15N同位素标记的金属氮化物内嵌富勒烯的合成与表征

doi:10.6023/A22020087

化学学报 ›› 2022, Vol. 80 ›› Issue (7): 874-878.DOI: 10.6023/A22020087 上一篇下一篇

研究论文

¹⁵N同位素标记的金属氮化物内嵌富勒烯的合成与表征

邱玲^a, 梁家艺^a, 张竹霞^a^,^b^,^c^,^*(), 王太山^d^,^*()

a 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
b 太原理工大学化学学院太原 030024
c 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
d 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

投稿日期:2022-02-25 发布日期:2022-04-26
通讯作者: 张竹霞, 王太山
基金资助:
国家自然科学基金(51832008); 国家自然科学基金(52022098); 国家自然科学基金(51972309); 中科院青促会(Y201910); 固体表面物理化学国家重点实验室(厦门大学)开放课题(201928); 山西省自然科学基金(201901D111109)

Synthesis and Characterizations of ¹⁵N Isotope Labeling Metal Nitride Clusterfullerene

Ling Qiu^a, Jiayi Liang^a, Zhuxia Zhang^a^,^b^,^c(), Taishan Wang^d()

a Key Laboratory of Interface Science and Engineering in Advanced Materials Ministry of Eduacation, Taiyuan University of Technology, Taiyuan 030024, China
b College of Chemistry, Taiyuan University of Technology, Taiyuan 030024, China
c Key Laboratory of Magnetic Molecules and Magnetic Information Materials Ministry of Eduacation, Shanxi Normal University, Taiyuan 030000, China
d CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, China

Received:2022-02-25 Published:2022-04-26
Contact: Zhuxia Zhang, Taishan Wang
Supported by:
National Natural Science Foundation of China(51832008); National Natural Science Foundation of China(52022098); National Natural Science Foundation of China(51972309); Youth Innovation Promotion Association of Chinese Academy of Sciences(Y201910); Opening Project of PCOSS, Xiamen University(201928); Natural Science Foundation of Shanxi Province(201901D111109)

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摘要/Abstract

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I_h-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.

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

In this work, we prepared the ¹⁵N-labeled metal nitride clusterfullerene by arc discharge method. In the synthetic process, scandium metal, graphite powder, and ¹⁵NH₄Cl were atomized by arc discharge method under helium atmosphere with ¹⁵NH₄Cl as solid nitrogen source, and finally Sc₃¹⁵N@C₈₀ and Sc₃¹⁵N@C₇₈ were obtained. Sc₃¹⁵N@C₈₀ 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 ¹³C NMR. These results demonstrate the successful labeling of ¹⁵N and also illustrate that the prepared Sc₃¹⁵N@C₈₀ has an I_h-C₈₀ cage. The prepared ¹⁵N-labeled metal nitride clusterfullerenes contain more than 98% of the ¹⁵N 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 Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈ were obtained. Mass spectrometry was used to characterize the molecular weight of Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈. According to the isotopic distributions of Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈ in mass spectra, their molecular weight values have increased by 1 compared to those of unlabeled Sc₃N@C₈₀-I_h and Sc₃N@C₇₈, revealing the successful labeling of isotope ¹⁵N on the Sc₃N cluster. At the same time, we added Y₃N@C₈₀ as an internal standard into Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈ samples to further confirm the labeling of ¹⁵N atom on the Sc₃N cluster. Moreover, the UV-Vis absorption spectrum showed that the absorption of Sc₃¹⁵N@C₈₀ begins at 820 nm, and the lowest energy transition was observed at 735 nm. Based on the absorption onset, the optical energy gap of Sc₃¹⁵N@C₈₀ can be calculated, which is about 1.51 eV. According to the reported UV-Vis absorption spectra in literature, the carbon cage of the isolated Sc₃¹⁵N@C₈₀ can be characterized as I_h-symmetry. The carbon nuclear magnetic resonance spectroscopy (¹³C NMR) was executed by dissolving Sc₃¹⁵N@C₈₀ in 1,2-dichlorobenzene-d₄ at 293 K. The ¹³C NMR spectrum consists of only two NMR lines of chemical shifts of 143.60 and 136.37 with an intensity ratio of 3:1. This is a characteristic ¹³C NMR spectrum of the I_h-symmetric C₈₀ carbon cage.

Key words: metal nitride clusterfullerenes, isotope labeling, solid nitrogen source, arc-discharge method, rare earth scandium

引用此文

邱玲, 梁家艺, 张竹霞, 王太山. ¹⁵N同位素标记的金属氮化物内嵌富勒烯的合成与表征[J]. 化学学报, 2022, 80(7): 874-878.

Ling Qiu, Jiayi Liang, Zhuxia Zhang, Taishan Wang. Synthesis and Characterizations of ¹⁵N Isotope Labeling Metal Nitride Clusterfullerene[J]. Acta Chimica Sinica, 2022, 80(7): 874-878.

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图/表 5

图1. 基于直流电弧放电法, 用15NH4Cl作为固体氮源合成钪基氮化物内嵌富勒烯. Sc315N@C2n和C2n分别代表同位素标记的钪基氮化物内嵌富勒烯(Sc315N@C80, Sc315N@C78等)和空笼富勒烯(C60, C70, C76, C78, C84等)

Figure 1. Based on the dc-arc discharge method, 15NH4Cl was used as an inorganic solid nitrogen source to synthesize Sc-based metal nitride clusterfullerenes. Sc315N@C2n and C2n represent the isotope-labeled Sc-based metal nitride clusterfullerenes (Sc315N@C80, Sc315N@C78) and hollow fullerenes (C60, C70, C76, C78, C84, etc.), respectively

图2. (a)纯Sc315N@C80的MALDI-TOF质谱图. (b) Sc315N@C80实验中的同位素分布图. (c) Y3N@C80和Sc315N@C80混合后的MALDI-TOF质谱图. 插图是它们各自的分子结构图, 在碳笼中C是灰色; 在内嵌团簇中15N是青色, Sc是洋红色, 14N是蓝色, Y是绿色

Figure 2. (a) MALDI-TOF mass spectrum of pure Sc315N@C80. (b) Isotope distribution map of Sc315N@C80. (c) MALDI-TOF mass spectrum of Y3N@C80 and Sc315N@C80 mixture. The insets show their respective molecular structures. In the carbon cage, C is gray; in the encaged cluster, 15N is cyan, Sc is magenta, 14N is blue, and Y is green

样品	实验同位素峰质荷比	模拟同位素峰质荷比
Sc₃¹⁵N@C₈₀	1110.00, 1111.00, 1112.02, 1113.02, 1114.02	1109.89, 1110.89, 1111.89, 1112.89, 1113.89
Sc₃¹⁵N@C₇₈	1086.00, 1087.00, 1088.02, 1089.02, 1090.02	1085.89, 1086.89, 1087.89, 1088.89, 1089.89
Y₃N@C₈₀	1241.84, 1242.84, 1243.86, 1244.86, 1245.86	1241.73, 1242.73, 1243.73, 1244.73, 1245.73

表1. Sc315N@C80, Sc315N@C78, Y3N@C80实验的和模拟的同位素峰质荷比

Table 1. The experimental and simulated isotope peak mass-to-charge ratio of Sc315N@C80, Sc315N@C78 and Y3N@C80

图3. (a)纯Sc315N@C78的MALDI-TOF质谱图. (b) Sc315N@C78实验中的同位素分布图. (c) Y3N@C80和Sc315N@C78混合后的MALDI-TOF质谱图. 插图是它们各自的分子结构图, 在碳笼中C是灰色; 在内嵌团簇中15N是青色, Sc是洋红色, 14N是蓝色, Y是绿色

Figure 3. (a) MALDI-TOF mass spectrum of pure Sc315N@C78. (b) Isotope distribution map of Sc315N@C78. (c) The MALDI-TOF mass spectrum of Y3N@C80 and Sc315N@C78 mixture. The insets show their respective molecular structures. In the carbon cage, C is gray; in the encaged cluster, 15N is cyan, Sc is magenta, 14N is blue, and Y is green

图4. (a) Sc315N@C80的紫外可见吸收光谱. (b) Sc315N@C80的核磁共振碳谱图. 插图为两条谱线的积分面积, 左右谱线的面积积分分别为68279.89, 22795.17, 谱线位移强度比为3∶1

Figure 4. (a) The UV-Vis absorption spectrum of Sc315N@C80. (b) Carbon NMR spectrum of Sc315N@C80. The inset is the integral area of the two spectral lines. The area integrals of the left and right spectral lines are 68279.89 and 22795.17. The spectral line displacement intensity ratio is 3∶1

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¹⁵N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 ¹⁵N Isotope Labeling Metal Nitride Clusterfullerene

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