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研究生: 張齡元
Ricky Lucano Chandra Prayogo
論文名稱: 微電漿輔助石墨烯量子點合成及其過氧化氫及鈷離子感測
Microplasma-assisted Synthesis of Graphene Quantum Dots for Detection of H2O2 and Cobalt (II) ion
指導教授: 江偉宏
Wei-Hung Chiang
口試委員: 邱昱誠
Yu-Cheng Chiu
郭霽慶
Chi-Ching Kuo
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2021
畢業學年度: 109
語文別: 英文
論文頁數: 99
中文關鍵詞: 石墨烯量子點微電漿金子感測器
外文關鍵詞: Microplasma, cobalt ion sensing, peroxidase-like mimetic activity, hydrogen peroxide sensing
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  • 石墨烯量子点是最近出现的一种碳基材料,因其光学特性、带隙可调、生物相容性、低毒性等显着特性而备受关注。由于量子限制效应,石墨烯量子点还具有光致发光特性;它还可以通过调整表面官能团、粒径等参数进行修饰。除了其光致发光特性外,石墨烯量子点还可以模拟类似过氧化物酶的活性,可用于检测过氧化氢。
    合成石墨烯量子点的一些常用方法是水热法、氧化裂解、热解或碳化。然而,这种方法存在合成时间长、反应温度高等缺点,因为它需要达到热平衡才能产生石墨烯量子点。在这项研究中,常压微等离子体用于在室温和常压下以蔗糖为前驱体合成石墨烯量子点。大气压微等离子体可以更快地达到热平衡,因为它发射高能量的电子作为其驱动力,因此与其他常规方法相比,微等离子体具有更快的反应动力学。
    在这项研究中,石墨烯量子点可以检测0-4 M 之间的钴离子,最低检测到0.01427 M。这些石墨烯量子点还用于检测 0.02-1.80 M 之间的过氧化氢,最低检测值为 0.02 M。


    Graphene quantum dots is a recently emerged carbon-based material and attracted a lot of attention for their notable properties such as optical property, tunable bandgap, biocompatibility, low toxicity, etc. Graphene quantum dots also have a photoluminescence property due to the quantum confinement effect; it also can be modified by adjusting the parameter of surface functional groups, particle size, etc. Besides its photoluminescence property, graphene quantum dots also can mimic a peroxidase-like activity which can be used to detect hydrogen peroxide.
    Some of the common methods to synthesize graphene quantum dots are the hydrothermal method, oxidative cleavage, pyrolysis, or carbonization. However, this method has disadvantages such as long synthesis time, high-temperature reaction, because it needs to reach a thermal equilibrium to produce the graphene quantum dots. In this research, an atmospheric pressure microplasma was used to synthesis graphene quantum dots with sucrose as a precursor at room temperature and atmospheric pressure. An atmospheric pressure microplasma can reach thermal equilibrium faster because it shooting high energy of electrons as its driving force, so the microplasma has a faster reaction kinetic compared to the other conventional methods.
    In this research, the graphene quantum dots can detect cobalt ions between 0-4 M with the lowest of detection at 0.01427 M. These graphene quantum dots are also used to detect hydrogen peroxide between 0.02-1.80 M with the lowest of detection at 0.02 M.

    1. Introduction………………………………………………………………………………1 1.1. Graphene quantum dots…………………………………………………………….1 1.1.1. Synthesis method…………………………………………………………3 1.1.2. Photoluminescence……………………………………………………….6 1.2. Non thermal microplasma method ………………………………………………..13 1.3. Photoluminescence sensing (PL sensing) …………………………………............16 1.3.1. GQD as a sensor…………………………………………………............17 1.3.2. Heavy metal sensing…………………………………………………….21 1.3.3. Chelation enhanced fluorescence………………………………………23 1.4. Peroxidase mimetic activity for H2O2 sensin………………………………………25 1.4.1. Peroxidase mimetic activity…………………………………………….26 2. Experimental procedure……………………………………………………………………32 2.1. Chemicals and materials …………………………………………………………...32 2.2. Characterization methods………………………………………………………….32 2.2.1. Raman spectroscopy……………………………………………………32 2.2.2. Ultraviolet visible spectroscopy………………………………………...33 2.2.3. Photoluminescence spectroscopy………………………………………33 2.3. GQD synthesis by microplasma……………………………………………………34 2.3.1. Synthesis of GQD………………………………………………………..34 2.4. PL sensing experiment………………………………………………………….......35 2.5. H2O2 sensing experiment……………………………………………………………35 2.6. Peroxidase mimetic activity of GQD……………………………………………….35 3. Result and Discussion ………………………………………………………………………36 3.1. Characterization of GQDs………………………………………………………...36 3.1.1. Synthesis of GQD by microplasma………………………….......……..36 3.1.2. UV-Vis spectroscopy…………………………….............................…...38 3.1.3. Photoluminescence spectroscopy (PL)………………………………...40 3.1.4. Raman spectroscopy……………………………………………………46 3.1.5. FTIR spectra of GQDs.............................................................................50 3.2. PL sensing using GQD……………………………………………………………..52 3.2.1. Co2+ ion sensing using GQD……………………………………………52 3.3. H2O2 sensing using GQDs…………………………………………………………63 3.3.1. Study of peroxidase mimetic catalytic activity of GQDs……………..63 3.3.2. TMB oxidation by H2O2 without catalyst..............................................72 3.3.3. TMB oxidation by H2O2 without catalyst..……………………………73 4. Conclusion…………………………………………………………………………………..76 5. Reference……………………………………………………………………………………77

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