硫氮共掺杂碳量子点的制备及应用

doi:10.19894/j.issn.1000-0518.200268

摘要/Abstract

摘要： 以中性红和硫脲为原料,一步水热法制备了近红外荧光硫氮共掺杂碳量子点(SN-CQDs)。通过透射电子显微镜(TEM)、紫外-可见吸收光谱、荧光光谱、X射线光电子能谱等技术对制备的SN-CQDs进行形貌及光学性质表征。制备的SN-CQDs尺寸均匀,稳定性高,在荧光光谱中,发射波长最大值在628 nm处,最佳激发为510 nm。铬离子(Cr³⁺)和4-硝基酚(4-NP)对SN-CQDs产生荧光猝灭作用,且具有良好的选择性,将制备的SN-CQDs作为荧光探针用于Cr³⁺和4-NP的检测。 Cr³⁺浓度在0～170 μmol/L范围内与SN-CQDs的荧光猝灭程度呈现良好的线性关系,相关系数为0.9922。 4-NP的浓度在0～240 μmol/L范围内与SN-CQDs的荧光猝灭程度呈现良好的线性关系,相关系数为0.9955。制备的碳量子点用于实际水样检测准确度较高,对Cr³⁺和4-NP具有高灵敏度以及较好的抗干扰能力,为检测 Cr³⁺、4-NP提供了新的检测方法。

关键词: 硫氮共掺杂, 碳量子点, 4-硝基酚检测, Cr³⁺检测

Abstract: Sulphur and nitrogen co-doped carbon quantum dots (SN-CQDs) were synthesized by one-step hydrothermal method using neutral red and thiourea as raw materials. The morphology and optical properties of the synthesized CQDs were characterized by transition electron microscopy (TEM), ultraviolet, X-ray photoelectron spectroscopy (XPS) and fluorescence techniques. The synthesized SN-CQDs have uniform size and high stability. In the fluorescence spectrum, the maximum emission wavelength is 628 nm, and the maximum excitation wavelength is 510 nm. Chromium ions (Cr³⁺) and 4-nitrophenol (4-NP) have a fluorescence quenching effect on SN-CQDs. Using SN-CQDs as fluorescent probes for Cr³⁺, 4-NP detection, the Cr³⁺ concentration in the range of 0～170 μmol/L has a good linear relationship with the fluorescence quenching degree of SN-CQDs, and the correlation coefficient is 0.9922. The concentration of 4-NP in the range of 0～240 μmol/L shows a good linear relationship with the fluorescence quenching, and the correlation coefficient is 0.9955. In the actual water sample detection, the SN-CQDs has high accuracy, high sensitivity and good anti-interference ability to Cr³⁺ and 4-NP detection. This work provides a new detection method for Cr³⁺ and 4-NP.

Key words: Sulfur and nitrogen co-doping, Carbon quantum dots, 4-Nitrophenol detection, Cr³⁺ detection

中图分类号:

O657.3

温广明, 焦婷, 杜孝艳, 李忠平. 硫氮共掺杂碳量子点的制备及应用[J]. 应用化学, 2021, 38(6): 722-730.

WEN Guang-Ming, JIAO Ting, DU Xiao-Yan, LI Zhong-Ping. Preparation and Application of Sulfur and Nitrogen Co-doped Carbon Quantum Dots[J]. Chinese Journal of Applied Chemistry, 2021, 38(6): 722-730.

参考文献

[1] GAO W L, SONG H H, WANG X, et al. Carbon dots with red emission for sensing of Pt²⁺, Au³⁺, and Pd²⁺ and their bioapplications in vitro and in vivo[J]. ACS Appl Mater Interfaces, 2017, 10(1): 1147-1154.
[2] BORA A, MOHAN K, DOLUI S K. Carbon dots as cosensitizers in dye-sensitized solar cells and fluorescence chemosensors for 2,4,6-trinitrophenol detection[J]. Ind Eng Chem Res, 2019, 58 (51): 22771-22778.
[3] PAN L L, SUN S, ZHANG A D, et al. Truly fluorescent excitation-dependent carbon dots and their applications in multicolor cellular imaging and multidimensional sensing[J]. Adv Mater, 2015, 27: 7782-7787.
[4] YU C Y, XUAN T T, CHEN Y W, et al. Gadolinium-doped carbon dots with high quantum yield as an effective fluorescence and magnetic resonance bimodal imaging probe[J]. J Alloys Compd, 2016, 688: 611-619.
[5] YU L L, YUE X, YANG R, et al. A sensitive and low toxicity electrochemical sensor for 2,4-dichlorophenol based on the nanocomposite of carbon dots, hexadecyltrimethyl ammonium bromide and chitosan[J]. Sens Actuators, B, 2016, 224: 241-247.
[6] ZHUO K L, SUN D, XU P P, et al. Green synthesis of sulfur- and nitrogen-co-doped carbon dots using ionic liquid as a precursor and their application in Hg²⁺ detection[J]. J Lumin, 2017, 187: 227-234.
[7] CUI X B, WANG Y L, LIU J, et al. Dual functional N- and S-co-doped carbon dots as the sensor for temperature and Fe³⁺ ions[J]. Sens Actuators, B, 2017, 242: 1272-1280.
[8] MIAO X, YAN X L, QU D, et al. Red emissive sulfur, nitrogen codoped carbon dots and their application in ion detection and theraonostics[J]. ACS Appl Mater Interfaces, 2017, 9: 18549-18556.
[9] WANG C X, JIANG K L, WU Q, et al. Green synthesis of red-emitting carbon nanodots as a novel “turn-on” nanothermometer in living cells[J]. Chem Eur J, 2016, 22: 14475-14479.
[10] TAM T V, KANG S G, BABU K F, et al. Synthesis of B-doped graphene quantum dots as a metal-free electrocatalyst for the oxygen reduction reaction[J]. J Mater Chem A, 2017, 5: 10537-10543.
[11] VÁZQUEZ-GONZÁLE M, LIAO W C, CAZELLES R, et al. Mimicking horseradish peroxidase functions using Cu²⁺-modified carbon nitride nanoparticles or Cu²⁺-modified carbon dots as heterogeneous catalysts[J]. ACS Nano, 2017, 11: 3247-3253.
[12] HUTTON G A M, REUILLARD B, MARTINDALE B C M, et al. Carbon dots as versatile photosensitizers for solar-driven catalysis with redox enzymes[J]. J Am Chem Soc, 2016, 138: 16722-16730.
[13] HOU Y, LU Q, DENG J, et al. One-pot electrochemical synthesis of functionalized fluorescent carbon dots and their selective sensing for mercury ion[J]. Anal Chim Acta, 2015, 866: 69-74.
[14] RAO H, LIU W, HE K, et al. Smartphone-based fluorescence detection of Al³⁺ and H₂O based on the use of dual-emission biomass carbon dots[J]. ACS Sustainable Chem Eng, 2020, 8: 8857-8867.
[15] HU S, LIU J, YANG J, et al. Laser synthesis and size tailor of carbon quantum dots[J]. Nanopart Res, 2011, 13: 7247-7252.
[16] WANG C, WANG Y, SHI H, et al. A strong blue fluorescent nanoprobe for highly sensitive and selective detection of mercury(II) based on sulfur doped carbon quantum dots[J]. Mater Chem Phys, 2019, 232: 145.
[17] MING F L, HOU J Z, HOU C J, et al. One-step synthesized fluorescent nitrogen doped carbon dots from thymidine for Cr(VI) detection in water[J]. Spectrochim Acta A, 2019, 222: 117165.
[18] LIU H J, WANG H, QIAN Y, et al. Nitrogen-doped graphene quantum dots as metal-free photocatalysts for near-infrared enhanced reduction of 4-nitrophenol[J]. ACS Appl Nano Mater, 2019, 2 (11): 7043-7050.
[19] CHAUDHARY S, KUMAR S, KAUR B, et al. Potential prospects for carbon dots as a fluorescence sensing probe for metal ions[J]. RSC Adv, 2016, 6(93): 90526-90536.
[20] PALIWAL S, WALES M, THERESA G, et al. Fluorescence-based sensing of p-nitrophenol and p-nitrophenyl substituent organophosphates[J]. Anal Chim Acta, 2007, 596: 9-15.
[21] QU F, CHEN P, ZHU S Y, et al. High selectivity of colorimetric detection of p-nitrophenol based on Ag nanoclusters[J]. Part A, 2017, 171: 449-453.
[22] ZHAI H Y, XIAO W L, LI Y, et al. Sensitive and selective determination of 4-nitrophenol in water and food using modified polyethyleneimine-capped carbon dots[J]. J Chinese Chem Soc-Taipei, 2020, 67(7): 1230-1238.
[23] REN G, TANG M, CHAI F, et al. One-pot synthesis of highly fluorescent carbon dots from spinach and multipurpose applications[J]. Eur J Inorg Chem, 2018, 2018(2): 153-158.
[24] DENG H, SU X, WANG H. Simultaneous determination of aflatoxin B1, bisphenol A, and 4-nonylphenol in peanut oils by liquid-liquid extraction combined with solid-phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Food Anal Methods, 2018, 11(5): 1303-1311.
[25] TARPANI L, MECARELLI E, NOCCHETTI M, et al. Spectrophotometric analysis of nickel colloid performances as catalysts for hydrogenation of nitro-phenol: influence of the stabilizing agents[J]. Catal Commun, 2016, 74: 28-32.
[26] HIRA S A, NALLAL M, PARK K H. Fabrication of PdAg nanoparticle infused metal-organic framework for electrochemical and solution-chemical reduction and detection of toxic 4-nitrophenol[J]. Sens Actuators B Chem, 2019, 298: 126861.
[27] LU H, XU S, LIU J. One pot generation of blue and red carbon dots in one binary solvent system for dual channel detection of Cr³⁺ and Pb²⁺ based on ion imprinted fluorescence polymers[J]. ACS Sens, 2019, 4(7): 1917-1924.
[28] CHANG M M F, GINJOM I R, NGU-SCHWEMLEIN M, et al. Synthesis of yellow fluorescent carbon dots and their application to the determination of chromium(III) with selectivity improved by pH tuning[J]. Microchim Acta, 2016, 183(6): 1899-1907.
[29] LIU L Q, LI Y F, ZHAN L, et al. One-step synthesis of fluorescent hydroxyls-coated carbon dots with hydrothermal reaction and its application to optical sensing of metal ions[J]. Sci China Chem, 2011, 54(8): 1342-1347.
[30] HUANG C F, HAO J, HAO C. Highly sensitive fluorescent probe for Cr³⁺ detection using carbon quantum dots: 3rd international forum on energy, environment science and materials[C]. Shenzhen, 2017, 120: 871-877.
[31] YANG Y X, XUE H M, CHEN L C, et al. Colorimetric and highly selective fluorescence “turn-on” detection of Cr³⁺ by using a simple Schiff base sensor[J]. Chinese J Chem, 2013, 31(3): 377-380.
[32] SAHA S, MAHATO P, REDDY U, et al. Recognition of Hg²⁺ and Cr³⁺ in physiological conditions by a rhodamine derivative and its application as a reagent for cell-imaging studies[J]. Inorg Chem, 2012, 51: 336.
[33] WAN Y, GUO Q J, WANG X F, et al. Photophysical properties of rhodamine isomers: a two-photon excited fluorescent sensor for trivalent chromium cation (Cr³⁺)[J]. Anal Chim Acta, 2010, 665: 215-220.
[34] CHEN X Q, PRADHAN T, WANG F, et al. Fluorescent chemosensors based on spiroring-opening of xanthenes and related derivatives[J]. Chem Rev, 2011, 112: 1910-1956.
[35] ZHANG M, SU R, ZHONG J, et al. Red/Orange dual-emissive carbon dots for pH sensing and cell imaging[J]. Nano Res, 2019, 12(4): 815-821.
[36] DANG D K, SUNDARAM C, NGO Y L T, et al. Pyromellitic acid-derived highly fluorescent N-doped carbon dots for the sensitive and selective determination of 4-nitrophenol[J]. Dyes Pigm, 2019, 165: 327-334.
[37] CHAUDHARY S, KUMAR S, KAUR B, et al. Potential prospects for carbon dots as a fluorescence sensing probe for metal ions[J]. RSC Adv, 2016, 6(93): 90526-90536.
[38] BOGIREDDY N K R, SILVA R C, VALENZUELA M A, et al. 4-Nitrophenol optical sensing with N doped oxidized carbon dots[J]. J Hazard Mater, 2020, 386: 121643.