黄瓜前驱体荧光碳量子点的合成及其在铜(Ⅱ)检测中的应用
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摘要
以食用黄瓜汁作为前驱体,在较低的温度下利用水热法一步合成了具有荧光性质的碳量子点(简称碳点)。考察了水热反应温度、水热反应时间、溶液pH值对该碳点荧光性能的影响,同时,从盐离子浓度、紫外光照时间以及存放时间这3方面探讨了其光稳定性。结果表明,于水热反应温度为150℃时反应6h,控制溶液酸度为pH 12时制备的碳点有较高的荧光量子产率(荧光量子产率3.9%),合成的碳点具有较好的光稳定性。进一步研究发现,Cu~(2+)对按照上述方法合成黄瓜汁碳点的荧光强度有明显的猝灭作用,据此建立了一种检测Cu~(2+)的新方法。实验表明,Cu~(2+)浓度在0.1×10~(-6)～5.8×10~(-6) mol/L范围内与黄瓜汁碳点的荧光猝灭程度呈良好的线性关系,检出限为0.041μmol/L。实验方法用于河水和生活污水中Cu~(2+)的测定,测得结果与原子吸收光谱法(AAS)基本一致,相对标准偏差(RSD,n=5)为3.4%～4.3%。
The carbon quantum dots(CQDs)with fluorescence property were one-step synthesized at low temperature by hydrothermal method using edible fresh cucumber juice as the precursor.The effect of hydrothermal reaction temperature,hydrothermal reaction time and pH of solution on the fluorescence property of CQDs was investigated.Meanwhile,the light stability was discussed from three aspects including salt ion concentration,UV-irradiation time and storage period.The results showed that the prepared CQDs exhibited high fluorescence quantum yield(3.9%)under the following experimental conditions:the hydrothermal reaction temperature was 150℃,the reaction time was 6 h,and the pH of solution was controlled at 12.Meanwhile,the CQDs had good light stability.The further study results indicated that Cu~(2+)showed obvious quenching effect on the fluorescence intensity of cucumber juice CQDs prepared above.Hereby a new detection method of Cu~(2+)was established.The concentration of Cu~(2+)in range of 0.1×10~(-6)-5.8×10~(-6) mol/L had good linear relationship with the fluorescence quenching level of cucumber juice CQDs.The detection limit was 0.041μmol/L.The proposed method was applied to the determination of Cu~(2+)in river water and domestic wastewater.The found results were basically consistent with those obtained by atomic absorption spectrometry(AAS).The relative standard deviations(RSD,n=5)were between 3.4%and 4.3%.
The carbon quantum dots(CQDs)with fluorescence property were one-step synthesized at low temperature by hydrothermal method using edible fresh cucumber juice as the precursor.The effect of hydrothermal reaction temperature,hydrothermal reaction time and pH of solution on the fluorescence property of CQDs was investigated.Meanwhile,the light stability was discussed from three aspects including salt ion concentration,UV-irradiation time and storage period.The results showed that the prepared CQDs exhibited high fluorescence quantum yield(3.9%)under the following experimental conditions:the hydrothermal reaction temperature was 150℃,the reaction time was 6 h,and the pH of solution was controlled at 12.Meanwhile,the CQDs had good light stability.The further study results indicated that Cu~(2+)showed obvious quenching effect on the fluorescence intensity of cucumber juice CQDs prepared above.Hereby a new detection method of Cu~(2+)was established.The concentration of Cu~(2+)in range of 0.1×10~(-6)-5.8×10~(-6) mol/L had good linear relationship with the fluorescence quenching level of cucumber juice CQDs.The detection limit was 0.041μmol/L.The proposed method was applied to the determination of Cu~(2+)in river water and domestic wastewater.The found results were basically consistent with those obtained by atomic absorption spectrometry(AAS).The relative standard deviations(RSD,n=5)were between 3.4%and 4.3%.
引文
[1]黄运瑞,张廉奉,卢驰元,等.分散液相微萃取光度法测定水中痕量铜[J].冶金分析,2016,36(12):65-68.HUANG Yun-rui,ZHANG Lian-feng,LU Chi-yuan,et al.Determination of trace copper in water by dispersive liquid phase microextraction combined with spectrophotometry[J].Metallurgical Analysis,2016,36(12):65-68.
[2]陈钰,龚正君,杨顺生,等.改性玉米秸秆吸附Cu2+的动力学和热力学[J].环境工程学报,2013,7(2):523-529.CHEN Yu,GONG Zheng-jun,YANG Shun-sheng,et al.Kinetic and thermodynamic research on Cu2+adsorption by modified wheat straw[J].Chinese Journal of Environmental Engineering,2013,7(2):523-529.
[3]陆丽丽,陶贤继,胡家文.水环境中Cu2+检测和处理研究进展[J].环境科技,2010,23(2):125-127.LU Li-li,TAO Xian-ji,HU Jia-wen.Research progress on determination and treatment of Cu2+in water environment[J].Environmental Science and Technology,2010,23(2):125-127.
[4]刘声燕,王益林,杨昆.近红外发射CdSeTe量子点测定铜离子[J].发光学报,2013,7(2):523-529.LIU Sheng-yan,WANG Yi-lin,YANG Kun.Determination of copper ion by near-infrared-emitting CdSeTe quantum dots[J].Chinese Journal of Luminescence,2013,7(2):523-529.
[5]杨海芬,张浩,李萍,等.基于氮掺杂碳点荧光猝灭法检测铜离子[J].光谱学与光谱分析,2016,36(10):369-370.YANG Hai-fen,ZHANG Hao,LI Ping,et al.The fluorescence quenching method for detecting copper ion based on nitrogen doped carbon dots[J].Spectroscopy and Spectral Analysis,2016,36(10):369-370.
[6]赵艳,高楼军,孙雪华,等.铁(III)的碳量子点荧光猝灭效应研究及其应用[J].冶金分析,2015,35(12):60-63.ZHAO Yan,GAO Lou-jun,SUN Xue-hua,et al.Study on carbon quantum dots fluorescence quenching effect of iron(III)and its application[J].Metallurgical Analysis,2015,35(12):60-63.
[7]Wen X P,Shi L H,Wen G M,et al.Green and facile synthesis of nitrogen-doped carbon nanodots formulticolor cellular imaging and Co2+sensing in living cells[J].Sens.Actuators B:Chem.,2016,235:179-187.
[8]LIU H P,YE T,MAO C D.Fluorescent carbon nanoparticles derived from candle soot[J].Angew.Chem.Int.Ed.,2007,46:6473-6475.
[9]ZHENG L Y,CHI Y W,DONG Y Q,et al.Electrochemiluminescence of water-soluble carbon nanocrystals released electrochemically from graphite[J].J.Am.Chem.Soc.,2009,131:4564-4565.
[10]LIU C J,ZHANG P,ZHAI X Y,et al.Nano-carrier for gene delivery and bioimaging based on carbon dots with PEI-passivation enhanced fluorescence[J].Biomaterials,2012,33:3604-3613.
[11]LI H T,HE X D,LIU Y,et al.One-step ultrasonic synthesis of water-soluble carbon nanoparticles with excellent photoluminescent properties[J].Carbon,2011,49:605-609.
[12]LIU S,TIAN J Q,WANG L,et al.Hydrothermal treatment of grass:alow-cost,green route to nitrogendoped,carbon-rich,photoluminescentpolymer nanodots as an effective fluorescent sensing platform for label-free detection of Cu(II)ions[J].Adv.Mater.,2012,24:2037-2041.
[13]刘文,李婷婷,张冰,等.基于绿色天然物质合成荧光碳点及其性质和应用综述[J].材料导报,2019,33(2):402-409.LIU Wen,LI Ting-ting,ZHANG Bing,et al.Properties and applications of fluorescent carbon dots prepared by green natural substances:a review[J].Materials Reports,2019,33(2):402-409.
[14]ZHONG D,MIAO H,YANG K,et al.Carbon dots originatedfrom carnation for fluorescence and colorimetric pH sensing[J].Mater.Lett.,2016,166:89-92.
[15]杨晓婧,李美丽,白建华.原子吸收光谱法测定废水中的重金属离子[J].光谱实验室,2010,27(1):247-249.YANG Xiao-jing,LI Mei-li,BAI Jian-hua.Determination of heavy metal ions in waste water by the flame atomic absorption spectrometry[J].Chinese Journal of Spectroscopy Laboratory,2010,27(1):247-249.
[2]陈钰,龚正君,杨顺生,等.改性玉米秸秆吸附Cu2+的动力学和热力学[J].环境工程学报,2013,7(2):523-529.CHEN Yu,GONG Zheng-jun,YANG Shun-sheng,et al.Kinetic and thermodynamic research on Cu2+adsorption by modified wheat straw[J].Chinese Journal of Environmental Engineering,2013,7(2):523-529.
[3]陆丽丽,陶贤继,胡家文.水环境中Cu2+检测和处理研究进展[J].环境科技,2010,23(2):125-127.LU Li-li,TAO Xian-ji,HU Jia-wen.Research progress on determination and treatment of Cu2+in water environment[J].Environmental Science and Technology,2010,23(2):125-127.
[4]刘声燕,王益林,杨昆.近红外发射CdSeTe量子点测定铜离子[J].发光学报,2013,7(2):523-529.LIU Sheng-yan,WANG Yi-lin,YANG Kun.Determination of copper ion by near-infrared-emitting CdSeTe quantum dots[J].Chinese Journal of Luminescence,2013,7(2):523-529.
[5]杨海芬,张浩,李萍,等.基于氮掺杂碳点荧光猝灭法检测铜离子[J].光谱学与光谱分析,2016,36(10):369-370.YANG Hai-fen,ZHANG Hao,LI Ping,et al.The fluorescence quenching method for detecting copper ion based on nitrogen doped carbon dots[J].Spectroscopy and Spectral Analysis,2016,36(10):369-370.
[6]赵艳,高楼军,孙雪华,等.铁(III)的碳量子点荧光猝灭效应研究及其应用[J].冶金分析,2015,35(12):60-63.ZHAO Yan,GAO Lou-jun,SUN Xue-hua,et al.Study on carbon quantum dots fluorescence quenching effect of iron(III)and its application[J].Metallurgical Analysis,2015,35(12):60-63.
[7]Wen X P,Shi L H,Wen G M,et al.Green and facile synthesis of nitrogen-doped carbon nanodots formulticolor cellular imaging and Co2+sensing in living cells[J].Sens.Actuators B:Chem.,2016,235:179-187.
[8]LIU H P,YE T,MAO C D.Fluorescent carbon nanoparticles derived from candle soot[J].Angew.Chem.Int.Ed.,2007,46:6473-6475.
[9]ZHENG L Y,CHI Y W,DONG Y Q,et al.Electrochemiluminescence of water-soluble carbon nanocrystals released electrochemically from graphite[J].J.Am.Chem.Soc.,2009,131:4564-4565.
[10]LIU C J,ZHANG P,ZHAI X Y,et al.Nano-carrier for gene delivery and bioimaging based on carbon dots with PEI-passivation enhanced fluorescence[J].Biomaterials,2012,33:3604-3613.
[11]LI H T,HE X D,LIU Y,et al.One-step ultrasonic synthesis of water-soluble carbon nanoparticles with excellent photoluminescent properties[J].Carbon,2011,49:605-609.
[12]LIU S,TIAN J Q,WANG L,et al.Hydrothermal treatment of grass:alow-cost,green route to nitrogendoped,carbon-rich,photoluminescentpolymer nanodots as an effective fluorescent sensing platform for label-free detection of Cu(II)ions[J].Adv.Mater.,2012,24:2037-2041.
[13]刘文,李婷婷,张冰,等.基于绿色天然物质合成荧光碳点及其性质和应用综述[J].材料导报,2019,33(2):402-409.LIU Wen,LI Ting-ting,ZHANG Bing,et al.Properties and applications of fluorescent carbon dots prepared by green natural substances:a review[J].Materials Reports,2019,33(2):402-409.
[14]ZHONG D,MIAO H,YANG K,et al.Carbon dots originatedfrom carnation for fluorescence and colorimetric pH sensing[J].Mater.Lett.,2016,166:89-92.
[15]杨晓婧,李美丽,白建华.原子吸收光谱法测定废水中的重金属离子[J].光谱实验室,2010,27(1):247-249.YANG Xiao-jing,LI Mei-li,BAI Jian-hua.Determination of heavy metal ions in waste water by the flame atomic absorption spectrometry[J].Chinese Journal of Spectroscopy Laboratory,2010,27(1):247-249.