CN116575230B - Plant-based quantum dot composite fluorescent fiber and preparation method and application thereof - Google Patents
Plant-based quantum dot composite fluorescent fiber and preparation method and application thereof Download PDFInfo
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/53—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with hydrogen sulfide or its salts; with polysulfides
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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Abstract
The invention discloses a preparation method of a plant-based quantum dot composite fluorescent fiber, which comprises the following steps: (1) Preparing quantum dots modified by surface ligands by adopting a one-step hydrothermal method; (2) Adding plant fiber into polyelectrolyte solution for soaking, and coating polyelectrolyte on the surface of the plant fiber by utilizing the interaction of charges between the surface of the plant fiber and the polyelectrolyte; (3) Immersing the plant fiber with the polyelectrolyte coated on the surface in a quantum dot aqueous solution with the concentration of 0.1-1 w%, and coating the quantum dot outside the fiber by utilizing the interaction of the group modified on the surface of the quantum dot and the polyelectrolyte to complete one-time assembly; (4) Repeating the assembling step (3) at least once, thereby obtaining the plant-based quantum dot composite fluorescent fiber. The method does not damage plant fibers, can regulate and control the luminous wavelength and intensity of the fluorescent fibers, and the prepared fluorescent fibers have stable performance and good washing fastness and can be applied to the anti-counterfeiting field.
Description
Technical Field
The invention belongs to the field of preparation methods of fluorescent fibers, and particularly relates to a plant-based quantum dot composite fluorescent fiber and a preparation method thereof.
Background
Fluorescent fibers are used as anti-counterfeiting fibers, and refer to fibers which emit light with a certain color under the irradiation of ultraviolet light or infrared light. The traditional fluorescent fiber adopts synthetic fiber as a base material, and the plant fiber belongs to natural fiber, has wide sources and rich yield, is biodegradable, and is a good base material for preparing the fluorescent fiber. At present, the plant-based fluorescent fiber is mostly dyed by adopting an organic fluorescent dye, the structure of the organic fluorescent dye is easy to be damaged, the stability is poor, and the photobleaching is easy to occur in the use process so as to influence the durability of the fluorescent fiber. The fluorescent quantum dot has the characteristics of adjustable emission wavelength, good light stability, light bleaching resistance, wide excitation spectrum, narrow emission spectrum, long fluorescence service life, good biocompatibility and the like, and can be used as a fluorescent functional substance to prepare composite fluorescent fibers. The existing plant-based quantum dot composite fluorescent fiber is prepared by a one-pot method, and because the one-pot method usually requires high temperature and long reaction time, the plant fiber is easy to degrade under the high-temperature reaction condition, the strength performance of the prepared fluorescent fiber can be obviously reduced, the fluorescence intensity of the prepared fluorescent fiber is not adjustable, and the emission wavelength is single. The layer-by-layer self-assembly technology is a technology for self-assembling a group assembly body and an assembly unit by taking electrostatic interaction, hydrogen bond interaction, coordination interaction, covalent bond interaction and the like as driving forces, and is widely used for film preparation. The layer-by-layer and assembly technology is utilized, the surface of the plant fiber is taken as a film forming base material, the quantum dot is taken as an assembly unit, a proper assembly ligand is selected, and the quantum dot film is self-assembled on the surface of the plant fiber. The fluorescent fiber prepared by the method can control the fluorescence intensity by adjusting the number of assembly layers, can also control the emission wavelength of the fluorescent fiber by controlling the quantum dot types, can not reduce the fiber intensity in the preparation process, and has great application value and potential in the anti-counterfeiting field.
Disclosure of Invention
The invention aims to provide a plant-based quantum dot composite fluorescent fiber and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
According to the invention, the quantum dot modified by the surface ligand is prepared firstly, then the plant fiber is taken as a substrate, and the quantum dot film is self-assembled layer by layer on the surface of the plant fiber by utilizing the interaction between the fiber and polyelectrolyte and between the polyelectrolyte and the groups modified on the surface of the quantum dot, so that the fluorescent fiber is obtained.
The preparation method of the plant-based quantum dot composite fluorescent fiber comprises the following steps:
(1) Preparing quantum dots modified by surface ligands by adopting a one-step hydrothermal method, and obtaining the quantum dots through ethanol precipitation, centrifugation and washing;
(2) Preparing polyelectrolyte solution with the concentration of 0.5-2 w%, adding plant fibers into the polyelectrolyte solution for soaking, and coating the polyelectrolyte on the surface of the plant fibers by utilizing the interaction of charges between the surface of the plant fibers and the polyelectrolyte;
(3) The plant fiber with the polyelectrolyte coated on the surface is soaked in a quantum dot aqueous solution with the concentration of 0.1-1 w%, and the quantum dot is coated outside the fiber by utilizing the interaction between the groups modified on the surface of the quantum dot and the polyelectrolyte, so that the polyelectrolyte-quantum dot film assembly is completed once;
(4) And (3) repeating the assembling step for at least one time by taking the covalent action of the surface groups of the quantum dots and polyelectrolyte as an assembling driving force, thereby obtaining the plant-based quantum dot composite fluorescent fiber.
Preferably, the surface ligand modified quantum dot is a thioglycollic acid modified AgInZnS quantum dot, a 3-mercaptopropionic acid modified AgInZnS quantum dot or an L-cysteine modified AgInZnS quantum dot.
Preferably, the polyelectrolyte is polyethylenimine and/or polydiene dimethyl ammonium chloride.
Preferably, the preparation of the surface ligand modified quantum dot: uniformly mixing a cation precursor solution, adding a ligand aqueous solution, regulating the pH value to be 6-10 after uniformly mixing, slowly adding an anion precursor solution under the action of magnetic stirring, adding a reaction mixed solution into a reaction kettle, reacting for 5+/-2 hours at the temperature of 110+/-20 ℃, and preparing the surface ligand modified quantum dot through ethanol precipitation, centrifugation and washing.
Preferably, the cation precursor is a compound of Ag +、Zn2+、In3+, the molar ratio of Ag +/In3+ is 0.05-0.20, and the molar ratio of Zn 2+/In3+ is 0.25-1.00; the anion precursor is a compound of S 2-, and the molar ratio of S 2-/In3+ is 0.5-2; the ligand is one of thioglycollic acid, 3-mercaptopropionic acid and L-cysteine, and the molar ratio of the ligand to In 3+ is 10-80.
Preferably, the reaction conditions of the one-step hydrothermal process are: the pH value is 6-10, the reaction temperature is 90-130 ℃, and the reaction time is 3-7h.
Preferably, the ratio of the plant fiber to the polyelectrolyte solution in step (3) is 1:20-1:100g/mL.
Preferably, the soaking time in the step (3) is 1-20min.
Preferably, the plant fiber is needle wood fiber, cotton fiber, broad-leaved wood fiber or bamboo fiber.
The plant-based quantum dot composite fluorescent fiber prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
The preparation method of the plant-based quantum dot composite fluorescent fiber provided by the invention is simple to operate, the preparation condition of the fluorescent fiber is mild, the plant fiber is not damaged, and the strength of the prepared fluorescent fiber is not affected. The fluorescent quantum dots can be stably combined on the surface of the plant fiber, and can be still stably combined on the surface of the fiber after washing for many times. The method can control the fluorescence intensity by controlling the number of assembly layers, and can adjust the emission wavelength by changing the types of assembled quantum dots, thereby realizing the regulation and control of the luminescence color without introducing new doping elements, and the fluorescent fiber prepared by the method has fluorescence adjustability. The fluorescent fiber prepared by the method can obtain fluorescence of different colors, the strength of the fluorescent fiber can keep the strength of the fibril, the performance of the fluorescent fiber is stable, the washing fastness is good, and the fluorescent fiber can be applied to the anti-counterfeiting field.
Drawings
FIG. 1 is a photograph showing a comparison of fluorescent fibers prepared by a layer-by-layer self-assembly method with ultraviolet light, wherein (a) and (b) are fluorescent fibers prepared in example 5, (c) and (d) are fluorescent fibers prepared in example 2, (e) and (f) are fluorescent fibers prepared in example 1, and (g) and (h) are fluorescent fibers prepared in example 4.
FIG. 2 shows photoluminescence spectra (PL) of fluorescent color-controllable fluorescent fibers prepared by a layer-by-layer self-assembly method, wherein 554nm, 618nm and 685nm are emission wavelength peaks of the fluorescent fibers prepared in example 5, example 1 and example 4, respectively.
FIG. 3 shows laser confocal images (CLSM) of fluorescent fibers with adjustable fluorescence intensity prepared by the layer-by-layer self-assembly method in example 2, wherein (a), (b), (c) and (d) are respectively 0, 3, 6 and 9 assembly cycles.
Fig. 4 shows the surface morphology (SEM) and elemental composition (EDS) of the fluorescent fibers prepared by the layer-by-layer self-assembly method in example 2, respectively (a) and (c) are SEM of cotton fibers and fluorescent fibers, and (b) and (d) are EDS of cotton fibers and fluorescent fibers.
FIG. 5 is a comparison of the zero gauge tensile index of the fiber versus the length of the fiber of the fluorescent fiber of example 6 prepared by the layer-by-layer self-assembly method and comparative example 1 prepared by the one pot method.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are for illustration of the application only and are not intended to limit the scope of the application. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Reagent source:
AgNO 3·H2O、Zn(NO3)2·2H2O、NaS·9H2 O, naOH (guangzhou chemical reagent plant); polyethyleneimine, polydiene dimethyl ammonium chloride, in (NO 3)3·H2 O, thioglycolic acid, 3-mercaptopropionic acid, L-cysteine, shanghai Ala Biochemical technologies Co., ltd.).
Example 1
A needle leaf wood fiber based quantum dot composite yellow fluorescent fiber based on thioglycollic acid modified AgInZnS quantum dots and a preparation method thereof comprise the following steps:
(1) Preparation of thioglycollic acid modified AgInZnS quantum dots: 0.1mL AgNO3·H2O(0.5M)、0.5mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL of deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.92g of thioglycollic acid is added into the mixed solution, the pH is regulated to 8.5 by NaOH solution, and then 1mL of NaS.9H 2 O (1M) is slowly dripped into the cation precursor solution. The mixed solution was transferred to a stainless steel reaction vessel with polytetrafluoroethylene lining and reacted at 100℃for 3 hours. After the reaction is finished, after the solution is cooled to room temperature, centrifuging to remove unreacted substances, taking supernatant, adding absolute ethyl alcohol with the volume ratio of 1:1 to precipitate quantum dots, centrifuging by a centrifuge to remove supernatant, washing by deionized water, precipitating again, repeating for three times, drying the precipitate, and refrigerating for storage.
(2) Preparing a polyethyleneimine solution with the concentration of 1%, weighing 1g of bleached needle wood fiber, immersing the bleached needle wood fiber in 50mL of polyethyleneimine solution, taking out the fiber after 3min, and fully washing the fiber with deionized water to obtain the fiber with the surface coated with polyethyleneimine.
(3) Preparing a quantum dot solution with the concentration of 0.1%, immersing the obtained fiber in 50mL of the quantum dot solution, soaking for 3min, taking out the fiber, and fully washing with deionized water to complete one-time assembly cycle, thereby obtaining the fluorescent fiber with the surface coated with a layer of quantum dot film.
(4) 9 Assembly cycles were completed, resulting in yellow fluorescent fibers with an emission wavelength of 618nm (FIG. 1e, f).
Example 2
A preparation method of a cotton fiber-based quantum dot composite fluorescent fiber based on 3-mercaptopropionic acid modified AgInZnS quantum dots comprises the following steps:
(1) Preparation of 3-mercaptopropionic acid modified AgInZnS quantum dots: 0.1mL AgNO3·H2O(0.5M)、0.5mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL of deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.106g of 3-mercaptopropionic acid is added into the mixed solution, the pH is regulated to 9.5 by NaOH solution, and then 1mL of NaS.9H 2 O (1M) is slowly dripped into the cation precursor solution. The mixed solution was transferred to a stainless steel reaction kettle with polytetrafluoroethylene lining and reacted at 120℃for 4 hours. After the reaction is finished, after the solution is cooled to room temperature, centrifuging to remove unreacted substances, taking supernatant, adding absolute ethyl alcohol with the volume ratio of 1:1 to precipitate quantum dots, centrifuging by a centrifuge to remove supernatant, washing by deionized water, precipitating again, repeating for three times, drying the precipitate, and refrigerating for storage.
(2) Preparing polydiene dimethyl ammonium chloride solution with the solubility of 1%, immersing cotton fibers in 30mL polydiene dimethyl ammonium chloride solution, taking out the fibers after 5min, and fully washing with deionized water to obtain the cotton fibers with the surfaces coated with the cationic polyelectrolyte.
(3) Preparing a quantum dot solution with the concentration of 0.2%, immersing the fiber in 30mL of the quantum dot solution, taking out the fiber after 5min, and fully washing with deionized water to complete one-time assembly, thereby obtaining the fluorescent fiber with the surface coated with a layer of quantum dot film.
(4) The assembly cycles were performed 3, 6,9 times, respectively, and the difference in fluorescence fiber intensity was observed using a laser confocal microscope (fig. 1c, d, 9 assembly cycles passed).
Example 3
A preparation method of a bamboo fiber-based quantum dot composite fluorescent fiber based on AgInZnS quantum dots modified by L-cysteine comprises the following steps:
(1) Preparation of L-cysteine modified AgInZnS quantum dots: 0.1mL AgNO3·H2O(0.5M)、0.5mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.991g L-cysteine is added into the mixed solution, and then 1mL NaS.9H264O (1M) is slowly added into the cation precursor solution in a dropwise manner. The mixed solution was transferred to a stainless steel reaction vessel with polytetrafluoroethylene lining and reacted at 110℃for 6 hours. After the reaction is finished, after the solution is cooled to room temperature, centrifuging to remove unreacted substances, taking supernatant, adding absolute ethyl alcohol with the volume ratio of 1:1 to precipitate quantum dots, centrifuging by a centrifuge to remove supernatant, washing by deionized water, precipitating again, repeating for three times, drying the precipitate, and refrigerating for storage.
(2) Preparing a polyethyleneimine solution with the solubility of 2%, weighing 1g of bamboo fiber, immersing the bamboo fiber in 100mL of polyethyleneimine solution, taking out the fiber after 10min, and fully washing the fiber with deionized water to obtain the fiber with the surface coated with polyethyleneimine.
(3) Preparing a quantum dot solution with the concentration of 0.1%, immersing the obtained fiber in 100mL of the quantum dot solution, soaking for 10min, taking out the fiber, fully washing with deionized water to obtain the fluorescent fiber with the surface coated with a layer of quantum dot film, and completing one assembly cycle.
(4) And (6) finishing the assembly cycle to obtain the fluorescent fiber.
Example 4
A preparation method of a bamboo fiber-based red fluorescent fiber based on AgInZnS quantum dots comprises the following steps:
(1) Preparation of thioglycollic acid modified AgInZnS quantum dots: 0.2mL AgNO3·H2O(0.5M)、0.5mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL of deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.92g of thioglycollic acid is added into the mixed solution, the pH is regulated to 8.0 by NaOH solution, and then 1mL of NaS.9H 2 O (1M) is slowly dripped into the cation precursor solution. The mixed solution was transferred to a stainless steel reaction vessel with polytetrafluoroethylene lining and reacted at 110℃for 5 hours. After the reaction is finished, after the solution is cooled to room temperature, centrifuging to remove unreacted substances, taking supernatant, adding absolute ethyl alcohol with the volume ratio of 1:1 to precipitate quantum dots, centrifuging by a centrifuge to remove supernatant, washing by deionized water, precipitating again, repeating for three times, drying the precipitate, and refrigerating for storage.
(2) Preparing polydiene dimethyl ammonium chloride solution with the concentration of 2%, weighing 1g of bleached bamboo fibers, immersing the bleached bamboo fibers in 25mL of polydiene dimethyl ammonium chloride solution for 10min, taking out the fibers, and fully washing the fibers with deionized water to obtain the fibers with surfaces coated with polydiene dimethyl ammonium chloride.
(3) Preparing a quantum dot solution with the concentration of 0.2%, immersing the obtained fiber in 25mL of the quantum dot solution, soaking for 10min, taking out the fiber, and fully washing with deionized water to complete one-time assembly cycle, thereby obtaining the fluorescent fiber with the surface coated with a layer of quantum dot film.
(4) After completion of 4 assembly cycles, a red light-emitting fluorescent fiber having an emission wavelength of 685nm was obtained (FIG. 1g, h).
Example 5
A preparation method of a broad-leaved wood fiber-based green fluorescent fiber based on AgInZnS quantum dots comprises the following steps:
(1) Preparation of thioglycollic acid modified AgInZnS quantum dots: 0.1mL AgNO3·H2O(0.5M)、1mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL of deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.92g of thioglycollic acid is added into the mixed solution, the pH is regulated to 9.0 by NaOH solution, and then 1mL of NaS.9H 2 O (1M) is slowly dripped into the cation precursor solution. The mixed solution was transferred to a stainless steel reaction vessel with polytetrafluoroethylene lining and reacted at 110℃for 5 hours. After the reaction is finished, after the solution is cooled to room temperature, centrifuging to remove unreacted substances, taking supernatant, adding absolute ethyl alcohol with the volume ratio of 1:1 to precipitate quantum dots, centrifuging by a centrifuge to remove supernatant, washing by deionized water, precipitating again, repeating for three times, drying the precipitate, and refrigerating for storage.
(2) Preparing polydiene dimethyl ammonium chloride solution with the concentration of 1%, weighing 1g of broadleaf wood fiber, immersing the broadleaf wood fiber in 50mL of polydiene dimethyl ammonium chloride solution for 20min, taking out the fiber, and fully washing the fiber with deionized water to obtain the fiber with the polydiene dimethyl ammonium chloride coated on the surface.
(3) Preparing a quantum dot solution with the concentration of 0.3%, immersing the obtained fiber in 50mL of the quantum dot solution, soaking for 20min, taking out the fiber, and fully washing with deionized water to complete one-time assembly cycle, thereby obtaining the fluorescent fiber with the surface coated with a layer of quantum dot film.
(4) 4 Assembly cycles were completed to give green fluorescent fibers with an emission wavelength of 554nm (FIGS. 1a, b).
Example 6
Needle leaf wood fiber based quantum dot composite orange fluorescent fiber based on thioglycollic acid modified AgInZnS quantum dot and a preparation method thereof, comprising the following steps:
(1) Preparation of thioglycollic acid modified AgInZnS quantum dots: 0.1mL AgNO3·H2O(0.5M)、0.5mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL of deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.92g of thioglycollic acid is added into the mixed solution, the pH is regulated to 8.5 by NaOH solution, and then 1mL of NaS.9H 2 O (1M) is slowly dripped into the cation precursor solution to prepare three identical solutions. The mixed solutions are respectively transferred into stainless steel reaction kettles with polytetrafluoroethylene lining, and are respectively reacted for 5 hours at 110 ℃,5 hours at 120 ℃ and 5 hours at 130 ℃. After the reaction is finished, after the solution is cooled to room temperature, centrifuging to remove unreacted substances, taking supernatant, adding absolute ethyl alcohol with the volume ratio of 1:1 to precipitate quantum dots, centrifuging by a centrifuge to remove supernatant, washing by deionized water, precipitating again, repeating for three times, drying the precipitate, and refrigerating for storage.
(2) Preparing polydiene dimethyl ammonium chloride solution with the concentration of 2%, weighing 1g of bleached needle wood fiber, immersing the bleached needle wood fiber in 20mL of polydiene dimethyl ammonium chloride solution for 3min, taking out the fiber, and fully washing the fiber with deionized water to obtain the fiber with the surface coated with polydiene dimethyl ammonium chloride.
(3) And (3) respectively preparing the three parts of quantum dots obtained in the step (1) into 80mL of aqueous solution, taking 20mL of quantum dot solution each time, soaking for 3min, taking out the fiber, and assembling the quantum dots on the fiber through four assembly cycles to prepare three parts of fluorescent fibers.
(4) And measuring the fiber strength of the fluorescent fiber prepared by the layer-by-layer self-assembly method by adopting a zero-distance tensile instrument, and measuring the fiber length by adopting fiber analysis.
Comparative example 1
(1) Preparing fluorescent fibers by a one-pot method: 0.1mL AgNO3·H2O(0.5M)、0.5mL Zn(NO3)2·H2O(0.5M)、1mL In(NO3)3·6H2O(0.5M), is added into 20mL of deionized water in sequence to obtain a cation precursor solution, magnetic stirring is carried out until the mixture is uniform, 0.92g of thioglycollic acid is added into the mixed solution, the pH is regulated to 8.5 by NaOH solution, and then 1mL of NaS.9H 2 O (1M) is slowly dripped into the cation precursor solution to prepare three identical solutions. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 1g of needle leaf wood fibers, uniformly stirring, and enabling the fibers to be completely immersed in the liquid, and reacting at 110 ℃ for 5h,120 ℃ for 5h and 130 ℃ for 5h respectively. After the reaction is finished, cooling to room temperature, filtering to obtain a fiber sample, and fully cleaning the fiber sample with deionized water and ethanol.
(2) The fiber strength of the fluorescent fiber prepared by the one-pot method was measured using a zero-gauge tensile tester, and the fiber length was measured using fiber analysis, and compared with the fluorescent fiber prepared by the layer-by-layer self-assembly method in example 6. As can be seen from fig. 5, the layer-by-layer self-assembly method of the present invention does not impair the strength and length of the fiber, but the one-pot method does, and the higher the reaction temperature, the greater the effect on the fiber strength.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the examples disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the embodiments described, and these modifications and variations should be considered as falling within the scope of the invention.
Claims (8)
1. The preparation method of the plant-based quantum dot composite fluorescent fiber is characterized by comprising the following steps of:
(1) Preparing quantum dots modified by surface ligands by adopting a one-step hydrothermal method;
(2) Preparing polyelectrolyte solution with the concentration of 0.5-2 w%, adding plant fibers into the polyelectrolyte solution for soaking, and coating the polyelectrolyte on the surface of the plant fibers by utilizing the interaction of charges between the surface of the plant fibers and the polyelectrolyte;
(3) Immersing the plant fiber with the polyelectrolyte coated on the surface in a quantum dot aqueous solution with the concentration of 0.1-1 w% for 1-20min, coating the quantum dot outside the fiber by utilizing the interaction between the group modified on the surface of the quantum dot and the polyelectrolyte, and completing the one-time assembly of the polyelectrolyte-quantum dot film;
(4) Repeating the polyelectrolyte-quantum dot assembly step for at least three times to obtain the plant-based quantum dot composite fluorescent fiber;
The quantum dot modified by the surface ligand is AgInZnS quantum dot modified by thioglycollic acid, agInZnS quantum dot modified by 3-mercaptopropionic acid or AgInZnS quantum dot modified by L-cysteine; the polyelectrolyte is polyethylenimine.
2. The method of claim 1, wherein the preparation of the surface ligand-modified quantum dots: uniformly mixing a cation precursor solution, adding a ligand aqueous solution, regulating the pH value to be 6-10 after uniformly mixing, slowly adding an anion precursor solution under the action of magnetic stirring, adding a reaction mixed solution into a reaction kettle, reacting for 5+/-2 hours at the temperature of 110+/-20 ℃, and preparing the surface ligand modified quantum dot through ethanol precipitation, centrifugation and washing.
3. The preparation method according to claim 2, wherein the cation precursor is a compound of Ag +、Zn2+、In3+, the molar ratio of Ag +/In3+ is 0.05-0.20, and the molar ratio of Zn 2+/In3+ is 0.25-1.00;
The anion precursor is a compound of S 2-, and the molar ratio of S 2-/In3+ is 0.5-2;
The ligand is one of thioglycollic acid, 3-mercaptopropionic acid and L-cysteine, and the molar ratio of the ligand to In 3+ is 10-80.
4. A process according to claim 1,2 or 3, wherein the reaction conditions of the one-step hydrothermal process of step (1) are: the pH value is 6-10, the reaction temperature is 90-130 ℃, and the reaction time is 3-7h.
5. The method of claim 4, wherein the ratio of the plant fiber to the polyelectrolyte solution in step (2) is 1:20-1:100g/mL.
6. The method according to claim 5, wherein the plant fiber is needle wood fiber, cotton fiber, hardwood fiber or bamboo fiber.
7. The plant-based quantum dot composite fluorescent fiber prepared by the method of any one of claims 1 to 6.
8. The application of the plant-based quantum dot composite fluorescent fiber in the anti-counterfeiting field.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391875A (en) * | 2011-08-30 | 2012-03-28 | 苏州大学 | Quantum dot-polyelectrolyte fluorescent nano complex and application thereof |
| US8349131B1 (en) * | 2006-10-31 | 2013-01-08 | Louisiana Tech Research Foundation: a division of Louisiana Tech University Foundation, Inc. | Method for the manufacture of smart paper and smart wood microfibers |
| CN103669110A (en) * | 2013-11-14 | 2014-03-26 | 华南理工大学 | Luminous plant fiber and preparation method thereof |
| CN105672038A (en) * | 2016-01-12 | 2016-06-15 | 华南理工大学 | Method for producing quantum dot fluorescent anti-counterfeiting paper |
| CN108084994A (en) * | 2017-12-13 | 2018-05-29 | 重庆大学 | A kind of method based on aqueous silver-colored indium zinc sulphur fluorescence quantum selective enumeration method cadmium ion |
| CN109056401A (en) * | 2018-07-30 | 2018-12-21 | 佛山科学技术学院 | A kind of biomass-based ultra-hydrophobic paper and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL234026B1 (en) * | 2015-08-11 | 2020-01-31 | Univ Wroclawski | Method for producing water-dispersible quantum dots, a colloid and method for producing the colloid |
-
2023
- 2023-05-19 CN CN202310569929.5A patent/CN116575230B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8349131B1 (en) * | 2006-10-31 | 2013-01-08 | Louisiana Tech Research Foundation: a division of Louisiana Tech University Foundation, Inc. | Method for the manufacture of smart paper and smart wood microfibers |
| CN102391875A (en) * | 2011-08-30 | 2012-03-28 | 苏州大学 | Quantum dot-polyelectrolyte fluorescent nano complex and application thereof |
| CN103669110A (en) * | 2013-11-14 | 2014-03-26 | 华南理工大学 | Luminous plant fiber and preparation method thereof |
| CN105672038A (en) * | 2016-01-12 | 2016-06-15 | 华南理工大学 | Method for producing quantum dot fluorescent anti-counterfeiting paper |
| CN108084994A (en) * | 2017-12-13 | 2018-05-29 | 重庆大学 | A kind of method based on aqueous silver-colored indium zinc sulphur fluorescence quantum selective enumeration method cadmium ion |
| CN109056401A (en) * | 2018-07-30 | 2018-12-21 | 佛山科学技术学院 | A kind of biomass-based ultra-hydrophobic paper and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHU Maoquan等.Fluorescent Silkworm Silk Prepared via Incorporation of Green, Yellow, Red, and Near-Infrared Fluorescent Quantum Dots.《IEEE Transactions on Nanotechnology》.2008,第7卷(第3期),第308—315页. * |
| Fluorescent Silkworm Silk Prepared via Incorporation of Green, Yellow, Red, and Near-Infrared Fluorescent Quantum Dots;CHU Maoquan等;《IEEE Transactions on Nanotechnology》;第7卷(第3期);第308—315页 * |
| Interfacial Polyelectrolyte Complexation Spinning of Cellulose Nanofibers/CdTe Quantum Dots for Anti-counterfeiting Fluorescent Textiles;CAI Shulin等;《Fibers and Polymers》;第23卷(第5期);第1235—1243页 * |
| Self-assembly method for the preparation of near-infrared fluorescent spider silk coated with CdTe nanocrystals;CHU Maoquan等;《Smart Materials and Structures》;第16卷;第2453—2456页 * |
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