^(15)N同位素标记的金属氮化物内嵌富勒烯的合成与表征  

Synthesis and Characterizations of ^(15)N Isotope Labeling Metal Nitride Clusterfullerene

作　　者：邱玲 梁家艺 张竹霞[1,2,3] 王太山 Qiu Ling;Liang Jiayi;Zhang Zhuxia;Wang Taishan(Key Laboratory of Interface Science and Engineering in Advanced Materials Ministry of Eduacation,Taiyuan University of Technology,Taiyuan 030024,China;College of Chemistry,Taiyuan University of Technology,Taiyuan 030024,China;Key Laboratory of Magnetic Molecules and Magnetic Information Materials Ministry of Eduacation,Shanxi Normal University,Taiyuan 030000,China;CAS Key Laboratory of Molecular Nanostructure and Nanotechnology,Institute of Chemistry Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]太原理工大学新材料界面科学与工程教育部重点实验室,太原030024 [2]太原理工大学化学学院,太原030024 [3]山西师范大学磁性分子与磁信息材料教育部重点实验室,太原030000 [4]中国科学院化学研究所分子纳米结构与纳米技术重点实验室,北京100190

出　　处：《化学学报》2022年第7期874-878,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.51832008,52022098,51972309);中科院青促会(No.Y201910);固体表面物理化学国家重点实验室(厦门大学)开放课题(No.201928);山西省自然科学基金(No.201901D111109)资助项目。

摘　　要：利用电弧放电法制备了^(15)N同位素标记的金属氮化物内嵌富勒烯. 制备过程中使用^(15)NH_(4)Cl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^(15)NH_(4)Cl高温原子化, 合成得到Sc3^(15)N@C_(80)和Sc3^(15)N@C_(78). 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Sc3^(15)N@C_(80), 验证了^(15)N的成功标记, 还表明合成的Sc3^(15)N@C_(80)具有I_(h)-C_(80)碳笼. 所制备的^(15)N标记的金属氮化物内嵌富勒烯中含有98%以上的^(15)N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.In this work, we prepared the ^(15)N-labeled metal nitride clusterfullerene by arc discharge method. In the synthetic process, scandium metal, graphite powder, and ^(15)NH_(4)Cl were atomized by arc discharge method under helium atmosphere with ^(15)NH_(4)Cl as solid nitrogen source, and finally Sc3^(15)N@C_(80) and Sc3^(15)N@C_(78) were obtained. Sc3^(15)N@C_(80) was isolated by high-performance liquid chromatography (HPLC) and characterized by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV-Vis absorption spectra, and ^(13)C NMR. These results demonstrate the successful labeling of ^(15)N and also illustrate that the prepared Sc3^(15)N@C_(80) has an I_(h)-C_(80) cage. The prepared ^(15)N-labeled metal nitride clusterfullerenes contain more than 98% of the ^(15)N isotope, which will expand the application fields of metallofullerene materials such as isotope tracing. In detail, clusterfullerenes were separated from hollow fullerenes by multistage HPLC. And then pure samples of Sc3^(15)N@C_(80)-I_(h) and Sc3^(15)N@C_(78) were obtained. Mass spectrometry was used to characterize the molecular weight of Sc3^(15)N@C_(80)-I_(h) and Sc3^(15)N@C78. According to the isotopic distributions of Sc3^(15)N@C_(80)-I_(h) and Sc3^(15)N@C_(78) in mass spectra, their molecular weight values have increased by 1 compared to those of unlabeled Sc_(3)N@C_(80)-I_(h) and Sc_(3)N@C_(78), revealing the successful labeling of isotope ^(15)N on the Sc_(3)N cluster. At the same time, we added Y_(3)N@C_(80) as an internal standard into Sc3^(15)N@C_(80)-I_(h) and Sc3^(15)N@C_(78) samples to further confirm the labeling of ^(15)N atom on the Sc_(3)N cluster. Moreover, the UV-Vis absorption spectrum showed that the absorption of Sc3^(15)N@C_(80) begins at 820 nm, and the lowest energy transition was observed at 735 nm. Based on the absorption onset, the optical energy gap of Sc3^(15)N@C_(80) can be calculated, which is about 1.51 eV. According to the reported UV-Vis absorption spectra in literature, t

关 键 词：金属富勒烯 同位素标记 固体氮源 电弧放电法 稀土钪 

分 类 号：O652[理学—分析化学] O611.6[理学—化学]