金属铜及氧化亚铜纳米材料的非模板法制备与性质研究
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摘要
论文用简单易行的无模板法制备铜及其氧化物纳米材料,并对材料性能进行了研究。
先用简单的液相回流还原法制备了Cu2O纳米空心球前驱物,再用氢气还原法还原得到了Cu纳米空心球。在Cu2O前驱物的制备过程中,有机溶剂对球径的大小有影响,无水乙醇中制备的Cu2O空心球的平均粒径比叔丁醇体系小。由于叔丁醇体系制备Cu2O空心球的产率(75%)比无水乙醇体系(70%)稍高,选择叔丁醇溶剂体系制备Cu2O空心球作为氢气还原的前驱物。考察了还原温度和还原时间对于氢气还原Cu2O效率的影响,当反应时间2小时,还原温度在170℃左右时,基本可得到较纯的产物Cu空心球。紫外-可见吸收的光学特征图谱显示Cu2O前驱物样品和Cu纳米空心球与块体相应颗粒相比,都发生了较大程度的蓝移。同时,回流法制备的Cu2O纳米空心球,在经过较长时间的低温保存后,逐渐演变为具有核壳结构的纳米十四面体。
在回流及氨气保护条件下,以叔丁醇为溶剂,乙酸铜为铜源,制备了纳米级金属铜空心球结构的。空心球的直径为400nm左右。还原剂的加入量对产物成分有重要影响。
In this paper, the convenient template free processes for the preparation of copper and cuprous oxide nanometer materials are reported, and the properties of the materials are studied.
Cu2O hollow nanospheres were first generated through a template free process, and then Cu hollow nanospheres were prepared with Cu2O hollow nanospheres as precursor and H2 as the reductant. During the preparation of the precursor, nanospheres formed in absolute alcohol were smaller in size than in tert-butyl alcohol in the similar reaction conditions. The Cu2O hollow nanospheres prepared in tert-butyl alcohol were chosen as the precursor, since the production rate(75%) is higher than in absolute alcohol(70%). The reduction time and temperature of hydrogen reduction were studied: the well-dispersed Cu hollow nanospheres can be fabricated at 170°C with a reduction time of 2 hours. Moreover, a remarkable blue-shift phenomenon was found in the ultraviolet–visible light (UV–visible) absorption spectra of both Cu and Cu2O hollow nanospheres. During the preservation of the Cu2O hollow nanospheres, a well-regulated tetrakaidecahedron of the surface morphology with a core-shell structure formed.
Under the protection of NH3 gas, Cu hollow nanospheres were prepared by a refluxing method, with Tert-Butyl alcohol as the organic solvent, and acetate monohydrateas as the source of copper. The produtions are hollow nanospheres with a diameter of about 400nm. The dose of the reducer plays an important role on the purity of the production.
先用简单的液相回流还原法制备了Cu2O纳米空心球前驱物,再用氢气还原法还原得到了Cu纳米空心球。在Cu2O前驱物的制备过程中,有机溶剂对球径的大小有影响,无水乙醇中制备的Cu2O空心球的平均粒径比叔丁醇体系小。由于叔丁醇体系制备Cu2O空心球的产率(75%)比无水乙醇体系(70%)稍高,选择叔丁醇溶剂体系制备Cu2O空心球作为氢气还原的前驱物。考察了还原温度和还原时间对于氢气还原Cu2O效率的影响,当反应时间2小时,还原温度在170℃左右时,基本可得到较纯的产物Cu空心球。紫外-可见吸收的光学特征图谱显示Cu2O前驱物样品和Cu纳米空心球与块体相应颗粒相比,都发生了较大程度的蓝移。同时,回流法制备的Cu2O纳米空心球,在经过较长时间的低温保存后,逐渐演变为具有核壳结构的纳米十四面体。
在回流及氨气保护条件下,以叔丁醇为溶剂,乙酸铜为铜源,制备了纳米级金属铜空心球结构的。空心球的直径为400nm左右。还原剂的加入量对产物成分有重要影响。
In this paper, the convenient template free processes for the preparation of copper and cuprous oxide nanometer materials are reported, and the properties of the materials are studied.
Cu2O hollow nanospheres were first generated through a template free process, and then Cu hollow nanospheres were prepared with Cu2O hollow nanospheres as precursor and H2 as the reductant. During the preparation of the precursor, nanospheres formed in absolute alcohol were smaller in size than in tert-butyl alcohol in the similar reaction conditions. The Cu2O hollow nanospheres prepared in tert-butyl alcohol were chosen as the precursor, since the production rate(75%) is higher than in absolute alcohol(70%). The reduction time and temperature of hydrogen reduction were studied: the well-dispersed Cu hollow nanospheres can be fabricated at 170°C with a reduction time of 2 hours. Moreover, a remarkable blue-shift phenomenon was found in the ultraviolet–visible light (UV–visible) absorption spectra of both Cu and Cu2O hollow nanospheres. During the preservation of the Cu2O hollow nanospheres, a well-regulated tetrakaidecahedron of the surface morphology with a core-shell structure formed.
Under the protection of NH3 gas, Cu hollow nanospheres were prepared by a refluxing method, with Tert-Butyl alcohol as the organic solvent, and acetate monohydrateas as the source of copper. The produtions are hollow nanospheres with a diameter of about 400nm. The dose of the reducer plays an important role on the purity of the production.
引文
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[16]陈焕春,杨绪杰,陆路德等.纳米材料的研究现状及展望[J].导弹与航天运载技术. 2000, (3) : 11-16.
[17]魏建红,官建国,袁润章.金属纳米粒子的制备与应用[J].武汉理工大学学报. 2001 , 23 (3) : 1-4.
[18]田荣璋等.金属材料知识手册[M].湖南科学技术出版社, 1993.
[19]柏振海,罗兵辉,金晓鸿.氧化亚铜粉末的制备[J].矿冶工程. 2001,21 (4): 67-69.
[20]孙晓昆,谢保华.电点火技术用Cu2O型和SiC型半导体陶瓷材料[J].火花塞与特种陶瓷. 1996, 3:25-26.
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[22]陈金毅,刘小玲,李阎轮等.纳米氧化亚铜可见光催化分解亚甲基蓝[J].华中师范大学学报(自然科学版). 2002, 36:200-203.
[23]郑惠梅.含铜纳米材料的制备与应用研究[D].南京理工大学, 2004.
[24]张志梅,韩喜江,孙淼鑫.纳米级铜粉的制备[J].精细化工. 2000, 17:69-71.
[25]楚广,唐勇建,刘伟等.纳米铜粉的制备及其应用[J].金属功能材料. 2005,12(3):18-21.
[26]陈庆春.铜纳米棒和纳米线水热还原制备的条件选择[J].精细化工. 2006, 22 (6): 417-419.
[27]刘伟,崔作林,张志焜.晶核生长法制备纳米铜粒子[J].中国粉体技术. 2004, 3 : 31-32.
[28]胡敏艺,徐锐,王崇国等.超细球形铜粉的制备[J].功能材料. 2007, 38: 1577-1579.
[29]贺军辉,陈洪敏,张林.无机微纳空心球[J].化工进展. 2007, 19(10): 1488 - 1494 .
[30]金娜,刘颖,李梦.金属空心微球的制备及应用现状[J].功能材料. 2007, 38: 4111-4115.
[31]M. Shao, Q. Li, L. Kong, et al.. The synthesis of hollow CdS nanospheres packed with square subunits[J]. Journal of Physics and Chemistry of Solids. 2003, 64:1147-1150.
[32]C. Jiang, W. Zhang, G. Zou, et al.. Hydrothermal synthesis and characterization of ZnS microspheres and hollow nanospheres[J]. Materials Chemistry and Physics. 2007, 103:24-27.
[33]J. H. Park, Y. G. Kim, C. Oh, et al.. Fabrication of hollow silver spheres byMPTMS-functionalized hollow silica spheres as templates[J]. Materials Research Bulletin. 2005,40:271-280.
[34]H. Zhou, T. Fan, D. Zhang. Hydrothermal synthesis of ZnO hollow spheres using spherobacterium as biotemplates[J]. Microporous and Mesoporous Materials. 2007,100:322-327.
[35]T. H. Kim, K. H. Lee, Y. K. Kwon. Monodisperse hollow titania nanospheres prepared using a cationic colloidal template[J]. Journal of Colloid and Interface Science. 2006, 304:370-377.
[36]C. Yin, Q. Huang, B. Liu, et al.. Synthesis and TEM observation of fluffy hollow carbon spheres by FeCl3 catalyzed solvent-thermal reaction[J]. Materials Letters. 2007, 61: 4015-4018.
[37]关锋,刘恒,李坤等.空心球壳型V2O5的制备研究[J].化学研究与应用. 2007,19(12):1382-1384.
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