生物质基碳量子点的绿色合成及其LED应用

doi:10.16085/j.issn.1000-6613.2022-2346

摘要/Abstract

摘要：

各类生态友好型生物质都可以作为绿色碳源制备新型零维碳纳米发光材料碳量子点（CQDs）。本文以农林废弃物、园林绿化垃圾、餐厨垃圾为原料，一步水热法制备生物质基CQDs。采用高分辨透射电镜、拉曼光谱、傅里叶红外光谱、X射线光电子能谱、紫外-可见光吸收光谱、荧光光谱等对各类CQDs进行表征分析，探究生物质种类对CQDs荧光性能的影响规律。实验结果表明：各类生物质基CQDs在紫外光激发下均发出蓝色荧光，农林废弃物制备的CQDs荧光量子产率（QY）普遍较低，鸡蛋壳、梧桐叶和柠檬皮基CQDs荧光QY分别达到9.29%、9.03%和4.51%，这三种生物质及制备的CQDs中均含有N或S元素，说明含有N或S元素的天然生物质有助于提高CQDs的荧光QY。将生物质基CQDs制作荧光粉，制成的发光二极管（LED）的光学性能指标与CQDs的荧光性能呈现出一定的映射关系，相关结论为生物质基CQDs的绿色合成及LED的绿色制备提供了有力指导。

关键词: 生物质, 纳米材料, 碳量子点, 荧光量子产率, 复合材料, 发光二极管

Abstract:

All kinds of eco-friendly biomass can be used as green carbon source to prepare carbon quantum dots (CQDs), a novel zero-dimensional carbon nano luminescent material. In this paper, biomass-based CQDs were prepared by one-step hydrothermal method using agricultural and forestry waste, garden and kitchen waste as raw materials. High resolution transmission electron microscopy, Raman spectroscopy, Fourier infrared spectroscopy, X-ray photoelectron spectroscopy, UV-visible absorption spectrum and fluorescence spectroscopy were used to characterize various types of CQDs, and to explore the influence of biomass on the fluorescence properties of CQDs. The experimental results showed that: All kinds of biomass-based CQDs emit blue fluorescence under UV excitation, and the fluorescence quantum yield (QY) of CQDs prepared by agricultural and forestry waste was generally low. The fluorescence QYs of CQDs prepared by egg shell, Chinese parasol leaves and lemon peel reached 9.29%, 9.03% and 4.51%, respectively. The three kinds of biomass and the prepared CQDs all contained N or S element. It showed that the biomass naturally containing N or S elements was helpful to improve the fluorescence QY of CQDs. By making phosphors from biomass-based CQDs, the optical properties of the light-emitting diode (LED) produced showed a certain mapping relationship with the fluorescence properties of CQDs. Relevant conclusions provide strong guidance for the green synthesis of biomass-based CQDs and the green preparation of LED.

Key words: biomass, nanomaterials, carbon quantum dots, fluorescence quantum yield, composites, light emitting diodes

中图分类号:

X712

曹瑾, 朱玲莉, 沈德魁. 生物质基碳量子点的绿色合成及其LED应用[J]. 化工进展, 2023, 42(11): 5852-5860.

CAO Jin, ZHU Lingli, SHEN Dekui. Green synthesis of biomass-based carbon quantum dots and LED application[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5852-5860.

图/表 10

图1 各类生物质基CQDs的荧光QY

图2 三种生物质基CQDs的光学性质

图3 三种生物质的FTIR图谱

图4 三种生物质基CQDs的TEM图像和粒径分布

图5 三种生物质基CQDs的Raman光谱

图6 三种生物质基CQDs的FTIR图谱

图7 三种生物质基CQDs的XPS扫描和C 1s、O 1s、N 1s和S 2p的高分辨率XPS图谱

表1 三种生物质基CQDs的元素组成

样品名	O/C	N/C	S/C
CQDs-1	0.54	0.06	—
CQDs-2	0.33	0.04	—
CQDs-3	0.34	0.17	0.02

图8 生物质基CQDs制作的LED器件

表2 蓝光LED的性能指标

样品名	照度/lx	CIE坐标
CQDs-1	7.13	（0.17，0.06）
CQDs-2	3.33	（0.16，0.06）
CQDs-3	7.84	（0.16，0.10）

参考文献 23

1	LI Shuo, LI Lin, TU Hanyu, et al. The development of carbon dots: From the perspective of materials chemistry[J]. Materials Today, 2021, 51: 188-207.
2	高雪, 孙靖, 刘晓, 等. 碳量子点的合成、性质及应用[J]. 化工进展, 2017, 36(5): 1734-1742.
	GAO Xue, SUN Jing, LIU Xiao, et al. Carbon quantum dots: Synthesis, properties and applications[J]. Chemical Industry and Engineering Progress, 2017, 36(5): 1734-1742.
3	MENG Weixue, BAI Xue, WANG Boyang, et al. Biomass-derived carbon dots and their applications[J]. Energy & Environmental Materials, 2019, 2(3): 172-192.
4	杨培. 荧光可调半纤维素基碳点的合成及发光机理研究[D]. 南京: 南京林业大学, 2020.
	YANG Pei. Synthesis and luminescence mechanism of fluorescent tunable hemicellulose-based carbon dots[D]. Nanjing: Nanjing Forestry University, 2020.
5	LIU Yingshuai, ZHAO Yanan, ZHANG Yuanyuan. One-step green synthesized fluorescent carbon nanodots from bamboo leaves for copper(Ⅱ) ion detection[J]. Sensors and Actuators B: Chemical, 2014, 196: 647-652.
6	DIAO Haipeng, LI Tingting, ZHANG Rong, et al. Facile and green synthesis of fluorescent carbon dots with tunable emission for sensors and cells imaging[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018, 200: 226-234.
7	SINGH Harpreet, BAMRAH Amy, KHATRI Madhu, et al. One-pot hydrothermal synthesis and characterization of carbon quantum dots (CQDs)[J]. Materials Today: Proceedings, 2020, 28: 1891-1894.
8	ATCHUDAN Raji, JEBAKUMAR IMMANUEL EDISON Thomas Nesakumar, SHANMUGAM Mani, et al. Sustainable synthesis of carbon quantum dots from banana peel waste using hydrothermal process for in vivo bioimaging[J]. Physica E: Low-Dimensional Systems and Nanostructures, 2021, 126: 114417.
9	YUAN Ming, ZHONG Ruibo, GAO Haiyang, et al. One-step, green, and economic synthesis of water-soluble photoluminescent carbon dots by hydrothermal treatment of wheat straw, and their bio-applications in labeling, imaging, and sensing[J]. Applied Surface Science, 2015, 355: 1136-1144.
10	MENG Weixue, WANG Boyang, AI Lin, et al. Engineering white light-emitting diodes with high color rendering index from biomass carbonized polymer dots[J]. Journal of Colloid and Interface Science, 2021, 598: 274-282.
11	WANG Cunjin, SHI Huanxian, YANG Min, et al. Facile synthesis of novel carbon quantum dots from biomass waste for highly sensitive detection of iron ions[J]. Materials Research Bulletin, 2020, 124: 110730.
12	SHAMSIPUR Mojtaba, BARATI Ali, KARAMI Sara. Long-wavelength, multicolor, and white-light emitting carbon-based dots: Achievements made, challenges remaining, and applications[J]. Carbon, 2017, 124: 429-472.
13	苗湘. 碳点的光学调控及其应用研究[D]. 长春: 中国科学院大学(中国科学院长春光学精密机械与物理研究所), 2018.
	MIAO Xiang. Synthesis of carbons dots with tunable optical properties and their applications[D]. Changchun: Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 2018.
14	ZHENG Kun, LI Xu, CHEN Mingjun, et al. Controllable synthesis highly efficient red, yellow and blue carbon nanodots for photo-luminescent light-emitting devices[J]. Chemical Engineering Journal, 2020, 380: 122503.
15	JING Shuangshuang, ZHAO Yushuang, SUN Runcang, et al. Facile and high-yield synthesis of carbon quantum dots from biomass-derived carbons at mild condition[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(8): 7833-7843.
16	ZHAO Siyu, SONG Xueping, CHAI Xinyu, et al. Green production of fluorescent carbon quantum dots based on pine wood and its application in the detection of Fe³⁺ [J]. Journal of Cleaner Production, 2020, 263: 121561.
17	DAI Ruoyu, CHEN Xipao, OUYANG Ning, et al. A pH-controlled synthetic route to violet, green, and orange fluorescent carbon dots for multicolor light-emitting diodes[J]. Chemical Engineering Journal, 2022, 431: 134172.
18	ZHANG Haimin, KANG Shenghong, WANG Guozhong, et al. Fluorescence determination of nitrite in water using prawn-shell derived nitrogen-doped carbon nanodots as fluorophores[J]. ACS Sensors, 2016, 1(7): 875-881.
19	ZHU Lingli, SHEN Dekui, LIU Qian, et al. Sustainable synthesis of bright green fluorescent carbon quantum dots from lignin for highly sensitive detection of Fe³⁺ ions[J]. Applied Surface Science, 2021, 565: 150526.
20	WANG Junli, ZHENG Jingxia, YANG Yongzhen, et al. Tunable full-color solid-state fluorescent carbon dots for light emitting diodes[J]. Carbon, 2022, 190: 22-31.
21	JI Chunyu, HAN Qiurui, ZHOU Yiqun, et al. Phenylenediamine-derived near infrared carbon dots: The kilogram-scale preparation, formation process, photoluminescence tuning mechanism and application as red phosphors[J]. Carbon, 2022, 192: 198-208.
22	LI Huiyu, ZHANG Zhaoxuan, DING Jie, et al. Diamond-like carbon structure-doped carbon dots: A new class of self-quenching-resistant solid-state fluorescence materials toward light-emitting diodes[J]. Carbon, 2019, 149: 342-349.
23	杜勤. 暖白光LED用高荧光量子产率长波长碳量子点的制备[D]. 太原: 太原理工大学, 2018.
	DU Qin. The synthesis of long wavelength fluorescent carbon dots with high quantum yield for warm white LED[D]. Taiyuan: Taiyuan University of Technology, 2018.

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