碳点透射电镜表征方法的探究与实践
梁国弘,邹少兰,石 璘,丁哲远,方 卉,翟 勇,刘士新,靳凤民*
(1.天津大学化工学院,大型仪器测试平台,天津300350;2.天津大学地球系统科学学院,天津300072;3.天津大学化工学院,天津300350)
摘 要 碳点(CDs)由于其独特的物理、化学特性,近年来受到科技工作者的广泛关注。透射电镜(TEM)作为材料表征的重要工具之一,能够直观地展示材料微观形态和微区结构。本文以普遍廉价易得、低毒性的生物质材料作为原料制备CDs。针对CDs在TEM表征中制备易团聚、寻样困难、成像衬度低的问题,本文对样品制备方法、TEM观察方法及参数进行优化,探索最佳电镜图像拍摄条件,提出了一种倾斜载网制样、邻位寻样和扫描透射(STEM)成像表征CDs的方法,为CDs的TEM表征工作提供指导思路。
关键词 透射电镜;碳点;样品制备;邻位寻样;图像衬度
中图分类号:TB32;TH742;TB82;TG115.21 文献标识码:B doi:10.3969/j.issn.1000-6281.2023.03.008
Characterization of carbon dots by transmission electron microscope
LIANG Guo-hong1,ZOU Shao-lan1,SHI Lin2,DING Zhe-yuan3,FANG Hui1,ZHAI Yong1,
LIU Shi-xin,JIN Feng-min1*
( 1. Instrument analysis and testing center, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350;
2. School of Earth System Science, Tianjin University, Tianjin 300072;3. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350,China)
Abstract Carbon dots (CDs) have attracted great attention in recent years due to their outstanding physical and chemical properties. As one of the important tools for material characterization, transmission electron microscope (TEM) can be used to characterize the micromorphology and micro-structure of materials. However, it is a great challenge to study carbon dots by TEM, including sample agglomeration, difficulty in finding samples, and low TEM image contrast. In this paper, we optimized the sample preparation, TEM observation and parameters. In order to quickly get high-quality TEM images, we introduced a special sample preparation technique and instrument operation techniques, which include the tilt of the copper grid about 10°, the neighborhood and the scanning transmission electron microscopy(STEM) imaging technique. This method provides a guideline for TEM characterization of CDs.
Keywords transmission electron microscope; carbon dots; specimen preparation; finding sample by neighborhood; image contrast
“全文下载请到同方知网,万方数据库或重庆维普等数据库中下载!”
[1] HE B W, ZHANG Y X, LIU X, et al.In-situ transmission electron microscope techniques for heterogeneous catalysis [J]. CHEMCATCHEM, 2020, 12:1853-1872.
[2] 欧阳,李松达,袁文涛,等.原位透射电镜在金属纳米颗粒氧化研究中的应用[J].电子显微学报, 2021, 40(5):623-634.
[3] 赵彦伟,李蕊,李艺,等.透射电镜在仿硅藻结构的介孔二氧化硅表征和制备中的应用[J].分析仪器, 2015, 2:28-32.
[4] 王乙潜,梁文双.高分辨电子显微学进展及其在材料科学中的应用[J].实验技术与管理, 2010, 27(3):25-28.
[5] 施云峰,薛巍.电子显微技术应用于生物纳米材料表征与测试的研究进展[J].分析测试学报, 2019, 38(5):631-634.
[6] 陈勇,张俊霞,江轶,等.新冠病毒感染机制的透射电镜研究评述[J].实验技术与管理, 2021, 38(12):1-9.
[7]KRIVANEK O L,DELLBY N, HACHTEL J A, et al. Progress in ultrahigh energy resolution EELS [J]. Ultramicroscopy, 2019, 203:60-67.
[8] SUN Y P, ZHOU B, LIN Y, et al. Quantum-sized carbon dots for bright and colorful photoluminescence [J]. Journal of the American Chemical Society, 2006, 128(24):7756-7757.
[9] BAKER S N, BAKER G A. Luminescent carbon nanodots: Emergent nanolights [J]. Angewandte Chemie International Edition, 2010, 49(38):6726-6744.
[10] 张路鹏,张清梅,何松杰,等. 碳点的功能化研究进展[J]. 发光学报, 2022, 43(7):1147-1163.
[11] CAO L, WANG X, MEZIANI M J, et al. Carbon dots for multiphoton bioimaging [J]. Journal of the American Chemical Society, 2007, 129(37):11318-11319.
[12] YU H J, SHI R, ZHAO Y F, et al. Smart utilization of carbon dots in semiconductor photocatalysis [J]. Advanced Materials, 2016, 28(43):9454-9477.
[13] BOURLINOS A B, TRIVIZAS G, KARAKASSIDES M A, et al. Green and simple route toward boron doped carbon dots with significantly enhanced non-linear optical properties[J]. Carbon, 2015,83:173-179.
[14] 章晓中. 电子显微分析[M]. 北京:清华大学出版社, 2006:132.
[15] 柳德橹,权茂华,吴杏芳. 电子显微分析实用方法[M].北京:中国质检出版社, 2018.
[16] 袁莉民,周天阳. 用于扫描电镜观察的水凝胶样品薄层制备技术[J]. 电子显微学报, 2022, 41(3):329-334.
[17] 周武. 石墨烯的低电压扫描透射电子显微学成像研究[J].电子显微学报, 2018, 37(5):524-531.
[18] URBAN K W. Studying atomic structures by aberration-corrected transmission electron microscopy [J]. Science, 2008, 321(5888):506-510.
[19] 袁文涛,李冠星,王勇,等. 透射电镜在纳米材料表面科学中的应用浅析:以二氧化钛为例[J].电子显微学报, 2020, 39(5):613-612.
[20] LIU R L, WU D Q, LIU S H, et al. An aqueous route to multicolor photoluminescent carbon dots using silica spheres as carriers [J]. Angewandte Chemie International Edition, 2009, 48:4598-4601.
[21] BOURLINOS A B, STASSINOPOULOS A, ANGLOS D, et al. Photoluminescent carbogenic dots[J]. Chemistry of Materials, 2008, 20(14):4539-4541.
[22] 刘丽月,曾江涛. 量子点在透射电镜中的电子辐照损伤行为[J]. 电子显微学报, 2022, 41(1):15-19.
[23] 冯远皓,柯小行,隋曼龄. 无机双钙钛矿太阳能电池材料Cs2AgBiBr6在电子束辐照下的降解行为研究[J]. 电子显微学报, 2020, 39(1):1-8.
[24] 王书运,谢英渤,低反差样品电镜图像衬度的提高[J].分析测试技术与仪器, 1997, 3(3):186-189.
[25] 刘志昂,谭青青,渠凤丽.一种碳量子点透射电子显微镜的样品制备方法[J].电子显微学报, 2019, 38(6):685-688.
[26] KONG W H, WU D, LI G L, et al. A facile carbon dots based fluorescent probe for ultrasensitive detection of ascorbic acid in biological fluids via non-oxidation reduction strategy [J]. Talanta, 2017, 165:677-684.
[27] 马秀梅.电子显微学专业课的透射电镜样品制备实习课[J]. 实验室研究与探索, 2021, 40(11):222-224.
[28] ZHANG X, ZHANG Z. Advanced techniques in TEM specimen preparation[M]. Progress in transmission electron microscopy I: Concepts and techniques. Beijing: Tsinghua University Press and Springer-Verlag, 2001:2-52.
[29] 王春省,封振宇. 磁性微纳米材料透射电镜测试的简单制样方法[J]. 实验技术与管理, 2019, 36(8):49-51.
[30] 刘湘花,张彩丽,张俊霞,等. 透射电镜负染色技术常见影响因素与对策[J].临床与实验病理学杂志, 2016, 32(10):1185-1186.
[31]WANG L, WANG Y L, XU T, et al. Gram-scale synthesis of single-crystalline graphene quantum dots with superior optical properties[J]. Nature Communications, 2014, 5:5357.