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1.
采用电弧放电法制备内嵌镧金属富勒烯的原灰,通过改变氦气压力及电流强度来提高内嵌镧金属富勒烯产率。原灰由1,2,4-三氯苯提取并回溶入甲苯后,利用分析型高相液相色谱(HPLC)对提取液中各富勒烯组分进行分析。通过分别衡量3种常见含镧金属富勒烯La@C2v-C82、La@Cs-C82和La2@C80与C84的相对峰面积比,探讨了氦气压力和电流强度等对3种金属富勒烯产率的影响。实验结果表明,氦气压力与电流强度共同决定了金属富勒烯的产率,在(1)低电流高氦气压、(2)中等电流中等氦气压、(3)高电流低氦气压的条件下都可以高产率地获得含镧金属富勒烯。此外,调整电流强度和氦气压力可以改变La@C2v-C82和La@Cs-C82的相对比例。例如,在电流为100、120 A或氦气压为20、35 kPa时,此前认为的"minor"异构体La@Cs-C82的含量甚至高于"major"异构体La@C2v-C82。我们还发现,降低电流强度或减小氦气压力可促进La2@C80的生成,这表明La2@C80与La@C82的形成过程可能是不同的。 相似文献
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利用电弧放电法制备了15N同位素标记的金属氮化物内嵌富勒烯. 制备过程中使用15NH4Cl作为固体氮源, 基于电弧放电方法在氦气气氛中将石墨、金属钪和15NH4Cl高温原子化, 合成得到Sc315N@C80和Sc315N@C78. 利用高效液相色谱法进行分离纯化, 并通过质谱、紫外可见吸收光谱和核磁共振碳谱表征了Sc315N@C80, 验证了15N的成功标记, 还表明合成的Sc315N@C80具有Ih-C80碳笼. 所制备的15N标记的金属氮化物内嵌富勒烯中含有98%以上的15N同位素, 将拓展金属富勒烯材料在同位素示踪等领域的应用. 相似文献
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采用直流电弧法, 以掺有金属合金和B4C粉末的光谱纯石墨棒作为阳极, 在He和NH3混合气氛中进行电弧放电, 首次高产率合成了一系列Gd2@C2n(94≤2n≤142)的大分子双金属富勒烯包合物. 实验证明, 异相物质作为热的载体并同时催化产生了大分子富勒烯金属包合物, 而NH3则抑制了C60和C70等其它富勒烯的生成. 相似文献
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采用对掺入La2O3的石墨棒原位活化并结合交换电极回放方法制备了产率较高的金属富勒烯,并用甲苯温热提取的方法有效地提取的La@C2n,其中La@C71为可溶性金属富勒烯增加了新成员,同时,首次采用解吸电子轰击质谱对提取物进行了表征,讨论了提取物的ESR谱。 相似文献
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内嵌金属富勒烯的笼外化学修饰 总被引:1,自引:0,他引:1
内嵌金属富勒烯以其独特的结构和新奇的性质吸引了众多科学家的目光,对它们进行笼外化学修饰是最近十年来新兴的研究热点,这对于考察内嵌金属富勒烯的结构及化学物理性质并拓宽其应用范围具有重要意义。本文将内嵌金属富勒烯与各种底物的不同作用分类,以反应类型为线索,详细概括了已发表的内嵌金属富勒烯的各种笼外化学反应,包括各种环化反应、内嵌金属富勒烯与杯芳烃及冠醚的自组装、单键相连的衍生物、水溶性衍生物以及用内嵌金属富勒烯填充碳纳米管等。在对各种化学反应阐述的同时,对内嵌金属富勒烯的可能应用也进行了总结,并提出了自己的看法。 相似文献
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高温高压法提取金属富勒烯Lnm@C2nLn=Y, Gd, Tb) 总被引:5,自引:0,他引:5
笼内金属富勒烯以其独特的结构性质和潜在的应用价值而引起了人们极大的注意 [1~ 3] ,但因制备技术复杂、产率低以及将其从伴生的空心富勒烯中分离出来比较困难而使其研究受到很大的限制 .笼内金属富勒烯的分离提取始终是金属富勒烯研究的一个重要分支 .通常的方法是将放电得到的烟炱采用甲苯索氏提取的方法粗提 ,然后用高压液相色谱法分离得到纯品 ,笼内金属富勒烯的产率仅为烟炱的 0 .1 % [4~ 6] .我们改进了常规的提取方法 ,建立了一种新的提取方法—高温高压提取法 .具体的做法是采用甲苯索氏提取法从烟炱中提取出空心富勒烯和少量金… 相似文献
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内嵌混合金属氮化物原子簇富勒烯的发现极大地扩展了内嵌富勒烯家族。内嵌混合金属氮化物原子簇富勒烯是一类新型的内嵌富勒烯,其内嵌物为由2-3种不同的金属组成的氮化物原子簇。本文首先介绍了新型内嵌混合金属氮化物原子簇富勒烯的发现、合成和分离方法,并对目前所分离出来的内嵌混合金属氮化物原子簇富勒烯进行了分类。然后总结了目前所报导的内嵌混合金属氮化物原子簇富勒烯的结构表征手段,对于不同的内嵌混合金属氮化物原子簇富勒烯的分子结构分别进行了阐述。最后着重讨论了内嵌混合金属氮化物原子簇富勒烯的特殊电子性质以及物理和化学性质。本文还对内嵌混合金属氮化物原子簇富勒烯潜在的应用前景作了展望,在内嵌具有不同物理性质的两到三种金属原子的基础上,所形成的内嵌混合金属氮化物原子簇富勒烯有可能兼具不同金属原子各自的性质,从而成为多功能综合的功能材料。 相似文献
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Fullerene molecules have nano-scale cavities in which various metal or metal clusters of different sizes can be embedded to form metallofullerenes with unique core-shell structures. The physical and chemical properties of metallofullerenes can be modified through the interaction between the encapsulated metals and the fullerene cages. As such, the investigation of metallofullerenes with novel structures has been a principal research focus in the field of fullerenes. In this study, we investigated the size matching effect between encapsulated clusters and fullerene cages for the endohedral metal carbonitride clusterfullerenes in order to discover new metallofullerenes. The stability and electronic structure of the metallofullerenes formed by encapsulating M3NC clusters (M = Y, La, Gd) into D2(186)-C96 and D2(35)-C88 fullerenes were studied using quantum chemical calculations. It was found that the fullerene cages formed stable structures by accepting six electrons transferred from the encapsulated clusters. The change in configuration of the encapsulated clusters was clarified by a comparison with the corresponding M3N@C2n metal nitride clusterfullerenes; the size matching effect between M3NC cluster and fullerene cage was elucidated on the basis of the calculated results and previous studies on Sc3NC@Ih(7)-C80. For the D2(186)-C96 fullerene, the Gd3NC cluster was found to have smaller changes in the configuration as compared with the La3NC cluster, proving that Gd3NC is more suitable than La3NC for encapsulation in the D2(186)-C96 fullerene cage. In addition, it was determined that the La3NC cluster requires a large structural change to maintain its planar configuration. For the D2(35)-C88 fullerene cage, the Y3NC cluster is more suitable than Gd3NC for encapsulation owing to the smaller size of the Y3NC cluster. The spatial distribution of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of Gd3NC@D2(186)-C96 were found to be similar to those of Gd3N@D2(186)-C96. However, a unique endohedral cluster-based occupied molecular orbital was found for Gd3NC@D2(186)-C96. This orbital is derived from the interaction between the NC unit and the Gd atoms. The spatial distribution of the HOMO of Y3NC@D2(35)-C88 is similar to that of Y3N@D2(35)-C88, while the LUMO of Y3NC@D2(35)-C88 has a much larger contribution from the endohedral cluster as compared to Y3N@D2(35)-C88. Thus, the addition of a carbon atom in the cluster has a remarkable impact on the electronic structure of the metallofullerenes. With respect to structural characteristics, we found that the three fullerene cages, D2(186)-C96, D2(35)-C88, and Ih(7)-C80, have a uniform distribution of five-membered carbon atom rings; these fullerenes can be greatly stabilized in the form of C2n6- anions. However, the formation mechanism of fullerenes and metallofullerenes, at present, is poorly understood. Based on the structural analysis, we propose a direct mechanism for the formation of fullerenes without the Stone-Wales isomerization, i.e., the rearrangement of five-membered rings through the addition of carbon atoms and the transformation into larger carbon cages while maintaining stable structural units. 相似文献
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Endohedral metallofullerenes Er@ C2n were synthesized using the carbonarc discharge method of activating the Er2O3- containing graphite anode in situ and bask-burning technique. A toluene soxhlet and pyridine high-temperature high-pressure extraction technique were employed for the effective extraction of Er@ C2n. The formation of Er@ C2n was confirmed by LD-TOF and DEIMS characterization. 相似文献
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笼内金属富勒烯的合成与分析 总被引:1,自引:0,他引:1
自1985年,Smalleyr等人首次在飞行时间质谱仪中检测到C60以来,富勒烯碳原子族的研究便不断深入,最初发现的激光蒸发含稀土化合物的石墨只能得到微量的金属富勒烯,仅限于质谱检测,直到1990年,Kratschmer等人采用石墨电子弧放电首次得到宏观量的富勒烯,才使得富勒烯研究进入了实质性的研究阶段。富勒烯及其化合物的分子结构确定对于研究这类化合物无疑是非常重要的,红外光谱、核磁共振、X射线衍射、质谱以及电化学方法都是非常重要的手段。在富勒烯研究中,质谱是相当重要的,在80年代中期的富勒烯以及富勒烯衍生物如金属富勒烯多面体都在质谱中首次发现的。电弧法成功地得到富勒烯后,质谱因其灵敏度高、用量少、简便、快速等优点,成为富勒烯化合物物理化学性能研究以及结构表征工具,其中激光解吸电离为软电离技术只给出化合物分子质量而不产生碎片离子,已成为研究富勒烯首选的重要工具。 相似文献
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采用解析电子轰击质谱对电弧法合成的稀土富勒烯衍生物的提取液进行了质谱分析,有效地检测到富勒烯,稀土富勒烯单电荷、双电荷的分子离子峰。利用同位素贡献确证了某些稀土富勒烯的生成。采用高电流瞬间解析样品,使得谱图中的谱峰强度更加真实地反应出提取液中各组分的相对含量。 相似文献
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Becauseoftheirunusualstructureandmanyexpectednoveloptic,electricandmagneticproperties.endohedralmetallofullerenes(EMFs)haveintenselyattractedtheinterestofbothchemistsandmaterialscientists.TheoriginalyttriunlEMFsweresynthesizedbylaserablation:andarcburningmethod=.UPtonow,onlyY@C,=wasisolatedandpurifiedby'HPLC;inmilligramqLlantitiesandsolllespectroscopicandstructuralanalysesincludingXPSIEXAFS'.STMS.ESR",XRD:andRamalltecllniqtle'havebeenusedtocharacterizeit.However,furtherillvestiga… 相似文献
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两步法提取笼内金属富勒烯 总被引:3,自引:0,他引:3
两步法提取笼内金属富勒烯郝春雁,刘子阳,徐文国,郭兴华,刘淑莹(中国科学院长春应用化学研究所,吉林大学化学系,长春,130022)关键词金属富勒烯,索氏提取,DEI-MS,LDI-MS目前笼内包含金属的富勒烯化合物以其新颖独特的结构和性质而格外引人注... 相似文献
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Dr. Wangqiang Shen Shuaifeng Hu Prof. Xing Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5748-5757
Endohedral metallofullerenes (EMFs), namely fullerenes with metallic species encapsulated inside, represent an ideal platform to investigate metal–metal or metal–carbon interactions at the sub-nanometer scale by means of single-crystal X-ray diffraction (XRD) crystallography. Herein, recent progress in the identification of new structures and unprecedented properties are discussed according to the categories of monometallofullerenes, dimetallofullerenes, carbide clusterfullerenes, and nitride clusterfullerenes. In particular, the dimerization and the cage-isomer dependent oxidation state of the inner metal atom are summarized in terms of pristine monometallofullerenes. Metal–metal bonds involving lanthanide–lanthanides or actinide–actinides are discussed based on both experimental and theoretical studies. The cluster–cage matching and/or mutual selections, as well as the rarely seen M=C double bonds, are discovered in M2C2@C2n, U2C@C80, M2TiC@C80, and Ti3C3@C80. Subsequently, the geometries of different M3N clusters in various cages are discussed, revealing size-matching between the internal M3N cluster and the outer cage induced by the planarity of the cluster. Finally, an outlook regarding the future developments of the molecular structures and applications of EMFs is presented. 相似文献
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金属富勒烯的合成及结构研究是当前富勒烯化学研究的重要内容[1].一些稀土金属元素,如Sc[2]、Y[3]及大部分斓系元素(La、Ce、Nd、Sin、Eu、Gd、Tb、Ho)[4]形成的金属富勒烯已被合成出来.但仍有一些稀土富勒烯的合成尚未见报道,使人们难以对金属富勒烯的形成机制及物化性能作出全面的判断.本文采用原位活化、交换电极回放电弧放电及两步提取法首次得到含锡金属富勒烯.通过空白对比实验确定了Tin@C。怕9生成.对甲苯及毗院提取液的质谱研究表明含镀金属富勒烯具有区别于其它金属富勒烯的特殊的溶解性能,显示出其可能具有独特的… 相似文献