CN114894757A - Method for detecting multiple heavy metal ions by using lead-doped PEG (polyethylene glycol) passivated graphene quantum dot fluorescent probe - Google Patents
Method for detecting multiple heavy metal ions by using lead-doped PEG (polyethylene glycol) passivated graphene quantum dot fluorescent probe Download PDFInfo
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Abstract
The invention discloses a method for detecting various heavy metal ions by using a lead-doped PEG (polyethylene glycol) passivated graphene quantum dot fluorescent probe. Dissolving cane molasses in deionized water, and adding Pb (Ac) 2; after ultrasonic treatment and centrifugation, taking supernatant fluid to be put in a reaction kettle, reacting in an oven, and filtering to obtain lead-doped carbon quantum dot stock solution; diluting with a polyethylene glycol passivator to obtain a polyethylene glycol passivated lead doped carbon quantum dot solution; adding or not adding a masking agent, and adding a solution to be detected; fixing the volume of the solution by using a polyethylene glycol passivator, shaking up and standing; and calculating the content of the heavy metal ions according to the fluorescence intensity result. The invention can not only detect any one of seven metal ions in the presence of single metal ion, but also selectively detect Fe in 14 metal ion mixed solution 3+ 、Cu 2+ 、Ag + The method has the advantages of high detection speed, high detection sensitivity and low detection limit, and can be applied to the fields of nano-medicine, biological imaging, biological sensing, chemical sensing and the like.
Description
Technical Field
The invention relates to the field of fluorescent nano materials, in particular to a method for detecting various heavy metal ions by using a lead-doped PEG (polyethylene glycol) passivated graphene quantum dot fluorescent probe.
Background
Heavy metal means a density of greater than 4.5g/cm 3 The metals of (1) have 60 natural metal elements with atomic numbers from 23(V) to 92(U), and the rest 54 metals except 6 of them are heavy metals in terms of density (Zhujialong, Xuwei Jie, Guo Shuo Cheng, Zhou Jia Yan, Lu Tong, Cili Peihong, Chuai Qiang, Sunrong. harm of heavy metal pollution in water and treatment technology [ J ] is]Modern agricultural technology, 2022 (06): 129-132), heavy metal pollution and the environmental pollution and health problems caused by the heavy metal pollution become one of the major problems in the world. The pollution of heavy metal ions in water mainly comprises mercury, cadmium, lead, chromium and other metal ions which can generate strong toxicity to organisms, for example, lead ions can influence the normal operation of nervous system, digestive system and heart, and are enriched in human body through the transmission action of biological chain (Wenxiang. harm and prevention and treatment measures of heavy metal pollution in water [ J]Chemical engineering and equipment, 2022 (02): 240-242.), heavy metal pollution can cause serious harm to human bodies, especially children, iron deficiency can cause anemia, and excessive intake of iron ions can seriously damage human organs; when the concentration of copper ions is over-standard or insufficient, imbalance of physiological activities of the organism can be caused, the intelligence of children is reduced, the liver is damaged and other diseases (Yao Yang, Yao Zhong, Lishuaitong, Dunming, Yang Xiyan, Yao Mao, Yao) are caused, and research progress of harm of heavy metals in aquatic products to human bodies is advanced [ J]Agricultural technologies and equipment, 2020 (10): 55-56.). Therefore, it is necessary to invent a method for detecting various heavy metal ions by using functionalized graphene quantum dots.
Graphene Quantum Dots (GQDs) as a novel quasi-spherical carbon nano material (Rixistelline, Zusanli. preparation research of carbon Dots progresses [ J ] rare metal materials and engineering, 2019, 48 (10): 3401) -3416.), has the advantages of small volume, low toxicity, strong photoluminescence, good optical stability and the like, and is a research hotspot in the field of analysis and detection. Heteroatom doping is one of important means for improving the fluorescence property of the carbon dots, the graphene quantum dots are easy to carry out surface modification by doping metal ions to adjust the band gap of the graphene quantum dots, the electron transition mode is changed, and the fluorescence property of the carbon dots is adjusted, so that the graphene quantum dots have great application prospects in the fields of analysis and detection, biological imaging detection, biological sensing detection, medicine and the like.
At present, methods for detecting heavy metal ions mainly comprise an oxidation-reduction titration method, a gravimetric method, an atomic absorption spectrometry method, a plasma method, a colorimetric method and the like, wherein the colorimetric method is the most used method for detecting heavy metals in laboratory detection and industrial wastewater detection, but the detection accuracy is not high (summer red, pottery Chongqing, Toulon. explore the heavy metal detection technology in food and the development thereof [ J]A food safety journal, 2022 (01): 183 charge 185.); the atomic absorption spectrometry has the problems of long detection time, matrix interference, background absorption and the like (Zhuangzhijia, Yingshiming, Imperata, Jiehong, and the progress of analysis and detection research on heavy metals in environment [ J]University of Guizhou university (Nature science edition), 2021, 39 (06): 83-90.); inductively coupled plasma mass spectrometry (ICP-MS) requires expensive equipment, has multiple analysis steps, and has high requirements on operators (Sunxuickweed, great Zengxuejia, Tang thinking, high courage-oriented. research progress of heavy metal detection method in water environment [ J]Resource saving and environmental protection, 2018 (12): 113+116.), the above method has the disadvantages of long detection period, many analysis steps, impurity interference and the like, and greatly restricts the commercial application of the methods in the fields of electrocatalysis, photocatalysis, biological imaging detection, environmental detection and the like; in addition, most of the existing fluorescence detection technologies based on graphene quantum dots can only detect Fe 3 + 、Cu 2+ 、Ag + Etc., and a plurality of metal ions cannot be selectively detected. Therefore, it is necessary to find a method for detecting various metal ions with high efficiency, rapidness and sensitivity.
Disclosure of Invention
The invention aims to provide a method for detecting various heavy metal ions by using a lead-doped PEG (polyethylene glycol) passivated graphene quantum dot fluorescent probe.
The method for detecting various heavy metal ions by using the lead-doped PEG passivated graphene quantum dot fluorescent probe comprises the following specific steps:
(1) dissolving 1.5-2.0mL of cane molasses in 25-30mL of deionized water, and adding 1-3mL of Pb (Ac) with the concentration of 0.1mol/L 2 A solution;
(2) performing ultrasonic treatment and centrifugation on the solution obtained in the step (1), taking 20-25mL of supernatant fluid to be placed in a 30mL reaction kettle with a polytetrafluoroethylene lining, reacting in an oven at 190 ℃ for 20-24 hours, cooling, and filtering to obtain a lead-doped graphene quantum dot stock solution;
(3) and (3) taking 100-.
(4) Adding or not adding 800 mu L of masking agent with the total volume of 600-; fixing the volume of the solution to 5mL by using analytically pure polyethylene glycol passivator, shaking up, and standing for 5 minutes; and (3) putting the solution into a cuvette of a VARIAN fluorescence spectrophotometer, selecting 550V voltage, performing fluorescence spectrum test under the test conditions that excitation slits and emission slits are respectively 5nm and excitation wavelength is 350-400nm, and calculating the content of heavy metal ions according to a fluorescence intensity result.
The polyethylene glycol passivator is one or more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-600, preferably polyethylene glycol-200.
The masking agent is two or more than two of Ethylene Diamine Tetraacetic Acid (EDTA), thiourea, sodium fluoride (NaF) and potassium thiocyanate (KSCN).
The prepared PEG-Pb-GQDs solution has the following characteristics:
(1) the surface of the graphene quantum dot contains divalent Pb 2+ Ion, Pb 2+ The introduction of the lead-doped graphene quantum dot influences the formation of a lead-doped graphene quantum dot crystal nucleus and the growth of a crystal;
(2) the graphene quantum dot solution contains a passivating agent polyethylene glycol;
(3) the graphene quantum dots are spherical in shape, the average particle size is 1.0-2.0nm, and the interplanar spacing is 0.21 nm.
The method can be used for selectively detecting various metal ions conveniently and at low cost, and the detection reagent of the method is a lead-doped passivated modified graphene quantum dot solution (PEG-Pb-GQDs). In the presence of single metal ions, the method can separately detect Fe 3+ 、Cu 2+ 、Ag + 、Co 2+ 、Ni 2+ 、Mn 2+ And Pb 2+ The corresponding detection linear ranges of the seven metal ions are respectively 12.00-52.00 mu mol/L, 12.00-28.00 mu mol/L, 28.00-52.00 mu mol/L, 40.00-56.00 mu mol/L, 64.00-92.00 mu mol/L, 40.00-60.00 mu mol/L and 44.00-110.00 mu mol/L, the corresponding detection Limits (LOD) are respectively 9.76 mu mol/L, 11.11 mu mol/L, 16.21 mu mol/L, 17.32 mu mol/L, 26.45 mu mol/L, 27.98 mu mol/L and 29.10 mu mol/L, and the corresponding linear correlation coefficients (R) are respectively 2 ) Respectively as follows: 0.9980, 0.9835, 0.9908, 0.9930, 0.9914, 0.9893, 0.9956. In the presence of the masking agent, Fe can be selectively detected in the solution with a plurality of metal ions 3+ 、Cu 2+ 、Ag + The corresponding detection linear ranges of the three metal ions are respectively as follows: 28.00-44.00 mu mol/L, 20.00-140.00 mu mol/L and 20.00-160.00 mu mol/L, and the corresponding LOD is 8.56 mu mol/L, 9.33 mu mol/L and 10.29 mu mol/L respectively.
The solution to be detected comprises but is not limited to preparation solution, domestic wastewater, tap water and factory sewage. The domestic wastewater refers to wastewater discharged in daily life of houses, schools, hospitals, shops, public places, industrial enterprise toilets and the like; the tap water refers to water which is purified and disinfected by a tap water treatment plant and is produced by the tap water treatment plant, meets the corresponding standard and is used for life and production of people; factory wastewater refers to water discharged from chemical plants or the like after treatment.
The beneficial effects of the invention are:
surface passivation and heteroatom doping are effective ways for improving the fluorescence property of GQDs. Doping with metal ions can alter the electron transfer form of GQDs compared to non-metal doping. Therefore, the surface passivation and the metal doping can realize the effect of double enhancement of the fluorescence performance of the GQDs. According to the invention, the quantum yield of the functionalized GQDs and the selective response to various metals are greatly enhanced by means of surface passivation and metal doping, and the interference of other metal ions is avoided by different masking agents, so that the selective detection of various metal ions is realized.
The detection method has the advantages of high speed, high sensitivity and low limit, and can respectively detect Fe by using PEG-Pb-GQDs in the presence of single metal ions 3+ 、Cu 2+ 、Ag + 、Co 2+ 、Ni 2+ 、Mn 2+ And Pb 2+ Seven kinds of metal ions; two mixed solutions of EDTA, thiourea, NaF and KSCN are used as masking agents, and Fe can be added 3+ 、Cr 3+ 、Ca 2+ 、Al 3+ 、Cu 2+ 、Pb 2+ 、Mn 2+ 、Ag + 、Ba 2+ 、Co 2+ 、Cd 2+ 、Zn 2+ 、Hg 2+ 、Mg 2+ 、Ni 2+ Selective detection of Fe in mixed solution of plasma metal ions 3+ 、Cu 2+ 、Ag + Three kinds of metal ions. The detection method is simple and rapid, does not need large-scale instruments and equipment, greatly saves time and energy, can be rapidly popularized in the fields of nano medicine, biological imaging, biological sensing, chemical sensing and the like, and promotes the rapid development of related fields.
Drawings
FIG. 1 is a graph showing fluorescence spectra of PEG-Pb-GQDs of example 1 at different excitation wavelengths.
FIG. 2 is a TEM image of PEG-Pb-GQDs in example 1 and the corresponding particle size distribution diagram (lower right insert).
FIG. 3 is a graph showing the fluorescent response of PEG-Pb-GQDs to different metal ions without masking agents.
FIG. 4 shows the PEG-Pb-GQDs vs. Fe in the presence of EDTA and thiourea mixed masking agent of example 2 3+ Fluorescence response pattern of metal ions.
FIG. 5 shows the fluorescence quenching degree of PEG-Pb-GQDs in the presence of EDTA and thiourea mixed masking agent and Fe in example 2 3+ Linear relationship between concentrations.
FIG. 6 shows the PEG-Pb-GQDs vs. Cu in the presence of NaF and KSCN mixed masking agents of example 3 2+ MetalFluorescence response plot of ions.
FIG. 7 is a graph of the degree of fluorescence quenching of PEG-Pb-GQDs with Cu under the masking of the mixing of NaF and KSCN in example 3 2+ Linear relationship between concentrations.
FIG. 8 shows PEG-Pb-GQDs vs. Ag in the presence of EDTA and NaF mixed masking agent of example 4 + Fluorescence response pattern of metal ions.
FIG. 9 shows the fluorescence quenching degree of PEG-Pb-GQDs masked by the mixing of EDTA and NaF and Ag in example 4 + Linear relationship between concentrations.
Detailed Description
Example 1:
(1) 1.8mL of cane molasses was dissolved in 26.2mL of deionized water, and 2mL of Pb (Ac) was added at a concentration of 0.1mol/L 2 A solution;
(2) performing ultrasonic treatment and centrifugation on the solution obtained in the step (1), taking 20mL of supernate to react in a 30mL reaction kettle with polytetrafluoroethylene as an inner liner in an oven at 190 ℃ for 24 hours, cooling, and filtering to obtain a lead-doped graphene quantum dot stock solution;
(3) diluting 100 mu L of the lead-doped graphene quantum dot stock solution obtained in the step (2) to 2mL by using analytically pure polyethylene glycol-200 to obtain a lead-doped polyethylene glycol passivated graphene quantum dot (PEG-Pb-GQDs) solution;
(4) the PEG-Pb-GQDs solution obtained in the step (3) is bright blue fluorescence under the irradiation of ultraviolet light and has dependence (see figure 1); transmission electron microscope TEM and HRTEM observation show that PEG-Pb-GQDs are spherical, the interplanar spacing is 0.21nm, and the average particle size is 1.0-2.0nm (see figure 2);
(5) adding 200 mu L of the PEG-Pb-GQDs solution obtained in the step (3) into the Fe-containing solution respectively 3+ 、Cu 2+ 、Ag + 、Co 2+ 、Ni 2+ 、Mn 2+ And Pb 2+ A solution to be tested of any one of the seven metals;
(6) continuously using PEG-200 to fix the volume of the solution obtained in the step (5) to 5mL, shaking up and standing for 5 minutes;
(7) and (3) putting the solution obtained in the step (6) into a cuvette of a VARIAN fluorescence spectrophotometer, selecting 550V voltage, and performing fluorescence spectrum test under the conditions that an excitation slit and an emission slit are respectively 5nm and an excitation wavelength is 376 nm.
The result shows that the lead-doped polyethylene glycol passivated graphene quantum dots can respectively detect Fe in the presence of single metal ions 3+ 、Cu 2+ 、Ag + 、Co 2+ 、Ni 2+ 、Mn 2+ And Pb 2+ Seven metals, corresponding detection linearity ranges of 12.00-52.00 mu mol/L, 12.00-28.00 mu mol/L, 28.00-52.00 mu mol/L, 40.00-56.00 mu mol/L, 64.00-92.00 mu mol/L, 40.00-60.00 mu mol/L and 44.00-110.00 mu mol/L, corresponding detection Limits (LOD) of 9.76 mu mol/L, 11.11 mu mol/L, 16.21 mu mol/L, 17.32 mu mol/L, 26.45 mu mol/L, 27.98 mu mol/L and 29.10 mu mol/L, corresponding linear correlation coefficients (R) 2 ) 0.9980, 0.9835, 0.9908, 0.9930, 0.9914, 0.9893 and 0.9956 respectively.
Example 2:
(1) 1.8mL of cane molasses was dissolved in 26.2mL of deionized water, and 2mL of Pb (Ac) was added at a concentration of 0.1mol/L 2 A solution;
(2) performing ultrasonic treatment and centrifugation on the solution obtained in the step (1), taking 20mL of supernatant fluid to be placed in a 30mL reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in a baking oven at 190 ℃, cooling, and filtering to obtain a lead-doped graphene quantum dot stock solution;
(3) diluting 100 mu L of the lead-doped graphene quantum dot stock solution obtained in the step (2) to 2mL by using analytically pure polyethylene glycol-200 to obtain a lead-doped polyethylene glycol passivated graphene quantum dot (PEG-Pb-GQDs) solution;
(4) the PEG-Pb-GQDs solution obtained in the step (3) emits bright blue fluorescence under the irradiation of ultraviolet light and has dependence (see figure 1); transmission electron microscope TEM and HRTEM observation show that PEG-Pb-GQDs are spherical, the interplanar spacing is 0.21nm, and the average particle size is 1.0-2.0nm (see FIG. 2).
(5) Adding 200 mu L of EDTA aqueous solution with the concentration of 0.1mol/L and 400 mu L of thiourea aqueous solution with the concentration of 0.1mol/L into the solution obtained in the step (3);
(6) adding 200 mu L of solution obtained in the step (5) containing Fe 3+ 、Cr 3+ 、Ca 2+ 、Al 3+ 、Cu 2+ 、Pb 2+ 、Mn 2+ 、Ag + 、Ba 2+ 、Co 2+ 、Cd 2+ 、Zn 2+ 、Hg 2+ 、Mg 2+ 、Ni 2+ 14 kinds of metal ion to be detected;
(7) continuously using PEG-200 to fix the volume of the solution obtained in the step (6) to 5mL, shaking up and standing for 5 minutes;
(8) and (3) putting the solution obtained in the step (7) into a cuvette of a VARIAN fluorescence spectrophotometer, selecting 550V voltage, and performing fluorescence spectrum test under the conditions that an excitation slit and an emission slit are respectively 5nm and an excitation wavelength is 376 nm.
The results show that the PEG-Pb-GQDs can react with Fe 3+ The metal ions were selectively detected (see FIG. 4), corresponding to a linear detection range of 28.00-44.00. mu. mol/L (see FIG. 5), a limit of detection (LOD) of 8.56. mu. mol/L, and a corresponding linear correlation coefficient of 0.9976.
Example 3:
(1) 1.8mL of waste cane molasses was dissolved in 26.2mL of deionized water, and 2mL of Pb (Ac) having a concentration of 0.1mol/L was added 2 A solution;
(2) performing ultrasonic treatment and centrifugation on the solution obtained in the step (1), taking 20mL of supernatant fluid to be placed in a 30mL reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in a baking oven at 190 ℃, cooling, and filtering to obtain a lead-doped graphene quantum dot stock solution;
(3) diluting 100 mu L of the lead-doped graphene quantum dot stock solution obtained in the step (2) to 2mL by using analytically pure polyethylene glycol-200 to obtain a lead-doped polyethylene glycol passivated graphene quantum dot (PEG-Pb-GQDs) solution;
(4) adding 400 mu L of NaF aqueous solution with the concentration of 0.1mol/L and 400 mu L of KSCN aqueous solution with the concentration of 0.1mol/L into the PEG-Pb-GQDs solution obtained in the step (3);
(5) adding 200 mu L of Fe into the solution obtained in the step (4) 3+ 、Cr 3+ 、Ca 2+ 、Al 3+ 、Cu 2+ 、pb 2+ 、Mn 2+ 、Ag + 、Ba 2+ 、Co 2+ 、Cd 2+ 、Zn 2+ 、Hg 2+ 、Mg 2+ 、Ni 2+ 14 kinds of metal ion to be detected;
(6) continuously using PEG-200 to fix the volume of the solution obtained in the step (5) to 5mL, shaking up and standing for 5 minutes;
(7) and (3) putting the solution obtained in the step (6) into a cuvette of a VARIAN fluorescence spectrophotometer, selecting 550V voltage, and performing fluorescence spectrum test under the test conditions that excitation slits and emission slits are respectively 5nm and excitation wavelength is 376 nm.
The results show that the PEG-Pb-GQDs can be used for treating Cu 2+ The metal ions were selectively detected (see FIG. 6), and the corresponding linear range of detection was 20.00-140.00. mu. mol/L (see FIG. 7), with a limit of detection (LOD) of 9.33. mu. mol/L.
Example 4:
(1) 1.8mL of cane molasses was dissolved in 26.2mL of deionized water, and 2mL of Pb (Ac) was added at a concentration of 0.1mol/L 2 A solution;
(2) performing ultrasonic treatment and centrifugation on the solution obtained in the step (1), taking 20mL of supernatant fluid to be placed in a 30mL reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in a baking oven at 190 ℃, cooling, and filtering to obtain a lead-doped graphene quantum dot stock solution;
(3) diluting 100 mu L of the lead-doped graphene quantum dot stock solution obtained in the step (2) to 2mL by using analytically pure polyethylene glycol-200 to obtain a lead-doped polyethylene glycol passivated graphene quantum dot (PEG-Pb-GQDs) solution;
(4) the PEG-Pb-GQDs solution obtained in the step (3) emits bright blue fluorescence under the irradiation of ultraviolet light and has dependence (see figure 1); transmission electron microscope TEM and HRTEM observation show that PEG-Pb-GQDs are spherical, the interplanar spacing is 0.21nm, and the average particle size is 1.0-2.0nm (see figure 2);
(5) adding 200 mu L of EDTA aqueous solution with the concentration of 0.1mol/L and 400 mu L of NaF aqueous solution with the concentration of 0.1mol/L into the PEG-Pb-GQDs solution obtained in the step (3);
(6) adding 200 mu L of Fe into the solution obtained in the step (5) 3+ 、Cr 3+ 、Ca 2+ 、Al 3+ 、Cu 2+ 、pb 2+ 、Mn 2+ 、Ag + 、Ba 2+ 、Co 2+ 、Cd 2+ 、Zn 2+ 、Hg 2+ 、Mg 2+ 、Ni 2+ 14 kinds of metal ion to be detected;
(7) continuously using PEG-200 to fix the volume of the solution obtained in the step (6) to 5mL, shaking up and standing for 5 minutes;
(8) and (3) putting the solution obtained in the step (7) into a cuvette of a VARIAN fluorescence spectrophotometer, selecting 550V voltage, and performing fluorescence spectrum test under the test conditions that an excitation slit and an emission slit are respectively 5nm and an excitation wavelength is 376 nm.
The results show that the PEG-Pb-GQDs can be applied to Ag + The metal ions were selectively detected (see FIG. 8), and the corresponding linear detection ranges were 20.00-160.00 μmol/L (see FIG. 9), respectively, and the limit of detection (LOD) was 10.29 μmol/L.
Claims (1)
1. A method for detecting various heavy metal ions by using a lead-doped PEG passivated graphene quantum dot fluorescent probe is characterized by comprising the following specific steps:
(1) dissolving 1.5-2.0mL of cane molasses in 25-30mL of deionized water, and then adding 1-3mL of Pb (Ac)2 solution with the concentration of 0.1 mol/L;
(2) performing ultrasonic treatment and centrifugation on the solution obtained in the step (1), taking 20-25mL of supernatant fluid to be placed in a 30mL reaction kettle with a polytetrafluoroethylene lining, reacting in an oven at 190 ℃ for 20-24 hours, cooling, and filtering to obtain a lead-doped graphene quantum dot stock solution;
(3) taking 100-; the lead-doped polyethylene glycol passivated graphene quantum dots are spherical in shape, the average particle size is 1.0-2.0nm, and the interplanar spacing is 0.21 nm;
(4) adding or not adding the PEG-Pb-GQDs solution obtained in the step (3) into 800 mu L of masking agent with the total volume of 600- 3+ 、Cu 2+ 、Ag + 、Co 2+ 、Ni 2+ 、Mn 2+ And Pb 2+ Any one metal ion or ions containing a plurality of metalsThe solution to be tested; fixing the volume of the solution to 5mL by using analytically pure polyethylene glycol passivator, shaking up, and standing for 5 minutes; placing the solution into a cuvette of a VARIAN fluorescence spectrophotometer, selecting 550V voltage, performing fluorescence spectrum test under the test conditions that excitation slits and emission slits are respectively 5nm and excitation wavelength is 350-400nm, and calculating the content of heavy metal ions according to a fluorescence intensity result;
the polyethylene glycol passivator is one or more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-600;
the masking agent is two or more than two of ethylenediamine tetraacetic acid, thiourea, sodium fluoride and potassium thiocyanate.
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