化学法制备纳米尺寸镧系金属氢化物及纳米镧系金属粉末
|
摘要
本项研究工作为国家科学自然基金——“化学法制备纳米稀土金属和稀土氢化物及其性能应用的研究”的资助课题。首次在温和条件下(1 个大气压、45 ℃) ,有机相中,用两种方法:卤代烃引发和金属经活化后利用溶剂效应,取代需在高温(300 ℃)下进行的传统方法,镧与氢气直接反应合成出纳米尺寸氢化镧。比较了不同引发剂和溶剂对该反应的影响。透射电镜(TEM)表征结果:氢化镧的基本颗粒尺寸约为20-40 nm。X粉末衍射(XRD)表征结果表明,其结构为立方晶体。制得的氢化镧粉末活性极高,暴露在空气中着火。
选取镧系中的镧、钕、钐、镝、镱五种金属,在温和条件下(1个大气压、45 ℃),有机相中,用卤代烃引发合成蒽镧系金属有机化合物,真空热解首次制备出纳米尺寸镧系金属粉末。TEM测试结果:金属粉末的基本颗粒尺寸为20-40 nm。制备的蒽镧系金属有机化合物及纳米镧系金属粉末活性高,暴露在空气着火。
我们所合成的纳米尺寸镧系金属氢化物,蒽镧系金属有机化合物及纳米镧系金属粉末对空气和水气十分敏感,所有实验操作均采用无水无氧的Schlenk 技术。
软件开发是目前新兴产业之一,它已成为计算机应用的主流。我们使用Visual Basic 6.0 计算机语言研制出“物理化学实验数据处理软件”,用以解决物理化学实验课教学问题。该软件即将由高等教育出版社出版。
Lanthanum hydride is prepared easily by two chemical methods under mild conditions (45 ℃,normal pressure). We investigated the influent of initiating agent and solvent to reactions. Transmission electron micrographs showed that lanthanum hydrides generated are in the form of nanoparticles with an average primary particle size around 20-40 nm. The structure of the lanthanum hydride characterized by the X-ray powder diffraction (XRD) is cube.
The reaction of lanthanide powders with anthracene in the presence of initiating agent in tetrahydrofuran(THF)under mild conditions generated organolanthanide compounds. It was found that the decomposition of the organolanthanide compounds in vacuum could give rise to lanthanide powders of nanometric size. Transmission electron micrographs showed that the lanthanide powders formed were in the form of nanoparticles with an average primary particle size around 20-40 nm.
Nanometric lanthanide hydrides, organolanthanid complex and nanometric lanthanide metal powders are sensitive to air and moisture, so all manipulations are carried under Ar atmosphere with Schlenk technology.
We develop the data processing software of the physical chemistry experiment programmed by Visual Basic 6.0 and sign contract with higher education press.
选取镧系中的镧、钕、钐、镝、镱五种金属,在温和条件下(1个大气压、45 ℃),有机相中,用卤代烃引发合成蒽镧系金属有机化合物,真空热解首次制备出纳米尺寸镧系金属粉末。TEM测试结果:金属粉末的基本颗粒尺寸为20-40 nm。制备的蒽镧系金属有机化合物及纳米镧系金属粉末活性高,暴露在空气着火。
我们所合成的纳米尺寸镧系金属氢化物,蒽镧系金属有机化合物及纳米镧系金属粉末对空气和水气十分敏感,所有实验操作均采用无水无氧的Schlenk 技术。
软件开发是目前新兴产业之一,它已成为计算机应用的主流。我们使用Visual Basic 6.0 计算机语言研制出“物理化学实验数据处理软件”,用以解决物理化学实验课教学问题。该软件即将由高等教育出版社出版。
Lanthanum hydride is prepared easily by two chemical methods under mild conditions (45 ℃,normal pressure). We investigated the influent of initiating agent and solvent to reactions. Transmission electron micrographs showed that lanthanum hydrides generated are in the form of nanoparticles with an average primary particle size around 20-40 nm. The structure of the lanthanum hydride characterized by the X-ray powder diffraction (XRD) is cube.
The reaction of lanthanide powders with anthracene in the presence of initiating agent in tetrahydrofuran(THF)under mild conditions generated organolanthanide compounds. It was found that the decomposition of the organolanthanide compounds in vacuum could give rise to lanthanide powders of nanometric size. Transmission electron micrographs showed that the lanthanide powders formed were in the form of nanoparticles with an average primary particle size around 20-40 nm.
Nanometric lanthanide hydrides, organolanthanid complex and nanometric lanthanide metal powders are sensitive to air and moisture, so all manipulations are carried under Ar atmosphere with Schlenk technology.
We develop the data processing software of the physical chemistry experiment programmed by Visual Basic 6.0 and sign contract with higher education press.
引文
1.沈丽,科技成果纵横,2003,3,60-61
2.薛群基,徐康,化学进展,2000,431-444
3. Robert D. Miller. Chem. Rev., 1999, vol.99, 7: 1641-1642
4. Feldheim D.L., Metal nanoparticles:Synthesis,Characterization,and Applications ,New York :MARCEL DEEKKER. INC.,2002
5.蔡卫权,陈进富,现代化工,第22卷增刊,2002,34
6.周艳琼,粉末冶金工业,Vol.11.N.o 4,2001,41
7.郑华均,刘华章 浙江化工 2003.34:2
8.蔡元霸、梁玉仓 结构化学,Vol.24,2001,425-438
9.化学世界,2000,11,64
10.阎子峰,纳米催化技术,北京:化学工业出版社,2003,559-600
11.张立德,中国粉体技术,2001,vol.7(5)
12.山本明夫(日),有机金属化学—基础与应用,科学出版社,1997,1-3
13.戚冠发,有机金属化合物化学基础,长春:东北师范大学出版社,1986,204-210
14.易宪武,黄春晖等 无机化学丛书 第七卷 钪、稀土元素,北京:科学出版社,1998,
15.陈晋阳,化学世界,2002,54
16.林河成,稀土,2003,vol.24,No.1,75
17.马莉,福建化工,2002,1,42
18. Mikhail N.Bochkarev,Chem.Rev., 2002,vol.102,No.6,2089-2117
19.Cotton, R,A. Am. Chem. Soc. 1986,108,4657
20.Correhl, H.,organometallics,1995,14,992
21.Seemayer, K,Organometallics, 1995. 14. 4465
22.Gibson,J. K,phys. Chem.,1996,100,15688
23.Heinemann.C,Chem. Ber, 1994,127,1807
24.Chauvin Y,Olivier H.,Saussine L.,Inorg,Chim.Acta,1989,12,13
25.D. M.Izv. Acad. Nank. S. Khim 1997.1667
26.JCPDS(32-481)
27. 王亚军, 冯长根, 王丽琼等,稀土在汽车尾气净化中的应用,工业催化,2000,8 (5): 3-7
28. 李青,环境保护, 1998(4): 19-22
29.顾翼东主编,化学词典,上海:上海辞书出版社,2003,989
30.Esso Research and Eng.Co. (inv.H.E.Ramsden), US Pat.3354 190, 1967.
31.Bogdanovic,B.; Liao,S-J.; Schwickardi,M,; Sidorsky,P.; Spliethoff,B., Angew.Chem.1990, 92; Angew. Chem. Int. Ed. Engl., 1980, 19.
32.Bogdanovic,B.; Chem. Int. Ed. Engl.,1985, 24.
33.刑其毅,徐瑞秋等,基础有机化学 上册,北京:高等教育出版社,1993,126-160
34. 大角泰章(日),金属氢化物的性质与应用,北京:化学工业出版社,1990
35.N.N格林伍德,A.厄恩肖著,曹庭礼等译,元素化学(上),北京:高等教育出版社,1997
36.kirk-othmer,Encyclopedia of chemical thchnology,3rd.Ed., 1980,vol.12, 772
37. 廖世健,自然杂志,1982,5(12),905
38. 易宪武,黄春晖等 无机化学丛书 第七卷 钪、稀土元素,北京:科学出版社,1998
39. E.A.Sullivan and R.C.Wade, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley &Sons, New York, 1980, 3rd Edit, Vol.12.p.772.
40. 申泮文,张靓华等,无机化学丛书 第一卷,北京:科学出版社,1984,203
41. 张文魁,王云刚,稀有金属材料与工程,2002,vol.31,6,432-436
42. Sullivan E. A.,In Kirk-Othmer Encyclopedia of Chemical Technology [M], Vol. 13, 4th Ed., John Wiley & Sons, New York, 1995: 613
43. Borislav Bogdanovic,Angew. Chem.Int. Ed. Engl,1985,24,262-273
44. Fan YinHeng, Wu Meixia, Chin. J. Chem., 2002, vol. 20, 11, 1450
45. Cotton,F.A.,Wiklinson,G.Advanced Inorganic Chemistry,4th Edn.,John Wiley &Sons,New York,1980,250
46. 范荫恒,李伟娜,应用化学,2001,vol.18,5,389-391
47. 张源魁,廖世健,徐筠等,催化学报,1996,17,489
48. 武美霞,辽宁师范大学硕士毕业论文,2003
49.《物理化学实验》(第二版,复旦大学等编),高等教育出版社
50.《精通Visual Basic 6.0》中文版,刘炳文编著,电子工业出版社
51. 邬勇奇,肖述超,刘智敏,计算机与应用化学,2000,vol.17,No.4,377
2.薛群基,徐康,化学进展,2000,431-444
3. Robert D. Miller. Chem. Rev., 1999, vol.99, 7: 1641-1642
4. Feldheim D.L., Metal nanoparticles:Synthesis,Characterization,and Applications ,New York :MARCEL DEEKKER. INC.,2002
5.蔡卫权,陈进富,现代化工,第22卷增刊,2002,34
6.周艳琼,粉末冶金工业,Vol.11.N.o 4,2001,41
7.郑华均,刘华章 浙江化工 2003.34:2
8.蔡元霸、梁玉仓 结构化学,Vol.24,2001,425-438
9.化学世界,2000,11,64
10.阎子峰,纳米催化技术,北京:化学工业出版社,2003,559-600
11.张立德,中国粉体技术,2001,vol.7(5)
12.山本明夫(日),有机金属化学—基础与应用,科学出版社,1997,1-3
13.戚冠发,有机金属化合物化学基础,长春:东北师范大学出版社,1986,204-210
14.易宪武,黄春晖等 无机化学丛书 第七卷 钪、稀土元素,北京:科学出版社,1998,
15.陈晋阳,化学世界,2002,54
16.林河成,稀土,2003,vol.24,No.1,75
17.马莉,福建化工,2002,1,42
18. Mikhail N.Bochkarev,Chem.Rev., 2002,vol.102,No.6,2089-2117
19.Cotton, R,A. Am. Chem. Soc. 1986,108,4657
20.Correhl, H.,organometallics,1995,14,992
21.Seemayer, K,Organometallics, 1995. 14. 4465
22.Gibson,J. K,phys. Chem.,1996,100,15688
23.Heinemann.C,Chem. Ber, 1994,127,1807
24.Chauvin Y,Olivier H.,Saussine L.,Inorg,Chim.Acta,1989,12,13
25.D. M.Izv. Acad. Nank. S. Khim 1997.1667
26.JCPDS(32-481)
27. 王亚军, 冯长根, 王丽琼等,稀土在汽车尾气净化中的应用,工业催化,2000,8 (5): 3-7
28. 李青,环境保护, 1998(4): 19-22
29.顾翼东主编,化学词典,上海:上海辞书出版社,2003,989
30.Esso Research and Eng.Co. (inv.H.E.Ramsden), US Pat.3354 190, 1967.
31.Bogdanovic,B.; Liao,S-J.; Schwickardi,M,; Sidorsky,P.; Spliethoff,B., Angew.Chem.1990, 92; Angew. Chem. Int. Ed. Engl., 1980, 19.
32.Bogdanovic,B.; Chem. Int. Ed. Engl.,1985, 24.
33.刑其毅,徐瑞秋等,基础有机化学 上册,北京:高等教育出版社,1993,126-160
34. 大角泰章(日),金属氢化物的性质与应用,北京:化学工业出版社,1990
35.N.N格林伍德,A.厄恩肖著,曹庭礼等译,元素化学(上),北京:高等教育出版社,1997
36.kirk-othmer,Encyclopedia of chemical thchnology,3rd.Ed., 1980,vol.12, 772
37. 廖世健,自然杂志,1982,5(12),905
38. 易宪武,黄春晖等 无机化学丛书 第七卷 钪、稀土元素,北京:科学出版社,1998
39. E.A.Sullivan and R.C.Wade, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley &Sons, New York, 1980, 3rd Edit, Vol.12.p.772.
40. 申泮文,张靓华等,无机化学丛书 第一卷,北京:科学出版社,1984,203
41. 张文魁,王云刚,稀有金属材料与工程,2002,vol.31,6,432-436
42. Sullivan E. A.,In Kirk-Othmer Encyclopedia of Chemical Technology [M], Vol. 13, 4th Ed., John Wiley & Sons, New York, 1995: 613
43. Borislav Bogdanovic,Angew. Chem.Int. Ed. Engl,1985,24,262-273
44. Fan YinHeng, Wu Meixia, Chin. J. Chem., 2002, vol. 20, 11, 1450
45. Cotton,F.A.,Wiklinson,G.Advanced Inorganic Chemistry,4th Edn.,John Wiley &Sons,New York,1980,250
46. 范荫恒,李伟娜,应用化学,2001,vol.18,5,389-391
47. 张源魁,廖世健,徐筠等,催化学报,1996,17,489
48. 武美霞,辽宁师范大学硕士毕业论文,2003
49.《物理化学实验》(第二版,复旦大学等编),高等教育出版社
50.《精通Visual Basic 6.0》中文版,刘炳文编著,电子工业出版社
51. 邬勇奇,肖述超,刘智敏,计算机与应用化学,2000,vol.17,No.4,377