Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co<sup>2+</sup>

Wen QIAN; Li HE; Wu-shuang PAN; Yan-hua CHEN; Hui WANG; Shu-liang LIU; Shu-juan CHEN; Ai-ping LIU

doi:10.37188/CJL.20210260

Your Location：

Home >

Browse articles >

Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co²⁺

Luminescence Applications and Interdisciplinary Fields | Updated：2021-11-23

- Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co²⁺
  Enhanced Publication
- role： First author , 第一作者 ,
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email： 1980385367@qq.com
  
  Introduction： [ "钱玟(1997-)，男，四川巴中人，硕士研究生，2019年于四川农业大学获得学士学位，主要从事食品检测荧光探针技术的研究。E-mail: 1980385367@qq.com" ]
  
  No information about the author is available
  QIAN Wen
  1 ,
  role： Corresponding author , 通讯作者 ,
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email： helifood@163.com
  
  Introduction： [ "何利(1984-)，女，重庆人，博士，副教授，硕士研究生导师，2011年于四川大学获得博士学位，主要从事食品资源综合利用、食品安全检测技术的研究。E-mail: helifood@163.com" ]
  
  No information about the author is available
  HE Li
  1 ,
  role：
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email：
  
  No information about the author is available
  PAN Wu-shuang
  1 ,
  role：
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email：
  
  No information about the author is available
  CHEN Yan-hua
  1 ,
  role：
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email：
  
  No information about the author is available
  WANG Hui
  1 ,
  role：
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email：
  
  No information about the author is available
  LIU Shu-liang
  1 ,
  role：
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email：
  
  No information about the author is available
  CHEN Shu-juan
  1 ,
  role：
  
  Affiliation：
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
  
  Email：
  
  No information about the author is available
  LIU Ai-ping
  1 ,
- Chinese Journal of Luminescence Vol. 42, Issue 11, Pages: 1818-1827(2021)
- Affiliations：
  
  College of Food Science, Sichuan Agricultural University, Yaan 625014, China
- Author bio：
- Funds：
  
  Sub-projects of the National Key Research and development Program(2019YFC1605302-3)
- DOI：10.37188/CJL.20210260
  CLC： O482.31
- Received：04 August 2021，
  
  Revised：11 August 2021，
  
  Published：01 November 2021
- Accepted：
Scan QR Code
Cite this article

PDF
Wen QIAN, Li HE, Wu-shuang PAN, et al. Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co²⁺[J]. Chinese journal of luminescence, 2021, 42(11): 1818-1827.
DOI：

Wen QIAN, Li HE, Wu-shuang PAN, et al. Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co²⁺[J]. Chinese journal of luminescence, 2021, 42(11): 1818-1827. DOI： 10.37188/CJL.20210260.

Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co²⁺ Enhanced Publication

QIAN Wen ; HE Li ; PAN Wu-shuang ; CHEN Yan-hua ; WANG Hui ; LIU Shu-liang ; CHEN Shu-juan ; LIU Ai-ping ;

PDF Download

Abstract

Nitrogen-doped carbon quantum dots(N-CQDs) were successfully synthesized using pig bone and ethylenediamine as carbon and nitrogen sources by one-step hydrothermal method. Structure, optical properties and element composition of N-CQDs have been studied by transmission electron microscope(TEM), Fourier transform infrared spectroscopy(FT-IR), X-ray diffractometer patterns(XRD), UV-Vis absorption spectroscopy(UV-Vis) and X-ray photoelectron spectroscopy(XPS) technologies. The synthesized N-CQDs have a high quantum yield(26.4%), an average particle size of 2.34 nm, showing bright blue fluorescence under a 365 nm UV lamp. The study found that Co²⁺ had a good quenching effect on N-CQDs, so as to establish a new method for rapid detection of Co²⁺. The fluorescence quenching intensity of N-CQDs has a good linear relationship with the concentration of Co²⁺ at 0-15 μg/mL and 30-80 μg/mL, the detection limit is 20 μg/L, and the recovery rate of standard addition is 97.26%-109.14%, RSD<3.24%, which can be applied to the determination of Co²⁺ content in actual water samples.

transl

Keywords

nitrogen-doped carbon quantum dots; pig bone; fluorescence detection; Co²⁺

transl

1　引言

碳量子点(Carbon quantum dots,CQDs)是一类尺寸小于10 nm具有量子限域效应的新型零维碳纳米材料^[

1]，与金属纳米团簇和传统的半导体量子点相比，CQDs由于其低毒性^{[Reference 2

Baidu Scholar

2]}、更宽的光致发光光谱^{[Reference 3

Baidu Scholar

3]}和高荧光稳定性^{[Reference 4

Baidu Scholar

4]}等独特优势，可被开发为具有快速、选择性好、灵敏度高和低毒性等出色性能的荧光探针，用于选择性检测有害物质。

transl

钴离子(Co²⁺)是人体必需的一种微量元素，可以促使红细胞和部分酶的合成、调节酶和辅助因子的催化活性，在人体中起着重要作用^[

5-6]。但是，过量摄入Co²⁺会使机体内的自由基过剩，导致细胞凋亡，进而使人患上哮喘、鼻炎、过敏性皮炎和心肌病等疾病^{[Reference 7

Baidu Scholar

7]}。考虑到Co²⁺引起的毒性作用，世界卫生组织(WHO)规定饮用水中Co²⁺的限量为40 μg/L^{[Reference 8

Baidu Scholar

8]}。现有的CQDs检测Co²⁺方法大多以化学物质为前体，对环境及人体健康造成一定的危害，且量子产率较低。田等^{[Reference 9

Baidu Scholar

9]}以化学物质对苯二胺和天冬酰胺为原料，通过一步水热法合成了绿色荧光的N-CQDs，用于检测Co²⁺及生物成像，但量子产率仅为15.5%。京等^{[Reference 10

Baidu Scholar

10]}以丙烯酸碳源，乙二胺为氮源，采用水热法制备了N-CQDs，量子产率为22.7%。因此，以生物质材料为碳源，采用简单、快速、可控的水热法合成高荧光CQDs，成为了分析检测研究的热点。

transl

我国是世界上禽、畜产量最多的国家之一，2018年中国猪肉总产量为5 400万吨，约占全球产量的50%，若以猪骨占猪肉的9%~14%计算^[

11]，我国年均产生486~756万吨猪骨。然而，除排骨和腔骨可直接用于饮食而被大量需求外，其他骨头的利用率均不高，造成了极大的资源浪费和环境危害。由于猪骨富含脂肪与蛋白质等物质，可作为制备碳量子点的良好碳源，因此本文以生物质废弃物猪骨(棒子骨)、乙二胺为前驱体，采用绿色经济的水热法合成猪骨氮掺杂碳量子点(N-CQDs)，通过各种表征技术研究了N-CQDs的结构和光学性质，探究了N-CQDs的稳定性，建立了一种快速检测Co²⁺的碳量子点荧光分析方法，并用于实际样品中Co²⁺的检测。

transl

2　实验

2.1　实验试剂与仪器

试剂:猪骨(棒子骨)收集于中国雅安苍坪山农贸市场(将猪骨剔除碎肉洗净后，置于60 ℃烘箱中烘干，然后用粉碎机研磨成粉末状，100目过筛保存备用)。乙二胺、CoCl₂、KCl、ZnCl₂、BaCl₂、MgCl₂、NaCl、CdCl₂、CaCl₂、NiCl₂、FeCl₃、CuCl₂、HgCl₂、AlCl₃、MnCl₂、CrCl₃、硝酸溶液均购于成都市科隆化学品有限公司(中国成都)。硫酸奎宁购自迈坤化工有限公司(中国上海)。其他化学药品和溶剂均购自万科试剂有限公司(中国雅安)，所有试剂均为分析纯。

transl

仪器:Varioskan Flash全波长扫描式酶标仪(美国赛默飞世尔科技有限公司);Lumina荧光分光光度计(美国赛默飞世尔科技有限公司);NICOLETiS10 型傅里叶变换红外光谱仪(美国赛默飞世尔科技有限公司);TEM-2100透射电子显微镜(日本LJEMOC);Milli-Q Gradient超纯水系统(美国密理博公司);Shimadzu D/Max-2500 X射线衍射仪(日本岛津公司)等。

transl

2.2　N-CQDs制备

本实验采用水热法制备绿色生物质猪骨氮掺杂碳量子点。制备方法如下:将骨粉与乙二胺混合在60 mL去离子水中搅拌均匀，然后将混合物转移到100 mL四氟乙烯内胆 Teflon反应釜中，并在烘箱中恒温加热，待反应液冷却得到黄褐色溶液。离心(4 000 r/20 min)后用0.22 μm滤膜过滤除去大颗粒杂质得到N-CQDs溶液，在4 ℃冰箱中避光保存。考察反应温度(160,180,200,220,240 ℃)、反应时间(8,10,12,14,16 h)、骨粉量(4,5,6,7,8 g)和乙二胺量(0.6,0.7,0.8,0.9,1 mL)对N-CQDs荧光强度的影响，确定最佳制备条件。

transl

2.3　N-CQDs表征

TEM-2100透射电子显微镜进行形貌特征分析；Lumina荧光分光光度计测量N-CQDs的荧光光谱；NICOLETiS10 型傅里叶变换红外光谱仪测定N-CQDs表面官能团；XRD-6000X射线衍射光谱仪测定XRD 谱图；Shimadzu D/Max-2500 X射线衍射仪测定XPS谱图；MAZ2012马尔文粒度仪测定Zeta电位。

transl

2.4　量子产率(QY)测定

使用硫酸奎宁(在350 nm的0.1 mol/L H₂SO₄中 QY=54%)为参比物质，分别测试N-CQDs和硫酸奎宁的紫外-可见吸收光谱及荧光光谱，代入公式(1):

transl

$\text{[math]}$

(1)

其中η为量子产率，I表示荧光发射强度，n表示溶剂的折射率，A表示吸光度。下标R和S分别表示已知的荧光标准样品和实验样品^[

10]。

transl

2.5　N-CQDs稳定性测定

将制备得到的N-CQDs溶液每隔7 d记录荧光发射光谱，考察N-CQDs储藏时间稳定性。将N-CQDs溶液置于365 nm紫外光下，分别照射0,30,60,90,120,150,180 min，考察N-CQDs光漂白稳定性。用0.5 mol/L的盐酸和氢氧化钠溶液调节N-CQDs溶液的pH值，考察N-CQDs的pH稳定性。在N-CQDs溶液中加入50 μL NaCl溶液，其浓度分别为0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1 mol/L，考察N-CQDs的离子稳定性。上述所有测试均是在417 nm激发波长下记录荧光发射光谱，平行测定3次。

transl

2.6　N-CQDs检测Co²⁺

在荧光比色皿中，加入1 mL 100倍分散体 N-CQDs 溶液、1 mL PBS(pH=7)以及分别加入浓度为 0.1,0.5,1,2,5,8,10,12,15, 20,25,30,40,50,60,70,80,90,100 μg/mL 的Co²⁺溶液，混合均匀后20 ℃反应10 min。417 nm激发波长下记录荧光发射光谱，以荧光猝灭率F/F₀为指标(F是加入Co²⁺溶液时的荧光强度，F₀是不加入Co²⁺溶液时的荧光强度)。

transl

在N-CQDs溶液中，分别加入1 mL浓度为100 μg/mL的金属离子水溶液(Co²⁺、K⁺、Zn²⁺、Ba²⁺、Mg²⁺、Na⁺、Cd²⁺、Ca²⁺、Ni²⁺、Fe³⁺、Cu²⁺、Hg²⁺、Al³⁺、Mn²⁺、Cr³⁺)，检测存在不同代表性离子的荧光强度，考察其选择性。

transl

在N-CQDs溶液中，加入1 mL浓度为100 μg/mL的Co²⁺溶液后，再分别加入不同倍数潜在干扰物离子溶液(Co²⁺、K⁺、Zn²⁺、Ba²⁺、Mg²⁺、Na⁺、Cd²⁺、Ca²⁺、Ni²⁺、Fe³⁺、Cu²⁺、Hg²⁺、Al³⁺、Mn²⁺、Cr³⁺ 、H₂P $\text{[math]}$ 、N $\text{[math]}$ 、C $\text{[math]}$ 、S $\text{[math]}$ 、OH^-、Lys、Asp、Cys、Trp、Thr、Gly、Phe)与体系混合，检测存在潜在干扰性离子条件下，体系的荧光强度变化，考察其抗干扰性。上述所有测试均是平行测定3次。

transl

2.7　实际样品测定

分别以来自实验室的自来水和青衣江(中国雅安)的河水作为实际检测样品，评估N-CQDs检测Co²⁺的实际适用性。根据HJ/T 91-2002采集样品后，将两种样品都分为两份。一份经0.45 μm微孔滤膜过滤，用硫酸溶液调节水样pH小于2，用于分光光度法检测(HJ 550-2015)；另一份经0.22 μm微孔滤膜过滤，用硫酸溶液调节水样pH至中性，用于N-CQDs检测。

transl

3　结果与讨论

3.1　N-CQDs制备条件优化

为了获得高荧光性能的N-CQDs，考察了水热反应温度、水热反应时间、骨粉量和乙二胺量对N-CQDs荧光强度的影响。由图2(a)可知，水热反应温度为200 ℃时(6 g骨粉，0.8 mL乙二胺，12 h),N-CQDs荧光强度最高。当水热反应温度开始升高，N-CQDs荧光强度也随之增加，可能是由于在碳化过程中合成了更多的N-CQDs颗粒；但随着温度进一步升高，N-CQDs荧光强度下降，这可能是由于N-CQDs颗粒发生了团聚^[

12]。由图2(b)可知，当水热反应时间为12 h时(6 g骨粉，0.8 mL乙二胺，200 ℃),N-CQDs荧光强度达到最高值。由图2(c)可知，在骨粉量为6 g时(0.8 mL乙二胺，水热12 h,200 ℃)N-CQDs荧光最强。由2(d)可知，在乙二胺量为0.8 mL时(6 g骨粉，0.8 mL乙二胺，12 h),N-CQDs荧光强度最高，随着乙二胺用量继续增加，N-CQDs荧光强度降低，可能是由于表面氨基数量增加，更易导致碳量子点聚合，产生自猝灭^{[Reference 13

Baidu Scholar

13]}。

transl

图1 N-CQDs的制备及检测Co²⁺示意图

Fig.1 Schematic representation of N-CQDs preparation and detection of Co²⁺

Download: Full-size image | High-res image | Low-res image

图2 水热反应温度(a)、水热反应时间(b)、骨粉量(c)、乙二胺量(d)对N-CQDs荧光强度的影响。插图:N-CQDs在紫外暗箱中的图片。

Fig.2 Influence of hydrothermal reaction temperature(a), hydrothermal reaction time(b), bone meal amount(c), ethylenediamine amount(d) on the fluorescence intensity of N-CQDs. Illustration: picture of N-CQDs in a UV dark box.

Download: Full-size image | High-res image | Low-res image

3.2　N-CQDs表征

图3(a)显示，所制备的N-CQDs呈圆球形，分散性好，且尺寸均一，插图表明，N-CQDs晶格条纹的晶面间距为0.21 nm，与石墨碳相符^[

14]。图3(b)是N-CQDs的粒径分布图，可以得到N-CQDs的平均粒径大小为2.34 nm。图3(c)是N-CQDs的XRD谱图，N-CQDs在2θ=22.2°出现宽峰，对应于石墨碳的(002)晶面，证实了N-CQDs的无定形结构^{[Reference 15-16

15-16]}。为了了解N-CQDs的表面官能团，对掺杂与不掺杂碳量子点(CQDs)进行了傅里叶变换红外光谱分析，如图3(d)所示。3 440 cm^-1处的峰归属于O—H和N—H的伸缩振动^{[Reference 17

Baidu Scholar

17]},2 962 cm^-1处的峰是由于C—H的伸缩振动^{[Reference 18

Baidu Scholar

18]},1 655 cm^-1和1 510 cm^-1处的峰是C $\text{[math]}$ O和C $\text{[math]}$ C基团不对称拉伸振动的结果^{[Reference 19

Baidu Scholar

19]},1 460 cm^-1处的峰归因于C—N的拉伸振动^{[Reference 20

Baidu Scholar

20]},1 041 cm^-1处的峰归因于C—O的伸缩振动^{[Reference 21

Baidu Scholar

21]}。CQDs的FT-IR谱图不含C—N的拉伸振动吸收峰，说明氮原子成功掺杂，并且N-CQDs表面含有氨基、羧基等官能团。N-CQDs水溶液的Zeta电位值为-31.3 mV,N-CQDs粒子带负电，并具有一定的稳定性。

transl

图3 N-CQDs的TEM图(a)、粒径分布图(b)、XRD谱图(c)、FT-IR谱图(d)。插图:N-CQDs的HRTEM图。

Fig.3 TEM image(a), particle size distribution(b), XRD spectrum(c), FT-IR spectra(d) of N-CQDs. Inset: HRTEM image of N-CQDs.

Download: Full-size image | High-res image | Low-res image

N-CQDs的光学性质通过紫外-可见吸收光谱和荧光光谱进行分析。图4(a)显示，N-CQDs在紫外吸收区表现出强烈的吸收，紫外吸收光谱在272 nm和332 nm处存在两个特征峰，在272 nm处的峰归因于C $\text{[math]}$ C的π-π^*轨道跃迁^[

22],332 nm处的峰归因于C $\text{[math]}$ O的n-π^*轨道跃迁^{[Reference 23

Baidu Scholar

23]}。荧光光谱表明，N-CQDs的最大发射峰位于488 nm，最大激发波长为417 nm。图4(a)插图显示，N-CQDs的水溶液在日光下呈黄褐色，在365 nm紫外光下呈蓝色。图4(b)显示，在340~460 nm的激发波长以20 nm的增量得到的N-CQDs发射光谱，随着激发波长的增加，最大发射峰发生红移，表明N-CQDs具有激发波长依赖性，这种现象可能与N-CQD表面不均匀的化学结构、分子状态及量子限域效应有关^{[Reference 24-25

24-25]}。以硫酸奎宁(0.1 mol/L H₂SO₄,QY=54%)为标准物质，测得的N-CQDs的量子产率为26.4%。

transl

图4 (a)N-CQDs的紫外-可见吸收光谱和荧光光谱，插图:N-CQDs水溶液在可见光(左)和紫外光(365 nm，右)下的照片；(b)不同激发波长下N-CQDs的发射光谱。

Fig.4 (a)UV-Vis absorption spectra and fluorescence spectra of N-CQDs. Inset: photograph of N-CQDs aqueous solution under visible light(left) and ultraviolet light(365 nm, right).(b)Emission spectra of N-CQDs at different excitation wavelengths.

Download: Full-size image | High-res image | Low-res image

采用XPS分析了N-CQDs表面的化学元素及化学键，如图5(a)所示，3个吸收峰分别对应C1s、N1s、O1s，键能分别为285.08,400.08,532.08 eV,3种元素的含量分别为64.41%、8.6%、26.98%。对XPS全谱图进行分峰，结果如图5(b)~(d)。图5(b)是C1s的分峰图，对应的键能分别为284.69,285.69,288.03 eV，分别对应C—C、C—N、C $\text{[math]}$ O/C $\text{[math]}$ N^[

26]。图5(c)是N1s的分峰图，对应的键能分别为399.05,399.9,401.16 eV，分别对应O $\text{[math]}$ C—N、C—N—C、N—H^{[Reference 27-28

27-28]}。图5(d)是O1s的分峰图，对应的键能分别为531.1,532.08,532.64 eV，分别对应C $\text{[math]}$ O、C—O、C—OH/C—O—C^{[Reference 29-30

29-30]}。这些结果与FT-IR结果一致，表明N-CQDs表面具有含氧和含氮基团，赋予了N-CQDs良好的水溶性。由图6可知，N-CQDs在4 ℃条件下保存60 d后荧光强度下降，可能是由于N-CQDs间产生团聚，造成荧光强度减弱。在紫外照射180 min、不同浓度NaCl条件和较宽的pH范围内，N-CQDs依然显示出强荧光、良好的稳定性和抗漂白性。

transl

图5 (a)N-CQDs的XPS谱图；(b)C1s的高分辨率XPS谱图；(c)N1s的高分辨率谱图；(d)O1s的高分辨率XPS谱图。

Fig.5 XPS of the N-CQDs(a) and C1s(b). N1s(c) and O1s(d) spectra of the CDs.

Download: Full-size image | High-res image | Low-res image

图6 储藏时间(a)、紫外照射时间(b)、pH(c)、NaCl浓度(d)对N-CQDs荧光强度的影响。

Fig.6 Influence of storage time(a), ultraviolet irradiation time(b), pH(c), NaCl concentration(d) on the fluorescence intensity of N-CQDs.

Download: Full-size image | High-res image | Low-res image

3.3　N-CQDs检测Co²⁺

如图7(a)所示，研究了N-CQDs对不同金属离子的选择性，将各种金属离子分别添加到N-CQDs的水溶液中，包括Co²⁺、K⁺、Zn²⁺、Ba²⁺、Mg²⁺、Na⁺、Cd²⁺、Ca²⁺、Ni²⁺、Fe³⁺、Cu²⁺、Hg²⁺、Al³⁺、Mn²⁺、Cr³⁺，金属离子的浓度均为100 μg/mL，仅Co²⁺具有猝灭N-CQDs荧光强度的能力，而其他金属离子几乎没有猝灭作用。图7(b)显示，在N-CQDs/Co²⁺溶液中加入其他干扰物质后，溶液的荧光强度无明显变化，表明这些干扰物质对Co²⁺的测定基本无干扰，这可能是由于Co²⁺与N-CQDs表面的某些官能团(—COOH、—OH、—CONH)反应形成复合物，促使电子从N-CQDs的激发态转移到Co²⁺的3d轨道，导致荧光猝灭^[

38]。如图7(c)、(d)所示，随着Co²⁺浓度的增加，N-CQDs在488 nm处的荧光强度逐渐降低。Co²⁺浓度为0~15 μg/mL(Y=-0.01104X+0.98879,R²=0.980 21)和30~80 μg/mL(Y=-0.0034X+0.85301,R²=0.990 06)时与N-CQDs猝灭程度呈线性关系，检出限(S/N=3)达到20 μg/L，低于WHO规定的限量值。与表1中Co²⁺检测方法相比较，本方法具有检出限较低、线性范围宽、成本低等优点。

transl

图7 (a)不同金属离子对N-CQDs荧光强度的影响；(b)其他物质存在时Co²⁺的测定；(c)不同Co²⁺浓度对N-CQDs荧光强度的影响；(d)F/F₀与Co²⁺浓度在0～100 μg·mL^-1的关系曲线(F是加入Co²⁺溶液时N-CQDs的荧光强度，F₀是不加入Co²⁺溶液时N-CQDs的荧光强度)，插图:F/F₀与Co²⁺浓度的线性关系(红色曲线:0～15 μg·mL^-1；蓝色曲线:30～80 μg·mL^-1);(e)在不同温度下Co²⁺猝灭的N-CQDs的Stern-Volmer曲线；(f)不存在和存在 Co²⁺ 时N-CQDs的紫外-可见吸收光谱。

Fig.7 (a)Influence of different metal ions on the fluorescence intensity of N-CQDs. (b)Determination of Co²⁺ in the presence of other substances. (c)Influence of different Co²⁺ concentrations on the fluorescence intensity of N-CQDs. (d)Relationship curve between F/F₀ and Co²⁺ concentration(F is the fluorescence intensity of N-CQDs when Co²⁺ solution is added, and F₀ is the fluorescence intensity of N-CQDs when Co²⁺ solution is not added). Inset: linear relationship between F/F₀ and Co²⁺ concentration(red curve: 0-15 μg·mL^-1; blue curve: 30-80 μg·mL^-1).(e)Stern-Volmer curves of Co²⁺ quenched N-CQDs at different temperature.(f)UV-Vis absorption spectra of N-CQDs in the absence and presence of Co²⁺.

Download: Full-size image | High-res image | Low-res image

表1 Co²⁺检测方法比较

Tab.1 Comparison of Co²⁺ detection methods

方法	材料	线性范围	检出限	参考文献
荧光	N-CQDs	0~15 μg·mL^-1, 30~80 μg·mL^-1	20 μg·L^-1(0.34 μmol·L^-1)	本方法
比色分析	硫化锌量子点	10~1 000 mg·L^-1	10 mg·L^-1	[31]
荧光	N-CQDs	0~90 μmol·L^-1	0.4 μmol·L^-1	[32]
荧光	CQDs	0.1~30 μmol·L^-1	0.052 μmol·L^-1	[33]
荧光	N-CQDs	5~30 μmol·L^-1	0.43 μmol·L^-1	[34]
荧光	CQDs	0~40 μmol·L^-1	0.45 μmol·L^-1	[35]
吸光度	金纳米粒子	1 000~15 000 μmol·L^-1	14 μmol·L^-1	[36]
荧光	N,S-CQDs	0.08~100 μmol·L^-1	0.08 μmol·L^-1	[37]

Download: CSV

Download: Table Images

荧光猝灭是荧光分子的表面基团与猝灭物质发生反应，导致荧光强度降低，通常分为静态猝灭和动态猝灭。静态猝灭的荧光猝灭常数随温度升高而减小，动态猝灭的荧光猝灭常数随温度升高而增大^[

29]。为了研究Co²⁺对N-CQDs荧光猝灭的机理，本文考察了不同温度下Co²⁺对N-CQDs的猝灭作用，并用Stern-Volmer方程来判断猝灭机理。Stern-Volmer方程为:

transl

$\text{[math]}$

(2)

其中F₀是不加入Co²⁺溶液时N-CQDs的荧光强度，F是加入Co²⁺溶液时N-CQDs的荧光强度，K_SV是Stern-Volmer猝灭常数，C为加入Co²⁺的浓度，曲线如图7(e)所示。在15,25,35 ℃下，猝灭常数K_SV分别为0.013 1,0.011 9,0.009，即随着温度升高，猝灭常数K_SV减小，表明Co²⁺是通过静态猝灭使得N-CQDs的荧光发生猝灭。此外，图7(f)显示，在N-CQDs溶液中加入Co²⁺后，其紫外吸收峰发生了变化，这可能是Co²⁺与N-CQDs的表面官能团形成了非荧光的基态复合物，并没有在N-CQDs的激发态发生反应。以上结果充分证明Co²⁺对N-CQDs的荧光猝灭类型为静态猝灭。

transl

3.4　实际样品中Co²⁺的检测

选择自来水和河水为实际样品，然后采用加标回收法检测水样中的Co²⁺，结果如表2所示。该方法的回收率为97.26%~109.14%,RSD<3.24%，回收率的准确度优于分光光度法分析结果96.15%~117.05%，表明N-CQDs能够用于实际水样中Co²⁺的检测。

transl

表2 自来水和河水中Co²⁺的检测结果

Tab.2 Test results of Co²⁺ in tap water and river water

Sample	Found/(μg·L^-1)	Added/ (μg·L^-1)	N-CQDs			HJ 550-2015
Sample	Found/(μg·L^-1)	Added/ (μg·L^-1)	Total found/(μg·L^-1)	Recover/%	RSD/%	Total found/(μg·L^-1)	Recover/%	RSD/%
River water	0	20	21.83	109.14	1.63	23.41	117.05	2.32
	0	40	39.25	98.13	3.24	44.70	111.75	5.71
	0	80	77.81	97.26	3.19	78.24	97.80	4.36
Tap water	0	20	19.57	97.85	1.91	19.23	96.15	4.60
	0	40	41.14	102.85	0.90	44.15	110.38	4.05
	0	80	79.26	99.08	1.25	84.17	105.21	2.83

Download: CSV

Download: Table Images

4　结论

本文以生物质废弃物猪骨为碳源，通过一步水热法合成了N-CQDs。XPS和FT-IR表征分析表明氮元素成功掺杂到碳量子点的结构中。N-CQDs的平均粒径为2.34 nm，颗粒分散均匀，表现出良好的溶解度、高稳定性和高荧光强度。基于Co²⁺能够有效猝灭N-CQDs的荧光，建立了一种高灵敏性和选择性的Co²⁺的检测方法，检测线性范围为0~15 μg/mL和30~80 μg/mL，检出限为20 μg/L，并能够用于实际样品中Co²⁺的检测，为环境分析提供了一种简单、快速、灵敏的检测Co²⁺的新方法。

transl

本文专家审稿意见及作者回复内容的下载地址:http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20210260.

transl

参考文献:

[1]

TRUFFAULT L, TA M T, DEVERS T, et al. On the curve-fitting of XPS Ce(3d) spectra of cerium oxides by E. Paparazzo, Materials Research Bulletin 46(2011) 323-326[J]. Mater. Res. Bull., 2012, 47(11): 3941-3942. [Baidu Scholar]

[2]

WANG C, ZHOU J D, RAN G X, et al. Bi-functional fluorescent polymer dots:a one-step synthesis via controlled hydrothermal treatment and application as probes for the detection of temperature and Fe3+[J]. J. Mater. Chem. C, 2017, 5(2): 434-443. [Baidu Scholar]

[3]

ZHANG H J, CHEN Y L, LIANG M J, et al. Solid-phase synthesis of highly fluorescent nitrogen-doped carbon dots for sensitive and selective probing ferric ions in living cells[J]. Anal. Chem., 2014, 86(19): 9846-9852. [Baidu Scholar]

[4]

ZHU X H, ZHAO T B, NIE Z, et al. Nitrogen-doped carbon nanoparticle modulated turn-on fluorescent probes for histidine detection and its imaging in living cells[J]. Nanoscale, 2016, 8(4): 2205-2211. [Baidu Scholar]

[5]

AWUAL M R, ISMAEL M, YAITA T. Efficient detection and extraction of cobalt(Ⅱ) from lithium ion batteries and wastewater by novel composite adsorbent[J]. Sens. Actuators B Chem., 2014, 191: 9-18. [Baidu Scholar]

[6]

LIAO S, ZHU F W, ZHAO X Y, et al. A reusable P, N-doped carbon quantum dot fluorescent sensor for cobalt ion[J]. Sens. Actuators B Chem., 2018, 260: 156-164. [Baidu Scholar]

[7]

STOICA A I, PELTEA M, BAIULESCU G E, et al. Determination of cobalt in pharmaceutical products[J]. J. Pharm. Biomed. Anal., 2004, 36(3): 653-656. [Baidu Scholar]

[8]

SIMONSEN L O, HARBAK H, BENNEKOU P. Cobalt metabolism and toxicology—a brief update[J]. Sci. Total Environ., 2012, 432: 210-215. [Baidu Scholar]

[9]

TIAN M, ZHANG J Q, LIU Y M, et al. One-pot synthesis of nitrogen-doped carbon dots for highly sensitive determination of cobalt ions and biological imaging[J]. Spectrochim. Acta A Mol. Biomol. Spectrosc., 2021, 252: 119541. [Baidu Scholar]

[10]

JING N, TIAN M, WANG Y T, et al. Nitrogen-doped carbon dots synthesized from acrylic acid and ethylenediamine for simple and selective determination of cobalt ions in aqueous media[J]. J. Lumin., 2019, 206: 169-175. [Baidu Scholar]

[11]

张崟, 卓勇贤, 张佳敏, 等. 猪骨利用的研究进展[J]. 农产品加工·学刊, 2010(11): 83-86. [Baidu Scholar]

ZHANG Y, ZHUO Y X, ZHANG J M, et al. Researches on application of pig bone[J]. Acad. Periodical Farm Products Process., 2010(11): 83-86. (in Chinese) [Baidu Scholar]

[12]

张正伟, 彭可睿, 陈建秋, 等. 生物质基碳量子点的制备及其光谱性质研究[J]. 生物质化学工程, 2014, 48(3): 30-35. [Baidu Scholar]

ZHANG Z W, PENG K R, CHEN J Q, et al. Preparation of carbon quantum dots by biologic matters and its spectrum properties[J]. Bio. Chem. Eng., 2014, 48(3): 30-35. (in Chinese) [Baidu Scholar]

[13]

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]. J. Mol. Liq., 2018, 269: 766-774. [Baidu Scholar]

[14]

WANG C J, SHI H X, YANG M, et al. Facile synthesis of novel carbon quantum dots from biomass waste for highly sensitive detection of iron ions[J]. Mater. Res. Bull., 2020, 124: 110730-1-8. [Baidu Scholar]

[15]

LIN L P, RONG M C, LU S S, et al. A facile synthesis of highly luminescent nitrogen-doped graphene quantum dots for the detection of 2, 4, 6-trinitrophenol in aqueous solution[J]. Nanoscale, 2015, 7(5): 1872-1878. [Baidu Scholar]

[16]

HSU P C, CHANG H T. Synthesis of high-quality carbon nanodots from hydrophilic compounds:role of functional groups[J]. Chem. Commun., 2012, 48(33): 3984-3986. [Baidu Scholar]

[17]

SHEN T Y, JIA P Y, CHEN D S, et al. Hydrothermal synthesis of N-doped carbon quantum dots and their application in ion-detection and cell-imaging[J]. Spectrochim. Acta A Mol. Biomol. Spectrosc., 2021, 248: 119282. [Baidu Scholar]

[18]

JOSEPH J, ANAPPARA A A. Ellagic acid-functionalized fluorescent carbon dots for ultrasensitive and selective detection of mercuric ions via quenching[J]. J. Lumin., 2017, 192: 761-766. [Baidu Scholar]

[19]

WU Z L, GAO M X, WANG T T, et al. A general quantitative pH sensor developed with dicyandiamide N-doped high quantum yield graphene quantum dots[J]. Nanoscale, 2014, 6(7): 3868-3874. [Baidu Scholar]

[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. [Baidu Scholar]

[21]

LIU W F, JIA H S, ZHANG J, et al. Preparation of nitrogen-doped carbon quantum dots(NCQDs) and application for non-enzymatic detection of glucose[J]. Microchem. J., 2020, 158: 105187. [Baidu Scholar]

[22]

GUO Y M, ZHANG L F, CAO F P, et al. Thermal treatment of hair for the synthesis of sustainable carbon quantum dots and the applications for sensing Hg2+[J]. Sci. Rep., 2016, 6: 35795-1-7. [Baidu Scholar]

[23]

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]. J. Colloid Interface Sci., 2019, 539: 332-341. [Baidu Scholar]

[24]

TANG Y, RAO L S, LI Z T, et al. Rapid synthesis of highly photoluminescent nitrogen-doped carbon quantum dots via a microreactor with foamy copper for the detection of Hg2+ ions[J]. Sens. Actuators B Chem., 2018, 258: 637-647. [Baidu Scholar]

[25]

LU D, TANG Y P, GAO J W, et al. Concentrated solar irradiation protocols for the efficient synthesis of tri-color emissive carbon dots and photophysical studies[J]. J. Mater. Chem. C, 2018, 6(47): 13013-13022. [Baidu Scholar]

[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 Chem., 2015, 218: 229-236. [Baidu Scholar]

[27]

HU X T, LI Y X, XU Y W, et al. Green one-step synthesis of carbon quantum dots from orange peel for fluorescent detection of Escherichia coli in milk[J]. Food Chem., 2021, 339: 127775. [Baidu Scholar]

[28]

LIU W, DIAO H P, CHANG H H, et al. Green synthesis of carbon dots from rose-heart radish and application for Fe3+ detection and cell imaging[J]. Sens. Actuators B Chem., 2017, 241: 190-198. [Baidu Scholar]

[29]

ZHAO C X, JIAO Y, HU F, et al. Green synthesis of carbon dots from pork and application as nanosensors for uric acid detection[J]. Spectrochim. Acta A Mol. Biomol. Spectrosc., 2018, 190: 360-367. [Baidu Scholar]

[30]

RAMEZANI Z, QORBANPOUR M, RAHBAR N. Green synthesis of carbon quantum dots using quince fruit(Cydonia oblonga) powder as carbon precursor:application in cell imaging and As3+ determination[J]. Colloids Surfaces A Physicochem. Eng. Aspects, 2018, 549: 58-66. [Baidu Scholar]

[31]

LIU X, YANG Y, LI Q, et al. Portably colorimetric paper sensor based on ZnS quantum dots for semi-quantitative detection of Co2+ through the measurement of grey level[J]. Sens. Actuators B Chem., 2018, 260: 1068-1075. [Baidu Scholar]

[32]

LIU X, WEI S G, DIAO Q P, et al. Hydrothermal synthesis of N-doped carbon dots for selective fluorescent sensing and cellular imaging of cobalt(Ⅱ)[J]. Microchim. Acta, 2017, 184(10): 3825-3831. [Baidu Scholar]

[33]

TIAN M, LIU Y M, WANG Y T, et al. Facile synthesis of yellow fluorescent carbon dots for highly sensitive sensing of cobalt ions and biological imaging[J]. Anal. Methods, 2019, 11(32): 4077-4083. [Baidu Scholar]

[34]

ATCHUDAN R, EDISON T N J I, PERUMAL S, et al. Betel-derived nitrogen-doped multicolor carbon dots for environmental and biological applications[J]. J. Mol. Liq., 2019, 296: 111817. [Baidu Scholar]

[35]

KONG D P, YAN F Y, HAN Z Y, et al. Cobalt(Ⅱ) ions detection using carbon dots as an sensitive and selective fluorescent probe[J]. RSC Adv., 2016, 6(72): 67481-67487. [Baidu Scholar]

[36]

ZHANG M, LIU Y Q, YE B C. Colorimetric assay for parallel detection of Cd2+, Ni2+ and Co2+ using peptide-modified gold nanoparticles[J]. Analyst, 2012, 137(3): 601-607. [Baidu Scholar]

[37]

CHEN Y M, SHANG P X, DONG Y Q, et al. Regulating the overlap between the absorption spectrum of metal ion-chromogenic agent and the emission spectrum of carbon-based dots to improve the sensing performance for metal ions[J]. Sens. Actuators B Chem., 2017, 242: 1210-1215. [Baidu Scholar]

[38]

SUN L L, LIU Y Y, WANG Y S, et al. Nitrogen and sulfur co-doped carbon dots as selective and visual sensors for monitoring cobalt ions[J]. Opt. Mater., 2021, 112: 110787. [Baidu Scholar]

摘要

以猪骨和乙二胺为碳源和氮源，通过一步水热法合成了氮掺杂碳量子点(N-CQDs)，并优化其制备条件。通过透射电子显微镜(TEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射图(XRD)、紫外-可见吸收光谱(UV-Vis)和X射线光电子能谱(XPS)技术，研究了N-CQDs的结构和光学性质及元素组成。所制备的N-CQDs具有较高的量子产率(26.4%)，平均粒径为2.34 nm，在365 nm紫外光照射下呈现出明亮的蓝色荧光。研究发现Co

对N-CQDs有良好的猝灭作用，从而建立了一种快速检测Co

的新方法。N-CQDs荧光猝灭强度与Co

浓度在0~15 μg/mL和30~80 μg/mL呈良好的线性关系，检出限为20 μg/L，加标回收率为97.26%~109.14%

RSD

3.24%，能够应用于实际水样中Co

含量的测定。

Abstract

Nitrogen-doped carbon quantum dots(N-CQDs) were successfully synthesized using pig bone and ethylenediamine as carbon and nitrogen sources by one-step hydrothermal method. Structure

optical properties and element composition of N-CQDs have been studied by transmission electron microscope(TEM)

Fourier transform infrared spectroscopy(FT-IR)

X-ray diffractometer patterns(XRD)

UV-Vis absorption spectroscopy(UV-Vis) and X-ray photoelectron spectroscopy(XPS) technologies. The synthesized N-CQDs have a high quantum yield(26.4%)

an average particle size of 2.34 nm

showing bright blue fluorescence under a 365 nm UV lamp. The study found that Co

had a good quenching effect on N-CQDs

so as to establish a new method for rapid detection of Co

. The fluorescence quenching intensity of N-CQDs has a good linear relationship with the concentration of Co

at 0-15 μg/mL and 30-80 μg/mL

the detection limit is 20 μg/L

and the recovery rate of standard addition is 97.26%-109.14%

RSD

3.24%

which can be applied to the determination of Co

content in actual water samples.

关键词

Keywords

references

TRUFFAULT L , TA M T , DEVERS T , et al . On the curve-fitting of XPS Ce(3d) spectra of cerium oxides by E. Paparazzo, Materials Research Bulletin 46(2011) 323-326 [J]. Mater. Res. Bull. , 2012 , 47 ( 11 ): 3941 - 3942 .

WANG C , ZHOU J D , RAN G X , et al . Bi-functional fluorescent polymer dots:a one-step synthesis via controlled hydrothermal treatment and application as probes for the detection of temperature and Fe3+ [J]. J. Mater. Chem. C , 2017 , 5 ( 2 ): 434 - 443 .

ZHANG H J , CHEN Y L , LIANG M J , et al . Solid-phase synthesis of highly fluorescent nitrogen-doped carbon dots for sensitive and selective probing ferric ions in living cells [J]. Anal. Chem. , 2014 , 86 ( 19 ): 9846 - 9852 .

ZHU X H , ZHAO T B , NIE Z , et al . Nitrogen-doped carbon nanoparticle modulated turn-on fluorescent probes for histidine detection and its imaging in living cells [J]. Nanoscale , 2016 , 8 ( 4 ): 2205 - 2211 .

AWUAL M R , ISMAEL M , YAITA T . Efficient detection and extraction of cobalt(Ⅱ) from lithium ion batteries and wastewater by novel composite adsorbent [J]. Sens. Actuators B Chem. , 2014 , 191 : 9 - 18 .

LIAO S , ZHU F W , ZHAO X Y , et al . A reusable P, N-doped carbon quantum dot fluorescent sensor for cobalt ion [J]. Sens. Actuators B Chem. , 2018 , 260 : 156 - 164 .

STOICA A I , PELTEA M , BAIULESCU G E , et al . Determination of cobalt in pharmaceutical products [J]. J. Pharm. Biomed. Anal. , 2004 , 36 ( 3 ): 653 - 656 .

SIMONSEN L O , HARBAK H , BENNEKOU P . Cobalt metabolism and toxicology—a brief update [J]. Sci. Total Environ. , 2012 , 432 : 210 - 215 .

TIAN M , ZHANG J Q , LIU Y M , et al . One-pot synthesis of nitrogen-doped carbon dots for highly sensitive determination of cobalt ions and biological imaging [J]. Spectrochim. Acta A Mol. Biomol. Spectrosc. , 2021 , 252 : 119541 .

JING N , TIAN M , WANG Y T , et al . Nitrogen-doped carbon dots synthesized from acrylic acid and ethylenediamine for simple and selective determination of cobalt ions in aqueous media [J]. J. Lumin. , 2019 , 206 : 169 - 175 .

张崟 , 卓勇贤 , 张佳敏 , 等 . 猪骨利用的研究进展 [J]. 农产品加工·学刊 , 2010 ( 11 ): 83 - 86 .

ZHANG Y , ZHUO Y X , ZHANG J M , et al . Researches on application of pig bone [J]. Acad. Periodical Farm Products Process. , 2010 ( 11 ): 83 - 86 . (in Chinese)

张正伟 , 彭可睿 , 陈建秋 , 等 . 生物质基碳量子点的制备及其光谱性质研究 [J]. 生物质化学工程 , 2014 , 48 ( 3 ): 30 - 35 .

ZHANG Z W , PENG K R , CHEN J Q , et al . Preparation of carbon quantum dots by biologic matters and its spectrum properties [J]. Bio. Chem. Eng. , 2014 , 48 ( 3 ): 30 - 35 . (in Chinese)

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]. J. Mol. Liq. , 2018 , 269 : 766 - 774 .

WANG C J , SHI H X , YANG M , et al . Facile synthesis of novel carbon quantum dots from biomass waste for highly sensitive detection of iron ions [J]. Mater. Res. Bull. , 2020 , 124 : 110730-1-8 .

LIN L P , RONG M C , LU S S , et al . A facile synthesis of highly luminescent nitrogen-doped graphene quantum dots for the detection of 2, 4, 6-trinitrophenol in aqueous solution [J]. Nanoscale , 2015 , 7 ( 5 ): 1872 - 1878 .

HSU P C , CHANG H T . Synthesis of high-quality carbon nanodots from hydrophilic compounds:role of functional groups [J]. Chem. Commun. , 2012 , 48 ( 33 ): 3984 - 3986 .

SHEN T Y , JIA P Y , CHEN D S , et al . Hydrothermal synthesis of N-doped carbon quantum dots and their application in ion-detection and cell-imaging [J]. Spectrochim. Acta A Mol. Biomol. Spectrosc. , 2021 , 248 : 119282 .

JOSEPH J , ANAPPARA A A . Ellagic acid-functionalized fluorescent carbon dots for ultrasensitive and selective detection of mercuric ions via quenching [J]. J. Lumin. , 2017 , 192 : 761 - 766 .

WU Z L , GAO M X , WANG T T , et al . A general quantitative pH sensor developed with dicyandiamide N-doped high quantum yield graphene quantum dots [J]. Nanoscale , 2014 , 6 ( 7 ): 3868 - 3874 .

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 .

LIU W F , JIA H S , ZHANG J , et al . Preparation of nitrogen-doped carbon quantum dots(NCQDs) and application for non-enzymatic detection of glucose [J]. Microchem. J. , 2020 , 158 : 105187 .

GUO Y M , ZHANG L F , CAO F P , et al . Thermal treatment of hair for the synthesis of sustainable carbon quantum dots and the applications for sensing Hg2+ [J]. Sci. Rep. , 2016 , 6 : 35795-1-7 .

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]. J. Colloid Interface Sci. , 2019 , 539 : 332 - 341 .

TANG Y , RAO L S , LI Z T , et al . Rapid synthesis of highly photoluminescent nitrogen-doped carbon quantum dots via a microreactor with foamy copper for the detection of Hg2+ ions [J]. Sens. Actuators B Chem. , 2018 , 258 : 637 - 647 .

LU D , TANG Y P , GAO J W , et al . Concentrated solar irradiation protocols for the efficient synthesis of tri-color emissive carbon dots and photophysical studies [J]. J. Mater. Chem. C , 2018 , 6 ( 47 ): 13013 - 13022 .

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 Chem. , 2015 , 218 : 229 - 236 .

HU X T , LI Y X , XU Y W , et al . Green one-step synthesis of carbon quantum dots from orange peel for fluorescent detection of Escherichia coli in milk [J]. Food Chem. , 2021 , 339 : 127775 .

LIU W , DIAO H P , CHANG H H , et al . Green synthesis of carbon dots from rose-heart radish and application for Fe3+ detection and cell imaging [J]. Sens. Actuators B Chem. , 2017 , 241 : 190 - 198 .

ZHAO C X , JIAO Y , HU F , et al . Green synthesis of carbon dots from pork and application as nanosensors for uric acid detection [J]. Spectrochim. Acta A Mol. Biomol. Spectrosc. , 2018 , 190 : 360 - 367 .

RAMEZANI Z , QORBANPOUR M , RAHBAR N . Green synthesis of carbon quantum dots using quince fruit(Cydonia oblonga) powder as carbon precursor:application in cell imaging and As3+ determination [J]. Colloids Surfaces A Physicochem. Eng. Aspects , 2018 , 549 : 58 - 66 .

LIU X , YANG Y , LI Q , et al . Portably colorimetric paper sensor based on ZnS quantum dots for semi-quantitative detection of Co2+ through the measurement of grey level [J]. Sens. Actuators B Chem. , 2018 , 260 : 1068 - 1075 .

LIU X , WEI S G , DIAO Q P , et al . Hydrothermal synthesis of N-doped carbon dots for selective fluorescent sensing and cellular imaging of cobalt(Ⅱ) [J]. Microchim. Acta , 2017 , 184 ( 10 ): 3825 - 3831 .

TIAN M , LIU Y M , WANG Y T , et al . Facile synthesis of yellow fluorescent carbon dots for highly sensitive sensing of cobalt ions and biological imaging [J]. Anal. Methods , 2019 , 11 ( 32 ): 4077 - 4083 .

ATCHUDAN R , EDISON T N J I , PERUMAL S , et al . Betel-derived nitrogen-doped multicolor carbon dots for environmental and biological applications [J]. J. Mol. Liq. , 2019 , 296 : 111817 .

KONG D P , YAN F Y , HAN Z Y , et al . Cobalt(Ⅱ) ions detection using carbon dots as an sensitive and selective fluorescent probe [J]. RSC Adv. , 2016 , 6 ( 72 ): 67481 - 67487 .

ZHANG M , LIU Y Q , YE B C . Colorimetric assay for parallel detection of Cd2+, Ni2+ and Co2+ using peptide-modified gold nanoparticles [J]. Analyst , 2012 , 137 ( 3 ): 601 - 607 .

CHEN Y M , SHANG P X , DONG Y Q , et al . Regulating the overlap between the absorption spectrum of metal ion-chromogenic agent and the emission spectrum of carbon-based dots to improve the sensing performance for metal ions [J]. Sens. Actuators B Chem. , 2017 , 242 : 1210 - 1215 .

SUN L L , LIU Y Y , WANG Y S , et al . Nitrogen and sulfur co-doped carbon dots as selective and visual sensors for monitoring cobalt ions [J]. Opt. Mater. , 2021 , 112 : 110787 .

Views

194

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Eu³⁺@MOF Constructed by Post Synthesis Modification Method and Its Application in Detection of Metal Ions

Cu(Ⅰ) Ion Detection with Europium (Ⅲ) Chelate Nanoparticles Based on Click Chemistry

Related Author

Wen QIAN

Li HE

Wu-shuang PAN

Yan-hua CHEN

Shu-liang LIU

Shu-juan CHEN

Ai-ping LIU

刘爱平

Related Institution

College of Food Science，Sichuan Agricultural University，Yaan

School of Chemistry and Environmental Engineering， Changchun University of Science and Technology

Jilin Petrochemical North Chemical Industrial Company

Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University

Laboratory of Analytical Chemistry for Life Science, Institute of Chemistry, Chinese Academy of Sciences (CAS)

Address：No.3888 Dong Nanhu Road, Changchun, Jilin, China Postal code：130033
Tel：0431-86176862 Email：fgxbt@126.com
Technical support is provided by Beijing Founder electronics co., LTD 吉ICP备11002662号-17 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰

Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co2+

QIAN Wen

HE Li

PAN Wu-shuang

CHEN Yan-hua

WANG Hui

LIU Shu-liang

CHEN Shu-juan

LIU Ai-ping

DOI：10.37188/CJL.20210260

Abstract

Keywords

1 引言

2 实验

2.1 实验试剂与仪器

2.2 N-CQDs制备

2.3 N-CQDs表征

2.4 量子产率(QY)测定

2.5 N-CQDs稳定性测定

2.6 N-CQDs检测Co2+

2.7 实际样品测定

3 结果与讨论

3.1 N-CQDs制备条件优化

3.2 N-CQDs表征

3.3 N-CQDs检测Co2+

3.4 实际样品中Co2+的检测

4 结论

参考文献:

摘要

Abstract

关键词

Keywords

references

Preparation of Pig Bone Nitrogen-doped Carbon Quantum Dots and Application in Detection of Co²⁺

1　引言

2　实验

2.1　实验试剂与仪器

2.2　N-CQDs制备

2.3　N-CQDs表征

2.4　量子产率(QY)测定

2.5　N-CQDs稳定性测定

2.6　N-CQDs检测Co²⁺

2.7　实际样品测定

3　结果与讨论

3.1　N-CQDs制备条件优化

3.2　N-CQDs表征

3.3　N-CQDs检测Co²⁺

3.4　实际样品中Co²⁺的检测

4　结论