氮磷共掺杂碳点的合成及其对Co~(2+)的检测
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摘要
以葡萄糖为碳源,通过乙二胺与浓磷酸中和放热碳化法合成氮磷共掺杂的荧光碳点,采用元素分析、TEM、FTIR、XPS、UV-vis和PL等分析测试技术对氮磷共掺杂碳点的形貌、结构、组成和光学性质进行了表征。实验结果表明,通过氮磷共掺杂得到的碳点不仅能增强其水溶性和光学稳定性,而且能有效提高碳点的量子产率。研究发现,Co2+能强烈猝灭氮磷共掺杂碳点的荧光,且Co2+浓度在0. 005～0. 250mmol·L-1范围内时与氮磷共掺杂碳点荧光的猝灭程度呈良好的线性关系,检出限为0. 6μmol·L-1。因此,建立了一种检测Co2+的荧光传感方法,该方法具有简单、快速、选择性高等优点。
In this work,phosphorous and nitrogen co-doped carbon dots( N,P-CDs) were synthesized by neutralization exothermic method of 1,2-ethylenediamine and concentrated phosphoric acid,using glucose as carbon source.Morphology,structure,components and optical properties of the obtained N,P-CDs were fully characterized by elemental analysis,TEM,FTIR,XPS,UV-vis and PL.The results indicated that the carbon dots obtained through co-doping of nitrogen and phosphorus could not only enhance the water solubility and optical stability,but also improve the quantum yield of carbon dots.It was found that the emission of N,P-CDs was efficiently quenched by Co2+,and there was a good linear relationship between the Co2+concentrations within0. 005 ～ 0. 250 mmol·L-1 and the fluorescence quenching rates of N,P-CDs. The detecting limit for Co2+was 0. 6 μmol·L-1. Therefore,a new fluorescence sensing method for Co2+detection can be established.The method has the advantages of simple,fast and high sensitivity.
In this work,phosphorous and nitrogen co-doped carbon dots( N,P-CDs) were synthesized by neutralization exothermic method of 1,2-ethylenediamine and concentrated phosphoric acid,using glucose as carbon source.Morphology,structure,components and optical properties of the obtained N,P-CDs were fully characterized by elemental analysis,TEM,FTIR,XPS,UV-vis and PL.The results indicated that the carbon dots obtained through co-doping of nitrogen and phosphorus could not only enhance the water solubility and optical stability,but also improve the quantum yield of carbon dots.It was found that the emission of N,P-CDs was efficiently quenched by Co2+,and there was a good linear relationship between the Co2+concentrations within0. 005 ～ 0. 250 mmol·L-1 and the fluorescence quenching rates of N,P-CDs. The detecting limit for Co2+was 0. 6 μmol·L-1. Therefore,a new fluorescence sensing method for Co2+detection can be established.The method has the advantages of simple,fast and high sensitivity.
引文
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[3]Aoki Y,Tomina G H,Nagai M. Hydrogenation of CO on molybdenum and cobalt molybdenum carbide catalystsmass and infarared spectroscopy studies[J].Catal Today,2013,215(15):169-175.
[4]霍燕燕,韩权,杨晓慧.钴(Ⅱ)与2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺络合物极谱吸附波的研究及其应用[J].冶金分析,2013,33(2):18-21.
[5]Liang P,Yu J,Yang E J,et al.Determination of cobalt in food and water samples by ultrasound-assisted surfactantenhanced emulsification microextraction and graphite furnace atomic absorption spectrometry[J].Food Anal Method,2014,7(7):1506-1512.
[6]齐艳娟,王晓菊,李红玫,等.催化动力学光度法测定痕量钴(Ⅱ)[J].光谱学与光谱分析,2002,22(3):499-450.
[7]Sun Y P,Zhou B,Lin Y,et a1.Quantum-sized carbon dots for bright and colorfhl photoluminescence[J]. J Am Chem Soc,2006,128(24):7756-7757.
[8]Zhou J G,Booker C,Li R Y,et al. An electrochemieal avenue to blue luminescent nanocrystals from multiwalled carbon nanotubes(MWCNTs)[J]. J Am Chem Soc,2007,129(4):744.
[9]Van T T,Trung N B,Kim H R,et a1.One-pot synthesis of N-doped graphene quantum dots as a nuorescent sensing platform for Fe3+ions detection[J]. Sensor Actuat B:Chem,2014,202(31):68-573.
[10]Zhu C,Zhai J,Dong S. Bifunctional fluorescent carbon nanodots:green syntllesis via soy milk and application as metal-free electmcatalysts for oxygen reduction[J].Chem Commun,2012,48(75):9367-9369.
[11]Prasannan A,Imae T. One-pot synthesis of fluorescent carbon dots from orange waste peels[J]. Ind Eng Chem Res,2013,52(44):15673-15678.
[12]Xu H,Yang X,Li G,et a1.Green synthesis of fluorescent carbon dots for selective detection of tartrazine in food samples[J]. J Agr Food Chem,2015,63(30):6707-6714.
[13]Li Y,Zhao Y,Cheng H H,et al.Nitrogen-doped graphene quantum dots with oxygen-rich functional groups[J]. J Am Chem Soc,2012,134(1):15-18.
[14]李满秀,刘秋文,李永霞,等.基于氨基化碳量子点荧光猝灭法检测苏丹Ⅳ的研究[J].化学研究与应用,2017,29(11):1647-1651.
[15]Dey S,Chithaiah P,Belawadi S,et a1. New methods of synthesis and varied pmpenies of carbon quantum dots with high nitrogen content[J]. J Mater Res,2014,29(3):383-391.
[16]Li W,Zhang Z H,Kong B,et al.Simple and green synthesis of nitrogen-doped Photoluminesc ioimaging[J].Angew Chem,2013,52(31):8151-8155.
[17]易凌亚,黎红,杨丽君.枸杞碳量子点的制备及氮修饰对荧光的影响[J].化学研究与应用,2017,29(4):529-532.
[18]杨凤,廖彩云,王美娜,等.水热法一步合成N/P-掺杂碳点及其荧光性能研究[J].化学研究与应用,2018,30(3):313-318.
[19]Liang Q H,Ma W J,Shi Y,et al.Easy synthesis of highly fluorescent carbon quantum dots from gelatin and their luminescent properties and applications[J]. Carbon,2013,60:421-428.
[20]Sun D,Ban R,Zhang P H,et al.Hair fiber as a precursor for synthesizing of sulfur-and nitrogen-co-doped carbon dots with tunable luminescence properties[J]. Carbon,2013,64:424-434.
[21]Wang Q L,Zheng H Z,Long Y J,et al.Microwave–hydrothermal synthesis of fluorescent carbon dots from graphite oxide[J].Carbon,2011,49(9):3134-3140.
[22]Gong X,Zhang Q,Gao Y,et al.Phosphorus and nitrogen dual-doped hollow carbon dot as a nanocarrier for doxorubicin delivery and biological imaging[J].ACS Appl Mater Inter,2016,8(18):11288-11297.
[23]张静,江玉亮,程钰,等.微波法制备丙三醇碳量子点并用作Fe3+探针[J].高等学校化学学报,2016,37(1):54-58.
[24]Jia X F,Li J,Wang E K.One-pot green synthesis of optically p H-sensitive carbon dots with upconversion luminescence[J].Nanoscale,2012,4(18):5572-5575.