYamamoto,YshinobuFujishiro,etal.[J].CSFT,1996.92:5089-5092
[58]Tsungio Sato, Katsuhiko Masaki, Ken-ichi Sato,et al. [J]. JCTB,1996.67:339-344
[59]Tsungio Sato, Katsuhiko Masaki, Ken-ichi Sato,et al. [J]. JCTB,1996.67:345-349
[60]段雪,张法智等.无机超分子材料的插层组装化学.北京：科学出版社,2009
[61]张莉莉,刘冠鹏,张维光等.[J].中国稀土学报,2006,24(4)：168-173
[62]陈亚芍,侯文华,颜其洁.[J].无机化学学报,1995,11(4)：399-403.
[63]袁坚,陈恺,陈铭夏.层间插入CdS/ZnS的K4Nb6O17的制备及其光解水制氢研究[J].太阳能学报,2005,26：89
[64]杨亚辉,陈启元,尹周澜,李洁,粱胜.Fe3+和Cr3+掺杂对K4Nb6O17光催化活性的.影响[J].中国稀土学报,2004,242(5)：647-650
[65]T. NAKATO,K. KURODA and C. KATO, Chem. Mater.,4 (1992) 128.
[66]Kudo K, Sayama A, Tanaka K, et al.Nickel loaded K4Nb6O17 photocatalysts in the decomposition of H2O into H2 and O2:Structure and Reaction Mechanism [J]. J. Catal,1989,120,337.
[67]Shangguan W, Yoshida A. Influence of catalyst structure and modification on the photocatalytic production of hydrogen from water on mixed metal oxides [J]. Hydrogen Energy,1999,24:425
[68]Xiaobo Zhang, Dongsheng Feng,Meifeng Chen, Zhidan Ding, Zhiwei Tong. Preparation and electrochemical behavior of methylene blue intercalated into layered niobate K4Nb5O17[J]. Springer Science And BusinessMedia,2009,44:3020-3025
[69](a) T. Nakato, D. Sakamoto, K. Kuroda, C. Kato, Bull. Chem. Soc. Jpn.,65 (1992)322; (b) S.P. Mishra, V.K. Singh, D. Tiwari, Appl. Radiat. Isot,49 (1998) 1467; (c) L. Magalhaes Nunes, A. Gouveia de Souza, R. Fernandes de Farias, J. Alloy.Compd,319(2001)94; (d) K. Yao, S. Nishimura, T. Ma, K. Okamoto, K. Inoue, E. Abe, H. Tateyama, A.Yamagishi, J. Electroanal. Chem.,510 (2001) 144; (e) A. Furube, T. Shiozawa, A. Ishikawa, A. Wada, C. Hirose, K. Domen, Chem.Phys.,285(2002)31.
[70]Z. Tong, T. Shichi, Y. Kasuga, K. Takagi, Chem. Lett.,(2002) 1206.
[71]N. Kinomura, N. Kumada, F. Muto, J. Chem. Soc. Dalton Trans, (1985) 2349.
[72]东北师范大学,华中师范大学,陕西师范大学,北京师范大学等编.分析化学(下)(第三版).高等教育出版社,2005
[73]Singh D..Characteristics and effects of y-Ni(OH)2 on cell performance and a method to quantify it in nickel electrode [J].J. Electrochem. Soc.,1998, 145(1):116-119.
[74]张红兵,浦坦,李道火.Al3+、Zn2+替代镍离子的纳米氢氧化镍电极材料[J].电源技术,2004,28(5)：276～281.
[75]Fujita.W., Awaga. K. Reversible Structural Transformation and Drastic Magnetic Change in a Copper Hydroxides Intercalation Compound. J. Am. Chem. Soc.,1997.119.4563-4564.
[76]] Fujita W., Kunio Awaga K..Intercalation of stable organic radicals into layered copper hydroxides. Synth. Met.,2001.122.569-572.
[77]天津化工研究院等编.无机盐工业手册(下)(第三版),[M].北京：化学工业出版社,1988(1)
[78]Xinyu Song, Sixiu Sun, Weimin Zhang. Synthesis of Cu(OH)2 Nanowires at Aqueous Organic Interfaces, [J] J. Phys Chem B,2004,108:5200-5205.
[79]Xiaogang Wen, Weixin Zhang, Shihe Yang.Solution PhaseSynthesis of Cu(OH)2 Nanoribbons by Coordination Self -Assembly Using CU2S Nanowires as Precursors [J]. Nano Letters,2002,12 (2):1397-1401.
[80]Xiaogang Wen, Weixin Zhang, Shihe Yang.Synthesis of Cu(OH)2 and CuO Nanoribbon Arrays on a Copper surface, [J]. Langmuir,2003,19:5898- 5903.
[81]吴新明,易求实,吴金平等.纳米氢氧化铜的均匀沉淀法制备及低温热容,[J].材料科学与工艺,2001,1(9)：71-73.
[82]李光,冯伟骏,李喜孟.功率超声作用下纳米氧化铜粉体的制备,[J].材料导报,2003,(17)：44-471.
[83]Jihuai Wu. Jianming Lin. Shu Yin,et al. [J].J.Mater Chem,2001.11:3343-3347
[84]Eugster HP. Science,1967,157:1177
[85]Lagaly G, Bene K, Weiss A. Am. Mineral.,1975,60:642
[86]Brandt A, Schwieger W, Bergk K H et al. Cryst. Res. Technol.,1989,24:47
[87]Dailey J S, Pinnavaia T J. J. Inclusion Phenom. Mol. Recognit. Chem.,1992,13:47
[88]Hatsushika T, Takei S, Suzuki T. Muki Materiaru,1996,3:319
[89]Kim C S, Yates D M, Heaney P J.Clays Clay Miner.,1997,45:881
[90]Fujita I, Kuroda K, Ogawa M. Chem. Mater.,2003,15:3134
[91]FudalaA, KOnya Z,Kiyozumi Y et al. Micropor. Mesopor. Mater.,2000,35-36:631
[2]段雪,张法智等.插层组装与功能材料.北京：化学工业出版社,2007
[3]Holger Borchert,Manfred Baerns. [J].J Cata,1997,168:315-320
[4]Tsuneo Matsuda. [J].J Cata,1997,168:26-34
[5]Lago R,Bini G, et al. [J].J Cata,1997,167:198-209
[6]Hyun G Kim,et al. [J]. Chem Commun,1999,1077-1078
[7]Tsungio Sato,Yositaka Yamamoto, Yshinobu Fujishiro, et al. [J].Chem Soc Faraday Trans,1996,92 : 5089-5092
[8]Tsungio Sato, Katsuhiko Masaki, Kenrichi Sato, et al. [J].J Chem Tech Biotechnol,1996,67:339-344
[9]Tsungio Sato, Katsuhiko Masaki, Kenrichi Sato, et al. [J].J Chem Tech Biotechnol,1996,67:345-349
[10]Jihuai Wu,Jianming Lin,Shu Yin,et al. [J].J Mater Chem.,2001,11:3343-3347
[11]Dan li, Juan Yang, Lili Zhang, et al. [J].J Mater Chem,2002,12,1796-1799
[12]Juan yang, Dan Li, Xin Wang, et al. [J].J Mater Sci,2003,38,2907-2911
[13]Juan yang, Dan Li, Henzhi Wang, et al. [J].Mater Lett,2001,50:230-234
[14]Saupe, G. B., Waraksa, C. C.,Kim, H.N.,Han, Y. J.,Kaschak, D.M.,Skinner, D. M.,Mallouk, T. E. Chem. Mater,2000,12,1556-1562.
[15]Nalwa H S. Handbook of nanostructured materal and nanotechnology. Chap. 1.Academic Press. San Diego,1999
[16]何白天,胡汉杰.[M].功能高分子与技术.北京：化学工业出版社,2001
[17]张玉清,彭淑鸽等.插层复合材料.北京：科学出版社,2008
[18]Jin-Ho Choy, Hyum Cheol Lee, Hyum Jung, et al. [J].J Mater Chem,2001,11:2232-2234
[19]Yanagisawa M,et al.[J].Chem Mater,2001 (13):174-178
[20]Ogawa M., Takizawa Y. [J]. Chem Mater,1999,11:30-32
[21]Zhang Z.W., Michael M., J.Chem.Mater.,1996,8,257.
[22]Z. P Xu, H. C. Zeng. Interconversion of brucite-like and hydrotalcite-like phases in cobalt hydroxide compounds. Chem. Mater.,2002 (12):5185-5185.
[23]Zhaoping Liu, Renzhi Ma, Minoru Osada, Nobuo Iyi, Yasuo Ebina,Kazunori Takada, Takayoshi Sasaki., J. Am. Chem. Soc.,2006,128,4872.
[24]F. Basile, G. Fornasari, V. Rosetti, et al. Effect of the Mg/Al ratio of the hydrotalcite-type precursor on the dispersion and activity of Rh and Rucatalysts for the partial oxidation of methane. Catal Today,2004 (91-92):293-297.
[25]ZhongSheng Wang, Takayoshi Sasaki, Masaru Muramatsu, Yasuo Ebina,Tomohiro Tanaka,Lianzhou Wang,Mamoru Watanabe.Chem.Mater.,2003,15,807
[26]Tawkaew S, Fujishiro Y, Shu Y, et al. [J]. Colloids and Surfaces, A:2001, 179:139-144.
[27]Furube A, Shiozawa T, Ishikawa A, et al. [J]. J.Phy. Chem.,B:2002,106: 3065-3072
[28]Prasad G K, Takei T, Yonesaki Y, Kumada N, Kinomura N(2006) Mater Lett,2006,60:3727
[29]张莉莉,陆路德.无机层状化合物及其应用述评[J].化工新型材料,2004,32：1
[30]Gateshki M, Hwang SJ, Park D H, et al. Structure of exfoliated titanate nanosheets determined by atomic pair distribution function analysis [J]. Chem Mater,2004,16:5153
[31]Alberti G, Cavalaglio S, Dionigi C, et al. Formation of aqueous colloidal dispersions of exfoliated γ-zirconium phosphate by intercalation of short alkylamines[J]. Langmuir,2000,16:7663
[32]Ebina Y, Sasaki T, Watanabe M. Study on exfoliation of layered perovskite-type niobates[J]. Solid State Ionics,2002,151:177
[33]Liu Z H, Ooi K, Kanoh H,et al.Swelling and delamination behaviors of birnessite-type manganese oxide by intercalation of tetraalky lammonium ions[J]. Langmuir,2000,16:4154
[34]Adachi-Pagano M,Forano C, Besse J P. Delamination of layered double hydroxides by use of surfactants [J]. Chem Commun,2000:91
[35]Hibino T. Delamination of layered double hydroxides containing amino acids [J]. Chem Mater,2004,16:5482
[36]Liu Z H, Wang Z M, Yang X J, et al. Intercalation of organic ammonium ions into layered graphite oxide[J]. Langmuir,2002,18:4926
[37]Benavente E, Santa Am M A, Mendizdbal F, et al. Intercalation chemistry of molybdenum disulfide. Coordination [J]. Chem Rev,2002,224:87
[38]沈家骢等.超分子层状结构-组装与功能.北京：科学出版社,2004
[39]张希,沈家骢.超分子科学：认识物质世界的新界面.科学通报,2003,14：1477
[40]王家俊,益小苏.高聚物/无机物插层型纳米复合材料[J].材料导报,1999,13(13)：54-56.
[41]Sayama K, Tanaka A, Domen K, Maruya K, Onishi T, J. Phys. Chem.,1991,95,1345
[42]Ebina Y, Sasaki T, Watanabe M.Study on exfoliation of layered perovskite-type niobates[J]. Solid State Ionics,2002,151:177
[43]Du,G.,Chen, Q.,Yu, Y., Zhang, S.,Zhou, W.,Peng,L.M. J. Mater.Chem.,2004, 14,1437-1442
[44]Zhang G K, Zou X, Gong J, et al. Characterization and Photocatalytic Activity of Cu-doped K2Nb4O11[J]. Journal of Molecular Catalysis A: Chemical,2006,255(1-2):109116.
[45]Zou Z G, Ye J H, Arakawa H. Structural Properties of InNbO4 and In TaO4-Co relation with Photocatalytic and Photophysical Properties[J]. Chemical Physics Letts,2000,332(3):271-277
[46]Li X K, Ye J H. Photocatalytic Degradation of Rhodamine Over Pb3Nb4O13/ Fumed SiO2 Composite Under Visible Light Irradiation[J]. J Physics Chem, 2007. 111:13109-13116.
[47]Garzatovar L L, Torrmartinez L M, Rodreguez D B, et al. Photocatalytic Degradation of Methylene Blue on Bi2MNbo7(M=AI, Fe, In, Sm)Solgel Catalysts [J]. Journal of Molecular Catalysis A:Chemical,2006,247(1-2):283-290
[48]Okazaki S, Kuroha H, Okuyama T. Effect of Nb2O5Addition on the Catalytic Activity of FeO for Reduction of NO with NH3 and O2[J]. Chemical Letters, 1985, (1):45.
[49]Parvulescu V, Ruwet M, Grange P, et al. Preparation, Characterization and Catalytic Behaviour of Cobaltniobia Catalysts[J]. Journal of Molecular Catalysis A:Chemical,1998,135(1):75-88.
[50]Ross J R H, Smits R H H, Scshan K. Preparation Physicochemical Properties and Catalytic Activities of Niobium M aterials International Symposium on Niobium Compounds[J]. Catal Today,1993,16(3-4):503-511.
[51]上官文锋.[J].无机化学学报,2001.17：619～626
[52]郭宪吉,侯文华等.[J].科学通报,2002.47：1681～1689
[53]Holger Borchert. Manfred Baerns. [J] J. Cata,1997.168:315-320
[54]Tsuneo Matsuda. [J].J.Cata,1997.168:26-34
[55]LagoR. Bini G,et al. [J].J.Cata,1997,167:198-209
[56]Hyun G Kim,et al. [J].C C.,1999.1077-1078
[57]TsungiSato,YositakaYamamoto,YshinobuFujishiro,etal.[J].CSFT,1996.92:5089-5092
[58]Tsungio Sato, Katsuhiko Masaki, Ken-ichi Sato,et al. [J]. JCTB,1996.67:339-344
[59]Tsungio Sato, Katsuhiko Masaki, Ken-ichi Sato,et al. [J]. JCTB,1996.67:345-349
[60]段雪,张法智等.无机超分子材料的插层组装化学.北京：科学出版社,2009
[61]张莉莉,刘冠鹏,张维光等.[J].中国稀土学报,2006,24(4)：168-173
[62]陈亚芍,侯文华,颜其洁.[J].无机化学学报,1995,11(4)：399-403.
[63]袁坚,陈恺,陈铭夏.层间插入CdS/ZnS的K4Nb6O17的制备及其光解水制氢研究[J].太阳能学报,2005,26：89
[64]杨亚辉,陈启元,尹周澜,李洁,粱胜.Fe3+和Cr3+掺杂对K4Nb6O17光催化活性的.影响[J].中国稀土学报,2004,242(5)：647-650
[65]T. NAKATO,K. KURODA and C. KATO, Chem. Mater.,4 (1992) 128.
[66]Kudo K, Sayama A, Tanaka K, et al.Nickel loaded K4Nb6O17 photocatalysts in the decomposition of H2O into H2 and O2:Structure and Reaction Mechanism [J]. J. Catal,1989,120,337.
[67]Shangguan W, Yoshida A. Influence of catalyst structure and modification on the photocatalytic production of hydrogen from water on mixed metal oxides [J]. Hydrogen Energy,1999,24:425
[68]Xiaobo Zhang, Dongsheng Feng,Meifeng Chen, Zhidan Ding, Zhiwei Tong. Preparation and electrochemical behavior of methylene blue intercalated into layered niobate K4Nb5O17[J]. Springer Science And BusinessMedia,2009,44:3020-3025
[69](a) T. Nakato, D. Sakamoto, K. Kuroda, C. Kato, Bull. Chem. Soc. Jpn.,65 (1992)322; (b) S.P. Mishra, V.K. Singh, D. Tiwari, Appl. Radiat. Isot,49 (1998) 1467; (c) L. Magalhaes Nunes, A. Gouveia de Souza, R. Fernandes de Farias, J. Alloy.Compd,319(2001)94; (d) K. Yao, S. Nishimura, T. Ma, K. Okamoto, K. Inoue, E. Abe, H. Tateyama, A.Yamagishi, J. Electroanal. Chem.,510 (2001) 144; (e) A. Furube, T. Shiozawa, A. Ishikawa, A. Wada, C. Hirose, K. Domen, Chem.Phys.,285(2002)31.
[70]Z. Tong, T. Shichi, Y. Kasuga, K. Takagi, Chem. Lett.,(2002) 1206.
[71]N. Kinomura, N. Kumada, F. Muto, J. Chem. Soc. Dalton Trans, (1985) 2349.
[72]东北师范大学,华中师范大学,陕西师范大学,北京师范大学等编.分析化学(下)(第三版).高等教育出版社,2005
[73]Singh D..Characteristics and effects of y-Ni(OH)2 on cell performance and a method to quantify it in nickel electrode [J].J. Electrochem. Soc.,1998, 145(1):116-119.
[74]张红兵,浦坦,李道火.Al3+、Zn2+替代镍离子的纳米氢氧化镍电极材料[J].电源技术,2004,28(5)：276～281.
[75]Fujita.W., Awaga. K. Reversible Structural Transformation and Drastic Magnetic Change in a Copper Hydroxides Intercalation Compound. J. Am. Chem. Soc.,1997.119.4563-4564.
[76]] Fujita W., Kunio Awaga K..Intercalation of stable organic radicals into layered copper hydroxides. Synth. Met.,2001.122.569-572.
[77]天津化工研究院等编.无机盐工业手册(下)(第三版),[M].北京：化学工业出版社,1988(1)
[78]Xinyu Song, Sixiu Sun, Weimin Zhang. Synthesis of Cu(OH)2 Nanowires at Aqueous Organic Interfaces, [J] J. Phys Chem B,2004,108:5200-5205.
[79]Xiaogang Wen, Weixin Zhang, Shihe Yang.Solution PhaseSynthesis of Cu(OH)2 Nanoribbons by Coordination Self -Assembly Using CU2S Nanowires as Precursors [J]. Nano Letters,2002,12 (2):1397-1401.
[80]Xiaogang Wen, Weixin Zhang, Shihe Yang.Synthesis of Cu(OH)2 and CuO Nanoribbon Arrays on a Copper surface, [J]. Langmuir,2003,19:5898- 5903.
[81]吴新明,易求实,吴金平等.纳米氢氧化铜的均匀沉淀法制备及低温热容,[J].材料科学与工艺,2001,1(9)：71-73.
[82]李光,冯伟骏,李喜孟.功率超声作用下纳米氧化铜粉体的制备,[J].材料导报,2003,(17)：44-471.
[83]Jihuai Wu. Jianming Lin. Shu Yin,et al. [J].J.Mater Chem,2001.11:3343-3347
[84]Eugster HP. Science,1967,157:1177
[85]Lagaly G, Bene K, Weiss A. Am. Mineral.,1975,60:642
[86]Brandt A, Schwieger W, Bergk K H et al. Cryst. Res. Technol.,1989,24:47
[87]Dailey J S, Pinnavaia T J. J. Inclusion Phenom. Mol. Recognit. Chem.,1992,13:47
[88]Hatsushika T, Takei S, Suzuki T. Muki Materiaru,1996,3:319
[89]Kim C S, Yates D M, Heaney P J.Clays Clay Miner.,1997,45:881
[90]Fujita I, Kuroda K, Ogawa M. Chem. Mater.,2003,15:3134
[91]FudalaA, KOnya Z,Kiyozumi Y et al. Micropor. Mesopor. Mater.,2000,35-36:631