土豆基碳量子点的制备、Mn掺杂及在Ag+检测中的应用

摘要/Abstract

摘要： 以土豆为碳源采用水热法合成了发光碳量子点(CQDs),向体系中加入碳酸锰,合成了锰掺杂的CQDs(Mn-CQDs)。用透射电镜、X射线衍射仪、X射线光电子能谱、紫外-可见吸收光谱、荧光光谱、红外光谱等对样品进行了表征。结果表明:CQDs和Mn-CQDs为球状,平均粒径3~5 nm;Mn掺杂增强了CQDs的荧光强度及稳定性;CQDs和Mn-CQDs最大激发波长分别为435 nm、395 nm,对应的发射波长分别为525 nm、465 nm。将CQDs、Mn-CQDs用于金属离子检测,它们都对Ag⁺具有很好的选择性,对Ag⁺的检测限分别为0.064 μmol/L、0.027 μmol/L,表明CQDs、Mn-CQDs可应用于水介质中Ag⁺的痕量检测,Mn-CQDs具有更高的灵敏度。

关键词: 碳量子点, 土豆基碳量子点, 水热法, Mn掺杂, 痕量检测, 银离子检测

Abstract: In this study, carbon quantum dots (CQDs) were prepared using potato as carbon source via hydrothermal method, and then Mn-doped CQDs (Mn-CQDs) were prepared by the addition of manganese carbonate as dopant in the reaction system. CQDs and Mn-CQDs were characterized by transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), UV-Vis absorption spectroscopy, photoluminescence (PL) spectroscopy, and infrared spectrometer. The results show that CQDs and Mn-CQDs are spherical with an average particle size of 3 nm to 5 nm. Mn doping enhanced the intensity and stability of photoluminescence of CQDs. The maximum excitation wavelengths of CQDs and Mn-CQDs are 435 nm and 395 nm, and the corresponding emission wavelengths are 525 nm and 465 nm, respectively. In the application of the detection of metal ions, both CQDs and Mn-CQDs exhibit good selectivity to Ag⁺, and the low detection limits of CQDs and Mn-CQDs to Ag⁺ are 0.064 μmol/L and 0.027 μmol/L, respectively, indicating the relatively high sensitivity of Mn-CQDs in the trace detection of Ag⁺compared to CQDs.

Key words: carbon quantum dot, potato-based carbon quantum dot, hydrothermal method, Mn doping, trace detection, Ag⁺detecting

中图分类号:

X832
O657.3

李家耀, 韩维杰, 杨周平, 施扬范, 卢世平, 刘新梅. 土豆基碳量子点的制备、Mn掺杂及在Ag⁺检测中的应用[J]. 人工晶体学报, 2021, 50(11): 2093-2102.

LI Jiayao, HAN Weijie, YANG Zhouping, SHI Yangfan, LU Shiping, LIU Xinmei. Synthesis of Potato-Based Carbon Quantum Dots, Mn Doping and Their Application in Ag⁺ Detection[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(11): 2093-2102.

参考文献

[1] ZHANG Y W, YE A Y, YAO Y W, et al. A sensitive near-infrared fluorescent probe for detecting heavy metal Ag⁺ in water samples[J]. Sensors, 2019, 19(2): 247.
[2] 周敏,陈志风,罗晓伟,等.Mn(Ⅱ)-CdTe量子点荧光猝灭法测定Ag⁺含量[J].西北师范大学学报(自然科学版),2020,56(6):63-68.
ZHOU M, CHEN Z F, LUO X W, et al. Fluorescence quenching of Mn(Ⅱ)-doped CdTe quantum dots for the determination of silver ions[J]. Journal of Northwest Normal University (Natural Science), 2020, 56(6): 63-68(in Chinese).
[3] 苗向阳,王孝英,朱钦舒.基于金纳米颗粒聚集的高灵敏Ag⁺电致化学发光生物传感器[J]. 南京师大学报(自然科学版), 2020, 44(3): 63-70.
MIAO X Y, WANG X Y, ZHU Q S. Highly sensitive Ag⁺ ECL biosensor based on gold nanoparticles aggregation[J]. Journal of Nanjing Normal University (Natural Science Edition), 2020, 43(3): 63-70(in Chinese).
[4] 魏胤,公维磊,杨金玲,等.基于酶辅助信号放大的纳米石墨传感器检测银离子的研究[J].化学研究与应用,2020,32(12):2245-2250.
WEI Y, GONG W L, YANG J L, et al. Research on nano-graphite sensor for silver ion detection based on enzyme-assisted signal amplification[J]. Chemical Research and Application, 2020, 32(12): 2245-2250(in Chinese).
[5] 师海雄,吴贵渊,李乔,等.基于水溶性柱[5]芳烃主体的合成及Ag⁺识别性能研究[J].兰州文理学院学报(自然科学版),2020,34(6):45-50.
SHI H X, WU G Y, LI Q, et al. Synthesis and ag⁺ recognition performance of pillar [5] arene based on water soluble column[J]. Journal of Lanzhou University of Arts and Science (Natural Science Edition), 2020, 34(6): 45-50(in Chinese).
[6] MENG W X, BAI X, WANG B Y, et al. Biomass-derived carbon dots and their applications[J]. Energy & Environmental Materials, 2019, 2(3): 172-192.
[7] RANI U A, NG L Y, NG C Y, et al. A review of carbon quantum dots and their applications in wastewater treatment[J]. Advances in Colloid and Interface Science, 2020, 278: 102124.
[8] 张琼,丁光月,王雅文,等.宽光谱响应CQDs/TiO₂复合材料的制备及其光催化活性[J].人工晶体学报,2018,47(6):1113-1118.
ZHANG Q, DING G Y, WANG Y W, et al. Preparation and photocatalytic activity of CQDs/TiO₂ composites with wide spectral response[J]. Journal of Synthetic Crystals, 2018, 47(6): 1113-1118(in Chinese).
[9] NAIK V M, GUNJAL D B, GORE A H, et al. Quick and low cost synthesis of sulphur doped carbon dots by simple acidic carbonization of sucrose for the detection of Fe³⁺ ions in highly acidic environment[J]. Diamond and Related Materials, 2018, 88: 262-268.
[10] LIU G H, JIA H S, LI N, et al. High-fluorescent carbon dots (CDs) originated from China grass carp scales (CGCS) for effective detection of Hg(Ⅱ) ions[J]. Microchemical Journal, 2019, 145: 718-728.
[11] SINGH H, BAMRAH A, KHATRI M, et al. One-pot hydrothermal synthesis and characterization of carbon quantum dots (CQDs)[J]. Materials Today: Proceedings, 2020, 28: 1891-1894.
[12] DAS R, BANDYOPADHYAY R, PRAMANIK P. Carbon quantum dots from natural resource: a review[J]. Materials Today Chemistry, 2018, 8: 96-109.
[13] ATCHUDAN R, EDISON T N J I, ASEER K R, et al. Hydrothermal conversion of Magnolia liliiflora into nitrogen-doped carbon dots as an effective turn-off fluorescence sensing, multi-colour cell imaging and fluorescent ink[J]. Colloids and Surfaces B: Biointerfaces, 2018, 169: 321-328.
[14] PRANEERAD J, THONGSAI N, SUPCHOCKSOONTHORN P, et al. Multipurpose sensing applications of biocompatible radish-derived carbon dots as Cu²⁺ and acetic acid vapor sensors[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 211: 59-70.
[15] ARUMUGAM N, KIM J. Synthesis of carbon quantum dots from Broccoli and their ability to detect silver ions[J]. Materials Letters, 2018, 219: 37-40.
[16] ZHAO X Y, LIAO S, WANG L M, et al. Facile green and one-pot synthesis of purple perilla derived carbon quantum dot as a fluorescent sensor for silver ion[J]. Talanta, 2019, 201: 1-8.
[17] XU J Y, ZHOU Y, LIU S X, et al. Low-cost synthesis of carbon nanodots from natural products used as a fluorescent probe for the detection of ferrum(iii) ions in lake water[J]. Analytical Methods, 2014, 6(7): 2086.
[18] OMER K M, TOFIQ D I, GHAFOOR D D. Highly photoluminescent label free probe for Chromium (Ⅱ) ions using carbon quantum dots co-doped with nitrogen and phosphorous[J]. Journal of Luminescence, 2019, 206: 540-546.
[19] QI H J, TENG M, LIU M, et al. Biomass-derived nitrogen-doped carbon quantum dots: highly selective fluorescent probe for detecting Fe³⁺ ions and tetracyclines[J]. Journal of Colloid and Interface Science, 2019, 539: 332-341.
[20] DENG X Y, FENG Y L, LI H R, et al. N-doped carbon quantum dots as fluorescent probes for highly selective and sensitive detection of Fe³⁺ ions[J]. Particuology, 2018, 41: 94-100.
[21] WANG J J, ZHANG H, ZHAO J H, et al. Simultaneous determination of paracetamol and p-aminophenol using glassy carbon electrode modified with nitrogen- and sulfur- co-doped carbon dots[J]. Microchimica Acta, 2019, 186(11): 1-9.
[22] SUN X, YANG S, GUO M, et al. Reversible fluorescence probe based on N-doped carbon dots for the determination of mercury ion and glutathione in waters and living cells[J]. Analytical Sciences, 2017, 33(7): 761-767.
[23] XU Q, LIU Y, SU R G, et al. Highly fluorescent Zn-doped carbon dots as Fenton reaction-based bio-sensors: an integrative experimental-theoretical consideration[J]. Nanoscale, 2016, 8(41): 17919-17927.
[24] XU Q, WEI J F, WANG J L, et al. Facile synthesis of copper doped carbon dots and their application as a “turn-off” fluorescent probe in the detection of Fe³⁺ ions[J]. RSC Advances, 2016, 6(34): 28745-28750.
[25] XU Q, SU R G, CHEN Y S, et al. Metal charge transfer doped carbon dots with reversibly switchable, ultra-high quantum yield photoluminescence[J]. ACS Applied Nano Materials, 2018, 1(4): 1886-1893.
[26] 鲁诗言,于淑娟,陈国全,等.氮、磷掺杂碳点的合成及在Pd²⁺传感中的应用[J].发光学报,2021,42(1):53-60.
LU S Y, YU S J, CHEN G Q, et al. Synthesis of nitrogen and phosphorus doped carbon dots and their application in Pd²⁺ sensing[J]. Chinese Journal of Luminescence, 2021, 42(1): 53-60(in Chinese).
[27] LU M C, DUAN Y X, SONG Y H, et al. Green preparation of versatile nitrogen-doped carbon quantum dots from watermelon juice for cell imaging, detection of Fe³⁺ ions and cysteine, and optical thermometry[J]. Journal of Molecular Liquids, 2018, 269: 766-774.