CN111560667B - Preparation method of modified electrospun carbon nanofiber for wastewater detection - Google Patents
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Abstract
The invention discloses a preparation method of modified electrospun carbon nanofibers for wastewater detection, which comprises the following steps: (1) placing aramid fiber in concentrated sulfuric acid and heating to form spinning solution; (2) electrostatic spinning the spinning solution to prepare electrospun fibers; (3) pre-oxidizing and carbonizing at high temperature to obtain electrospun carbon nanofibers; (4) modifying by using 2-methyl-1, 5-diaminopentane solution; (5) modifying with glutaraldehyde solution, and reacting in fluorescent carbon dot solution. The modified electrospun carbon nanofiber provided by the invention is loaded with the highly stable electrospun carbon nanofiber to form the fluorescent carbon dots for water quality detection, and is combined with specific targeting molecules through a chemical or physical method, so that the precise detection of pollutants in various water bodies can be realized.
Description
Technical Field
The invention belongs to the technical field, and particularly relates to a preparation method of modified electrospun carbon nanofibers for wastewater detection.
Background
Currently, the increasing water pollution problem poses serious threats to human health, wherein the discharge of industrial wastewater is one of the main causes of water resource pollution. The pollution of heavy metal ion wastewater in industrial wastewater is the most serious, and heavy metals in water environment are not only not degraded by organisms in water body, but also cause adverse reaction of organisms at all levels of an ecological system through the accumulation and amplification effect of a biological chain, and finally cause serious injury to human body. Therefore, the detection of the pollution components, especially heavy metal ions, in the water environment is of great significance. At present, the detection of heavy metal ions mainly depends on analytical methods of atomic spectrum \ mass spectrum, electrochemistry and the like, although the detection is accurate, the defects of expensive detection instruments, complex operation, complex pretreatment and the like exist, and the rapid detection is difficult to realize.
Fluorescent carbon Dots (carbon Dots, C-Dots or CDs), also known as carbon quantum Dots, are one of novel carbon nano functional materials following carbon nanotubes, nano diamonds and graphene, such carbon nanoparticles having a particle size generally less than 10nm and surface subjected to organic passivation treatment are organic-inorganic hybrid materials, have fluorescence properties comparable to those of conventional semiconductor quantum Dots, and have low toxicity and biocompatibility due to the fact that the carbon nanoparticles do not contain any toxic heavy metal elements, and are easy to functionally modify on the surface. However, the fluorescent carbon dots have extremely strong hydrophilicity, are difficult to remove when entering water, are easy to cause secondary pollution, and are not beneficial to realizing industrial application, so that a proper carrier needs to be developed for fixing in order to match the fluorescent carbon dots.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a preparation method of modified electrospun carbon nanofibers for wastewater detection.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of modified electrospun carbon nanofibers for wastewater detection comprises the following steps:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 80-90 ℃, dissolving the fiber to form 15-20% mass fraction aramid fiber/sulfuric acid spinning solution for later use;
(2) preparing the spinning solution into electrospun fibers through electrostatic spinning, and conveying the electrospun fibers into a vacuum oven for drying at room temperature;
(3) sending the dried electrospun fibers into a high-temperature furnace for pre-oxidation, and then carbonizing the fibers at high temperature in a vacuum furnace in the argon atmosphere to obtain electrospun carbon nanofibers for later use;
(4) putting the electrospun carbon nanofiber into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, then washing the electrospun carbon nanofiber by using pure water, immersing the electrospun carbon nanofiber into 2 mol/L2-methyl-1, 5-diaminopentane solution, and carrying out water bath at the temperature of 45-55 ℃ for 20-28 hours to obtain modified electrospun carbon nanofiber for later use;
(5) and (3) cleaning the obtained pure water, immersing the cleaned pure water into a 10% glutaraldehyde solution, carrying out shaking reaction at room temperature for 60-120 minutes, cleaning the solution by using the pure water, finally sending the solution into a fluorescent carbon dot solution to be detected, carrying out shaking reaction at room temperature for 12-24 hours, and cleaning the solution by using the pure water to obtain the modified electrospun carbon nanofiber.
Further, the electrostatic spinning conditions in the step 2 are as follows: the spinning voltage is 13-16kV, the feeding speed is 0.2-0.4mL/h, and the receiving distance is 15 cm.
Further, the pre-oxidation condition in the step 3 is to heat the mixture to 180 ℃ and 200 ℃ in a high temperature furnace at a heating rate of 1-2 ℃/min and keep the temperature for 3-4 hours.
Further, the temperature is raised to 650-750 ℃ at the temperature raising rate of 2-5 ℃/min during the high-temperature carbonization in the step 3, and the temperature is preserved for 2 hours.
Further, the shaking reaction rate in the step 5 is controlled to be 60 to 90 revolutions per minute.
Further, the fluorescent carbon dots in the step 5 comprise a metal ion probe, an anion probe and an organic small molecule probe.
A modified electrospun carbon nanofiber for wastewater detection is prepared by the preparation method.
An application of a modified electrospun carbon nanofiber for wastewater detection is used for detecting heavy metal ions, anion pollutants and organic micromolecular pollutants in wastewater.
The invention has the advantages that:
1. according to the invention, the electrospinning fiber is prepared from the aramid fiber through electrostatic spinning, and the aramid fiber is suitable for being used as a carrier of the fluorescent carbon dots due to the characteristics of high strength, high modulus, high temperature resistance, corrosion resistance and the like, and is easier to maintain physical and chemical stability in a polluted water body, thereby being beneficial to the stability of a detection result.
2. According to the invention, carbon atoms are introduced into the electrospun fiber through high-temperature oxidation and carbonization, and more active sites can overcome the defects of low chemical reaction activity and unsatisfactory composite enhancement effect of the aramid fiber caused by chemical stability, so that conditions are provided for loading of the fluorescent carbon dots.
3. The electrospun fiber is modified by two steps of 2-methyl-1, 5-diaminopentane and glutaraldehyde, and the surface of the fiber is grafted with hydrophilic group-NH2The regularity of the fiber is destroyed, so that the surface is rougher, the wettability of the surface of the fiber is improved, and meanwhile, the fluorescent carbon dots can be spread and fixed on the surface of the highly-wetted fiber by utilizing the extremely strong hydrophilicity of the fluorescent carbon dots, so that the stable load of the fluorescent carbon dots for detection is realized.
4. The modified electrospun carbon nanofiber obtained by the invention loads the electrospun carbon nanofiber with extremely high stability with the fluorescent carbon dots for water quality detection, and is combined with specific targeting molecules by a chemical or physical method, so that the accurate detection of pollutants in various water bodies can be realized.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
A preparation method of modified electrospun carbon nanofibers for wastewater detection comprises the following steps:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 80 ℃, dissolving the fiber to form an aramid fiber/sulfuric acid spinning solution with the mass fraction of 15% for later use;
(2) preparing the spinning solution into electrospun fiber through electrostatic spinning under the conditions that the spinning voltage is 13kV, the feeding speed is 0.2mL/h and the receiving distance is 15cm, and sending the electrospun fiber into a vacuum oven for drying at room temperature;
(3) sending the dried electrospun fiber into a high-temperature furnace, heating to 180 ℃ at the heating rate of 1 ℃/minute, keeping the temperature for 4 hours, heating to 650 ℃ at the heating rate of 2 ℃/minute in a vacuum furnace in the argon atmosphere, and keeping the temperature for 2 hours to obtain electrospun carbon nanofiber for later use;
(4) putting the electrospun carbon nanofiber into absolute ethyl alcohol, performing ultrasonic treatment for 30 minutes, cleaning the electrospun carbon nanofiber by using pure water, immersing the electrospun carbon nanofiber into 2 mol/L2-methyl-1, 5-diaminopentane solution, and performing water bath at 45 ℃ for 28 hours to obtain modified electrospun carbon nanofiber for later use;
(5) and (3) cleaning the obtained pure water, immersing the cleaned pure water into a 10% glutaraldehyde solution, carrying out shaking reaction at room temperature at 60 revolutions per minute for 120 minutes, cleaning the solution with the pure water, finally sending the solution into a fluorescent carbon dot solution to be detected, carrying out shaking reaction at room temperature at 60 revolutions per minute for 24 hours, and cleaning the solution with the pure water to obtain the modified electrospun carbon nanofiber.
Example 2
A preparation method of modified electrospun carbon nanofibers for wastewater detection comprises the following steps:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 90 ℃, dissolving the fiber to form aramid fiber/sulfuric acid spinning solution with the mass fraction of 20% for later use;
(2) preparing the spinning solution into electrospun fiber through electrostatic spinning under the conditions that the spinning voltage is 16kV, the feeding speed is 0.4mL/h and the receiving distance is 15cm, and sending the electrospun fiber into a vacuum oven for drying at room temperature;
(3) sending the dried electrospun fiber into a high-temperature furnace, heating to 200 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3 hours, then heating to 750 ℃ at the heating rate of 5 ℃/min in a vacuum furnace under the argon atmosphere, and keeping the temperature for 2 hours to obtain electrospun carbon nanofiber for later use;
(4) placing the electrospun carbon nanofiber in absolute ethyl alcohol for 30 minutes, cleaning with pure water, immersing in 2 mol/L2-methyl-1, 5-diaminopentane solution, and carrying out water bath at 55 ℃ for 20 hours to obtain modified electrospun carbon nanofiber for later use;
(5) and (3) cleaning the obtained pure water, immersing the cleaned pure water into a 10% glutaraldehyde solution, carrying out shaking reaction for 60 minutes at room temperature at 90 revolutions per minute, cleaning the solution with the pure water, finally sending the solution into a fluorescent carbon dot solution to be detected, carrying out shaking reaction for 12 hours at room temperature at 90 revolutions per minute, and cleaning the solution with the pure water to obtain the modified electrospun carbon nanofiber.
Example 3
A preparation method of modified electrospun carbon nanofibers for wastewater detection comprises the following steps:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 85 ℃, dissolving the fiber, and forming an aramid fiber/sulfuric acid spinning solution with the mass fraction of 18% for later use;
(2) preparing the spinning solution into electrospun fiber through electrostatic spinning under the conditions that the spinning voltage is 15kV, the feeding speed is 0.3mL/h and the receiving distance is 15cm, and sending the electrospun fiber into a vacuum oven for drying at room temperature;
(3) sending the dried electrospun fiber into a high-temperature furnace, heating to 190 ℃ at the heating rate of 1 ℃/minute, keeping the temperature for 4 hours, then heating to 700 ℃ at the heating rate of 3 ℃/minute in a vacuum furnace in the argon atmosphere, and keeping the temperature for 2 hours to obtain electrospun carbon nanofiber for later use;
(4) putting the electrospun carbon nanofiber into absolute ethyl alcohol, performing ultrasonic treatment for 30 minutes, cleaning the electrospun carbon nanofiber by using pure water, immersing the electrospun carbon nanofiber into 2 mol/L2-methyl-1, 5-diaminopentane solution, and performing water bath at 50 ℃ for 24 hours to obtain modified electrospun carbon nanofiber for later use;
(5) and (3) cleaning the obtained pure water, immersing the cleaned pure water into a 10% glutaraldehyde solution, carrying out shaking reaction for 90 minutes at room temperature at 75 revolutions per minute, cleaning the solution with the pure water, finally sending the solution into a fluorescent carbon dot solution to be detected, carrying out shaking reaction for 18 hours at room temperature at 75 revolutions per minute, and cleaning the solution with the pure water to obtain the modified electrospun carbon nanofiber.
Comparative example 1
Compared with the example 3, the method has the same steps without adding the high-temperature oxidation and carbonization processes, and comprises the following specific steps:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 85 ℃, dissolving the fiber, and forming an aramid fiber/sulfuric acid spinning solution with the mass fraction of 18% for later use;
(2) preparing the spinning solution into electrospun fibers through electrostatic spinning under the conditions that the spinning voltage is 15kV, the feeding speed is 0.3mL/h and the receiving distance is 15cm, and sending the electrospun fibers into a vacuum oven for drying at room temperature;
(3) putting the electrospun fiber into absolute ethyl alcohol, performing ultrasonic treatment for 30 minutes, cleaning the electrospun fiber by using pure water, immersing the electrospun fiber into 2 mol/L2-methyl-1, 5-diaminopentane solution, and performing water bath at 50 ℃ for 24 hours to obtain modified electrospun fiber for later use;
(4) and (3) cleaning the obtained product with pure water, immersing the cleaned product in a 10% glutaraldehyde solution, carrying out shaking reaction at room temperature at 75 revolutions per minute for 90 minutes, cleaning the product with pure water, finally sending the product into a fluorescent carbon dot solution to be detected, carrying out shaking reaction at room temperature at 75 revolutions per minute for 18 hours, and cleaning the product with pure water after the reaction is finished.
The modified electrospun fibers obtained in example 3 and comparative example 1 were subjected to electron microscope scanning, and the results are shown in table 1:
TABLE 1
From the results, the modified electrospun fiber after high-temperature oxidation and carbonization is beneficial to the formation of a disordered carbon structure, so that the reaction specific surface area is increased, the reaction contact area can be effectively increased, more grafting sites are provided for the subsequent modification of 2-methyl-1, 5-diaminopentane and glutaraldehyde, and a structural basis is provided for improving the overall hydrophilicity of the fiber material.
Comparative example 2
Compared with the example 3, the other steps are the same without adding the modification process of the electrospun fiber, and the specific steps are as follows:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 85 ℃, dissolving the fiber, and forming an aramid fiber/sulfuric acid spinning solution with the mass fraction of 18% for later use;
(2) preparing the spinning solution into electrospun fiber through electrostatic spinning under the conditions that the spinning voltage is 15kV, the feeding speed is 0.3mL/h and the receiving distance is 15cm, and sending the electrospun fiber into a vacuum oven for drying at room temperature;
(3) sending the dried electrospun fiber into a high-temperature furnace, heating to 190 ℃ at the heating rate of 1 ℃/minute, keeping the temperature for 4 hours, then heating to 700 ℃ at the heating rate of 3 ℃/minute in a vacuum furnace under the argon atmosphere, and keeping the temperature for 2 hours to obtain electrospun carbon nanofiber for later use;
(4) and (3) feeding the electrospun carbon nanofiber into a fluorescent carbon dot solution to be detected, shaking and reacting at room temperature at 75 rpm for 18 hours, and washing with pure water after reaction.
The modified electrospun carbon nanofibers obtained in example 3 and the electrospun carbon nanofibers obtained in comparative example 2 were subjected to electron microscope scanning and static contact angles before and after fixing the fluorescent carbon dots, respectively, and the results are shown in table 2:
TABLE 2
From the above results, it can be seen that the fibers after the two-step modification are grafted with hydrophilic group-NH2Compared with the comparative example 2, the regularity of the fiber is obviously damaged, so that the surface is rougher, the comparative example 2 basically keeps the shape of the carbonized fiber, the test result of the static contact angle also shows that the wettability of the fiber is greatly improved through the grafting of hydrophilic groups, and meanwhile, the extreme hydrophilicity of the fluorescent carbon dots also enables water drops on the modified fiber surface to be easily spread, so that the stable detection of the water environment is facilitated.
The specific water quality test is as follows:
the fluorescent carbon dots are prepared into a standard solution with the concentration of 0.0001mol/L for testing.
Making standard library data: preparing heavy metal ion solutions with different concentrations, wherein heavy metals can be copper, mercury, lead, cobalt, cadmium and other heavy metal ions, respectively adding the heavy metals into the fluorescent carbon dot standard solutions, respectively measuring fluorescence intensity of each solution after reaction, and drawing a quantitative standard curve between the fluorescence intensity variation before and after the addition of the heavy metal ion solutions and the concentration of the heavy metal ions.
Randomly selecting 3 sewage plant wastewater (1 part, 2 parts and 3 parts in the following) as a solution to be tested, wherein the volume of each part is 1L, respectively testing lead ions and cadmium ions, taking an average value 3 times in each test, respectively immersing the modified electrospun carbon nanofibers obtained in the examples 1, 2 and 3 into the solution to be tested during the test, measuring the fluorescence intensity after reaction, calculating the fluorescence intensity variation before and after the addition of the liquid to be tested, finding the concentration of heavy metal ions corresponding to the fluorescence intensity variation in a prepared quantitative standard curve, and simultaneously measuring by using an atomic spectrophotometry, wherein the comparison result is shown in table 3:
TABLE 3
As can be seen from the above table, the analysis results of examples 1, 2, and 3 have a good matching degree with the measurement results of an atomic spectrophotometer using an international standard method, which indicates that the detection accuracy of the modified electrospun carbon nanofibers of the present invention for pollutants and heavy metal ions in water is good, and meanwhile, since the modified electrospun carbon nanofibers of the present invention are tested by fixing the fluorescent carbon dots, the detection of the fluorescent carbon dots is more direct, which avoids the problem of secondary pollution caused by the fact that the fluorescent carbon dots are difficult to remove after entering water, thereby optimizing the use mode, being capable of directly and rapidly using and testing in a polluted water body, solving the problem that the fluorescent carbon dots have too strong water solubility and cannot be used industrially, and meanwhile, the extremely strong physicochemical stability of the fiber material ensures the consistency of the detection results, and being a good wastewater detection material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of modified electrospun carbon nanofibers for wastewater detection is characterized by comprising the following steps:
(1) placing the nano-scale aramid fiber in concentrated sulfuric acid, heating to 80-90 ℃, and dissolving the fiber to form 15-20% aramid fiber/sulfuric acid spinning solution for later use;
(2) preparing the spinning solution into electrospun fibers through electrostatic spinning, and conveying the electrospun fibers into a vacuum oven for drying at room temperature;
(3) sending the dried electrospun fibers into a high-temperature furnace for pre-oxidation, and then carbonizing the fibers at high temperature in a vacuum furnace in the argon atmosphere to obtain electrospun carbon nanofibers for later use;
(4) putting the electrospun carbon nanofiber into absolute ethyl alcohol for ultrasonic treatment for 30 minutes, then washing the electrospun carbon nanofiber by using pure water, immersing the electrospun carbon nanofiber into 2 mol/L2-methyl-1, 5-diaminopentane solution, and carrying out water bath at the temperature of 45-55 ℃ for 20-28 hours to obtain modified electrospun carbon nanofiber for later use;
(5) washing the obtained product with pure water, immersing the product in 10% glutaraldehyde solution, shaking for reaction at room temperature for 60-120 min, washing with pure water, feeding into fluorescent carbon dot solution to be detected, shaking for reaction at room temperature for 12-24 h, washing with pure water to obtain modified electrospun carbon nanofiber,
the pre-oxidation condition in the step 3 is to heat the mixture to 180 ℃ and 200 ℃ in a high temperature furnace at the heating rate of 1-2 ℃/min and keep the temperature for 3-4 hours,
raising the temperature to 650-750 ℃ at the temperature rise rate of 2-5 ℃/min during the high-temperature carbonization in the step 3, and preserving the temperature for 2 hours.
2. The method for preparing the modified electrospun carbon nanofiber for wastewater detection according to claim 1, wherein the conditions of electrospinning in the step 2 are as follows: the spinning voltage is 13-16kV, the feeding speed is 0.2-0.4mL/h, and the receiving distance is 15 cm.
3. The method for preparing the modified electrospun carbon nanofiber for wastewater detection according to claim 1, wherein the rate of shaking reaction in the step 5 is controlled to be 60-90 rpm.
4. The method for preparing the modified electrospun carbon nanofiber for wastewater detection according to claim 1, wherein the fluorescent carbon dots in the step 5 comprise a metal ion probe, an anion probe and an organic small molecule probe.
5. A modified electrospun carbon nanofiber for wastewater detection, which is prepared by the preparation method of any one of claims 1 to 4.
6. The use of the modified electrospun carbon nanofiber for wastewater detection according to claim 5 for the detection of heavy metal ions, anionic pollutants and organic small molecule pollutants in wastewater.
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