Gd@C_（82）的制备工艺及性质研究
摘要
本文研究并获得了电弧放电法制备内嵌金属富勒烯Gd@C_(82)的最佳工艺条件:氦气压力0.08MPa,摩尔比Gd:C=1:15-1:20,活化电流200A,活化时间30min以上,反应电流90~100A。详细研究并获得了制备烟灰中Gd@C_(82)分离纯化条件和方法:以DMF为溶剂,减压萃取至无色;再以Buckyprep-M柱为色谱柱,甲苯为流动相,流速为10mL/min,采用高效液相色谱分离,Gd@C_(82)保留时间为40~50min。研究了滴覆法及真空蒸镀法在富勒烯镀膜中的应用,并首次将旋涂法引入富勒烯镀膜,且取得了较好的结果,最终确定旋涂法及真空蒸镀法可以应用于富勒烯镀膜。研究了液-液界面微环境对富勒烯晶型的影响,并制备了常温下不易稳定存在的简单六方C60晶体,为以后Gd@C_(82)的镀膜研究提供了实验依据。最后使用Dmol3程序计算了C_(82)碳笼和Gd@C_(82)碳笼的一些性质,解释了Gd@C_(82)制备过程中遇到的一些现象,并预测了Gd@C_(82)的一些化学性质。
In this paper, process conditions preparing endohedral metallofullerene Gd@C_(82) by arc-discharge method are studied, and its best technological conditions are obtained: helium pressure 0.08 MPa, nGd: nC = 1:15-1:20, activation current 200A, activation time 30min, reaction current I = 90 ~ 100A; conditions of separation and extraction of Gd@C_(82) from soot are studied: firstly, the soot is extracted in vacuum with DMF as the solvent; secondly, Gd@C_(82) is separated by Buckyprep-M column and its retention time is about 40 ~ 50min when the mobile phase is toluene and flow rate is 10mL/min. Applications to fullerene film of drop-coating method and vacuum evaporation method are studied. Spin-coating is introduced into fullerene film in the first time, and achieves good results. Ultimately spin-coating method and vacuum evaporation coating method are determinted to can be applied to fullerene film. Effects of liquid - liquid interface micro-environment on of the fullerene crystal are studied, and simple cubic C60 crystal not easily prepared at room temperature are abtained. At last some properties of C_(82) and Gd@C_(82) carbon cage are calculated using the Dmol3, some phenomena encountered in the preparation of Gd@C_(82) are explained, and some chemical properties of Gd@C_(82) are predicted.
In this paper, process conditions preparing endohedral metallofullerene Gd@C_(82) by arc-discharge method are studied, and its best technological conditions are obtained: helium pressure 0.08 MPa, nGd: nC = 1:15-1:20, activation current 200A, activation time 30min, reaction current I = 90 ~ 100A; conditions of separation and extraction of Gd@C_(82) from soot are studied: firstly, the soot is extracted in vacuum with DMF as the solvent; secondly, Gd@C_(82) is separated by Buckyprep-M column and its retention time is about 40 ~ 50min when the mobile phase is toluene and flow rate is 10mL/min. Applications to fullerene film of drop-coating method and vacuum evaporation method are studied. Spin-coating is introduced into fullerene film in the first time, and achieves good results. Ultimately spin-coating method and vacuum evaporation coating method are determinted to can be applied to fullerene film. Effects of liquid - liquid interface micro-environment on of the fullerene crystal are studied, and simple cubic C60 crystal not easily prepared at room temperature are abtained. At last some properties of C_(82) and Gd@C_(82) carbon cage are calculated using the Dmol3, some phenomena encountered in the preparation of Gd@C_(82) are explained, and some chemical properties of Gd@C_(82) are predicted.
引文
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[6]张娅,施祖进,郝策,等. Ca@C88和Ca@C90的合成、分离和表征[J].物理化学学报, 2004, 20(6): 573-576
[7] Lian Y F, Shi Z J, Zhou X H, et al. High-yield preparation of dimetallofullerenes by the improved DC arc discharge method[J]. J. Phys. Chem. Solids., 2000, 61(7): 1037-1040
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[9] Lian Yongfu, Shi Zujin, Zhou Xihuang, et al. Preparation and Enrichment of Samarium Endohedral Fullerenes[J]. Chem. Mater., 2001, 13(1): 39-42
[10] Weiske T, Wong T, Kraschmer W, et al. Endohedral cluster compounds: Inclusion of helium within C60 and C70 through collision experiments[J]. Angew. Chem. Soc., 1991, 30(7): 884-886
[11] Lips K, Waiblinger M, Pietzak B, et al. Atomic Nitrogen Encapsulated in Fullerenes: Realization of a Chemical Faraday Cage[J]. Phys. Stat. Sol., 2000, 177(81): 81-91
[12] Murata Y, Murata M, Komatsu K. Synthesis, Structure, and Properties of Novel Open-Cage Fullerenes Having Heteroatom(s) on the Rim of the Orifice[J]. Chem. Eur. J., 2003, 9(7): 1600-1609
[13] Komatsu K, Murata M, Murata Y. Encapsulation of Molecular Hydrogen in Fullerene C60 by Organic Synthesis[J]. Science, 2005, 307(5707): 238-240
[14] Iwamatsu S I, Stanisky C M, Cross R J, et al. Carbon Monoxide Inside an Open Cage
Fullerene[J]. Angew. Chem. Int. Ed., 2006, 45(32): 5337-5340
[15] Stanisky C M, Cross R J, Saunders M, et al. Helium entry and escape through a chemically opened window in a fullerene[J]. J. Am. Chem. Soc., 2005, 127(1): 299-302
[16] Saunder M, Hugo A, et al. Incorporation of Helium, Neon, Argon, Krypton, and Xenon into Fullerenes using High Pressure[J]. J. Am. Chem. Soc., 1994, 116(5): 2193-2194
[17] Peng R F, Chu Sh J, Huang Y M, et al. Preparation of He@C_(60) and He_2@C_(60) by an explosive method[J]. J. Mater. Chem., 2009, 19(22): 3602-3605
[18] Robert L Murry, Gustavo E Scuseria. Theoretical Evidence for a C_(60)“window”Mechanism[J]. Science, 1994, 263(5148): 791-793
[19] Cagle D W , Thresh T P, Alford M, et al. Synthesis, characterization, and neutron activation of holmium metallofullerenes[J]. J. Am. Chem. Soc., 1996, 118(34): 8043-8047
[20] Capp C, Wood T D, Marshall A G, et al. High-pressure toluene extraction of La@Cn for even N from 74 to 90[J]. J. Am. Chem. Soc., 1994, 116(11): 4987-4988
[21] Sun Baoyun, Feng Lai. Improved extraction of metallofullerenes with DMF at high temperature[J]. Carbon, 2002, 40(9): 1591-1596
[22]孙淑清,刘志强,邢俊鹏,等.高温高压法提取金属富勒烯Lnm@C2n (Ln= Y, Gd, Tb) [J].高等学校化学学报, 2002, 23(2): 300-302
[23]张德文,柳翱,郐羽.笼内金属富勒烯的Gd@C_(82)合成[J].吉林工学院学报, 2002, 23(2): 47-48
[24]朱妙琴. Gd-富勒烯包合物合成提取及质谱表征[J].浙江教育学院学报, 2006, 4: 61-64
[25]孙宝云,李美仙,顾镇南. Sm金属富勒烯的高效提取和电化学性质研究[J].高等学校化学学报, 2002, 23 (7): 1389-1391
[26] Michael D Diener, Coleman A Smith, D Kirk Veirs. Anaerobic Preparation and Solvent-Free Separation of Uranium Endohedral Metallofullerenes[J]. Chem. Mater.,1997, 9 (8): 1773-1777
[27] Kato H, Kanazawa Y, Okumura M, et al. Lanthanoid endohedral metallofullerenols for MRI Contrast Agents[J]. J. Am. Chem. Soc., 2003, 125(14): 4391-4397
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