微波法制备掺氮碳点及其用作探针检测铁离子
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摘要
为了研究氮掺杂对纳米碳点荧光发射行为的影响和探索掺氮碳点的快速制备途径,以2-氨基对苯二甲酸为前驱体,与不同的修饰剂一起溶解于去离子水中,经微波辐射3 min,一步法合成了新型掺氮碳点。实验结果表明:制备的掺氮碳点水溶性好,发蓝色荧光,且发射行为不依赖于激发波长;颗粒近似为球形,尺寸5～8 nm,晶面间距为0.23 nm,接近石墨碳(100)面晶格结构;Fe~(3+)通过与掺氮碳点表面含氧基团的络合配位,可有效地猝灭其荧光,Fe~(3+)浓度在5～60μmol·L~(-1)的范围内与相对荧光强度呈现良好的线性关系,检出限约为1.01μmol·L~(-1),可以作为检测Fe~(3+)浓度的荧光探针。
In order to study the impact of nitrogen-doping on the photoluminescence properties of carbon nanodots and explore a facile preparing approach for nitrogen-doping carbon dots(N-CDs), 2-aminoterephthalic acid as the precursor and various modifiers were firstly dissolved in deionized water. Thereafter the as-prepared solution was treated by microwave irradiation of 1 kW for 3 min and consequently a novel N-CD was obtained by the one-pot method. Experimental results indicated that the as-synthesized N-CDs were very soluble in water and exhibited bright blue emission under ultraviolet light. Furthermore, the fluorescence emission was independent of excitation wavelengths. The N-CDs showed an approximately spheric particle with a size of 5-8 nm and an obvious fringe distance of 0.23 nm, close to the(100) crystal lattice distance of graphitic carbon structure. The fluorescence of the obtained N-CDs could be effectively quenched by ferric ions via interacting with functional groups on the surface of N-CDs to form complex compounds. The normalized intensity versus the concentration of ferric ions showed a good linear relationship under the concentration in the range of 5-60 μmol·L~(-1). The detection limit of ferric ions was estimated to be 1.01 μmol·L~(-1). These results suggested that the as-synthesized N-CDs could be used as an effective fluorescent sensing platform for ferric ions in water.
In order to study the impact of nitrogen-doping on the photoluminescence properties of carbon nanodots and explore a facile preparing approach for nitrogen-doping carbon dots(N-CDs), 2-aminoterephthalic acid as the precursor and various modifiers were firstly dissolved in deionized water. Thereafter the as-prepared solution was treated by microwave irradiation of 1 kW for 3 min and consequently a novel N-CD was obtained by the one-pot method. Experimental results indicated that the as-synthesized N-CDs were very soluble in water and exhibited bright blue emission under ultraviolet light. Furthermore, the fluorescence emission was independent of excitation wavelengths. The N-CDs showed an approximately spheric particle with a size of 5-8 nm and an obvious fringe distance of 0.23 nm, close to the(100) crystal lattice distance of graphitic carbon structure. The fluorescence of the obtained N-CDs could be effectively quenched by ferric ions via interacting with functional groups on the surface of N-CDs to form complex compounds. The normalized intensity versus the concentration of ferric ions showed a good linear relationship under the concentration in the range of 5-60 μmol·L~(-1). The detection limit of ferric ions was estimated to be 1.01 μmol·L~(-1). These results suggested that the as-synthesized N-CDs could be used as an effective fluorescent sensing platform for ferric ions in water.
引文
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[27] DING H,YU S B,WEI J S,et al..Full-color light-emitting carbon dots with a surface-state-controlled luminescence mechanism [J].ACS Nano,2016,10(1):484-491.
[2] ZHU S J,SONG Y B,ZHAO X H,et al..The photoluminescence mechanism in carbon dots (graphene quantum dots,carbon nanodots,and polymer dots):current state and future perspective [J].Nano Res.,2015,8(2):355-381.
[3] LI X M,RUI M C,SONG J Z,et al..Carbon and graphene quantum dots for optoelectronic and energy devices:a review [J].Adv.Funct.Mater.,2015,25(31):4929-4947.
[4] 张川洲,谭辉,毛燕,等.发光碳量子点的合成、性质和应用 [J].应用化学,2013,30(4):367-372.ZHANG C Z,TAN H,MAO Y,et al..Synthesis and properties of luminescent carbon dots and its applications [J].Chin.J.Appl.Chem.,2013,30(4):367-372.(in Chinese)
[5] SHAMSIPUR M,BARATI A,KARAMI S.Long-wavelength,multicolor,and white-light emitting carbon-based dots:achievements made,challenges remaining,and applications [J].Carbon,2017,124:429-472.
[6] TANG C,QIAN Z S,HUANG Y Y,et al..A fluorometric assay for alkaline phosphatase activity based on β-cyclodextrin-modified carbon quantum dots through host-guest recognition [J].Biosens.Bioelectron.,2016,83(9):274-280.
[7] WU M B,WANG Y,WU W T,et al..Preparation of functionalized water-soluble photoluminescent carbon quantum dots from petroleum coke [J].Carbon,2014,78:480-489.
[8] TANG D,LIU J,WU X Y,et al..Carbon quantum dot/NiFe layered double-hydroxide composite as a highly efficient electrocatalyst for water oxidation [J].ACS Appl.Mater.Interfaces,2014,6(10):7918-7925.
[9] XU X Y,RAY R,GU Y L,et al..Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments [J].J.Am.Chem.Soc.,2004,126(40):12736-12737.
[10] LIU Y,HU J,LI Y,et al..Synthesis of polyethyleneimine capped carbon dots for preconcentration and slurry sampling analysis of trace chromium in environmental water samples [J].Talanta,2015,134:16-23.
[11] HAO A J,GUO X J,WU Q,et al..Exploring the interactions between polyethyleneimine modified fluorescent carbon dots and bovine serum albumin by spectroscopic methods [J].J.Lumin.,2016,170:90-96.
[12] CAO X T,MA J,LIN Y P,et al..A facile microwave-assisted fabrication of fluorescent carbon nitride quantum dots and their application in the detection of mercury ions [J].Spectrochim.Acta Part A,2015,151:875-880.
[13] 王子儒,张光华,郭明媛.N掺杂碳量子点光稳定剂的制备及光学性能 [J].发光学报,2016,37(6):655-661.WANG Z R,ZHANG G H,GUO M Y.Preparation and optical properties of N-doped carbon dots as light stabilizer [J].Chin.J.Lumin.,2016,37(6):655-661.(in Chinese)
[14] CHEN X F,ZHANG W X,WANG Q J,et al..C8-structured carbon quantum dots:synthesis,blue and green double luminescence,and origins of surface defects [J].Carbon,2014,79(1):165-173.
[15] 王莉,吕婷,阮枫萍,等.水热法制备的荧光碳量子点 [J].发光学报,2014,35(6):706-709.WANG L,LYU T,RUAN F P,et al..Synthesis of photoluminescent carbon nanoparticles by hydrothermal method [J].Chin.J.Lumin.,2014,35(6):706-709.(in Chinese)
[16] 李晓峰,周明,龚爱华,等.氮掺杂碳量子点的合成、表征及其在细胞成像中的应用 [J].材料科学与工程学报,2015,33(1):41-45.LI X F,ZHOU M,GONG A H,et al..Synthesis,characterization and cell imaging application of nitrogen-doped carbon quantum dots [J].J.Mater.Sci.Eng.,2015,33(1):41-45.(in Chinese)
[17] JIANG K,SUN S,ZHANG L,et al..Red,green,and blue luminescence by carbon dots:full-color emission tuning and multicolor cellular imaging [J].Angew.Chem.Int.Ed.,2015,54(18):5360-5363.
[18] 张文宇,常青,周雨锋,等.一步合成硫、氮共掺杂的碳量子点及其在Fe3+检测中的应用 [J].发光学报,2016,37(4):410-415.ZHANG W Y,CHANG Q,ZHOU Y F,et al..One-step synthesis of sulfur- and nitrogen-co-doped carbon quantum dots for Fe(Ⅲ) detection [J].Chin.J.Lumin.,2016,37(4):410-415.(in Chinese)
[19] 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.ZHANG J,JIANG Y L,CHENG Y,et al..Microwave synthesis of glycerol carbon quantum dots and its application in Fe3+ probe [J].Chem.J.Chin.Univ.,2016,37(1):54-58.(in Chinese)
[20] JAHANBAKHSHI M,HABIBI B.A novel and facile synthesis of carbon quantum dots via salep hydrothermal treatment as the silver nanoparticles support:application to electroanalytical determination of H2O2 in fetal bovine serum [J].Biosens.Bioelectron.,2016,81:143-150.
[21] 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(12):421-428.
[22] BRISCOE J,MARINOVIC A,SEVILLA M,et al..Biomass-derived carbon quantum dot sensitizers for solid-state nanostructured solar cells [J].Angew.Chem.Int.Ed.,2015,54(15):4463-4468.
[23] KARABACAK M,CINAR M,UNAL Z,et al..FT-IR,UV spectroscopic and DFT quantum chemical study on the molecular conformation,vibrational and electronic transitions of 2-aminoterephthalic acid [J].J.Mol.Struct.,2010,982(1-3):22-27.
[24] DING H,XIONG H M.Exploring the blue luminescence origin of nitrogen-doped carbon dots by controlling the water amount in synthesis [J].RSC Adv.,2015,5(82):66528-66533.
[25] LI Z,YU H J,BIAN T,et al..Highly luminescent nitrogen-doped carbon quantum dots as effective fluorescent probes for mercuric and iodide ions [J].J.Mater.Chem.C,2015,3(9):1922-1928.
[26] NIU W J,LI Y,ZHU R H,et al..Ethylenediamine-assisted hydrothermal synthesis of nitrogen-doped carbon quantum dots as fluorescent probes for sensitive biosensing and bioimaging [J].Sens.Actuators B,2015,218:229-236.
[27] DING H,YU S B,WEI J S,et al..Full-color light-emitting carbon dots with a surface-state-controlled luminescence mechanism [J].ACS Nano,2016,10(1):484-491.