CN108998008B - Method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology - Google Patents
Method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology Download PDFInfo
- Publication number
- CN108998008B CN108998008B CN201810767639.0A CN201810767639A CN108998008B CN 108998008 B CN108998008 B CN 108998008B CN 201810767639 A CN201810767639 A CN 201810767639A CN 108998008 B CN108998008 B CN 108998008B
- Authority
- CN
- China
- Prior art keywords
- alginic acid
- electrodeposition
- solution
- zinc
- quantum dot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology. The method is characterized in that a mixed solution of sodium sulfide and alginic acid is used as an electrodeposition solution, and a metal zinc sheet is used as an anode metal electrode material for electrodeposition; in the electrodeposition process, zinc ions are generated by utilizing the electrochemical reaction generated on the metal zinc sheet, and then the coordination effect of alginic acid and the zinc ions and the reaction between sulfur ions and the zinc ions are utilized, so that the zinc sulfide quantum dot/alginic acid nano composite membrane is prepared in situ on the electrode. The method has the characteristics of simple operation, easy control, no use of organic solvent, environmental protection, mild preparation conditions, selectivity, controllability and the like; the prepared zinc sulfide quantum dot/alginic acid nano composite film material has the performance characteristics of good biocompatibility, nontoxicity, biodegradability and the like, and has good application prospect in the fields of biomedical functional materials, bioelectronic devices and the like.
Description
Technical Field
The invention belongs to the fields of nano materials, high polymer materials, biological materials and electrochemistry, relates to a method for preparing a quantum dot and natural high polymer composite membrane material in situ by utilizing an electrodeposition technology, and particularly relates to a method for preparing a zinc sulfide quantum dot/alginic acid nano composite membrane in situ by utilizing the electrodeposition technology.
Background
Quantum dots, also known as semiconductor nanocrystals, are nanomaterials composed of group II-VI or group III-V atoms, typically 2-10nm in size. Compared with organic fluorescent dyes and fluorescent proteins, the fluorescent dye has unique optical properties, such as adjustable emission spectrum, stronger fluorescence intensity, better light stability and the like, so the fluorescent dye has wide application prospects in the fields of biological imaging, biomarkers, light-emitting diodes, biological detection and the like [ Nature methods,2008,5:763-775 ]. At present, quantum dots are widely applied to different fields of biological imaging and biological fluorescent labeling, such as fixed cell labeling, living cell imaging, fluorescence detection and the like. However, some commonly used quantum dots often contain elements such as toxic heavy metals Cd, Hg, Pb and the like. When the quantum dots contact with organisms, certain damage can be caused to the organisms, especially the toxic and side effects of heavy metal elements in chemical composition components of the quantum dots on the organisms limit the application of the quantum dots in the biological field, and zinc sulfide quantum dots which do not contain the heavy metal elements are concerned by extensive researchers [ Nature materials,2013,12: 359-.
Alginic acid is a natural polymer extracted from Sargassum, and is a water-soluble biological polysaccharide with linear structure, and its molecular structure is a linear block copolymer formed by linking β -D-mannuronic acid (M segment) and α -L-guluronic acid (G segment) 2 kinds of structural units2+Ions) to form a three-dimensional network-structured gel. Alginic acid is rich in natural content, has a series of performance characteristics and advantages of wide source, no toxicity, good biocompatibility, biodegradability, pH sensitivity, film-forming property and the like, and is often applied to the fields of biomedical materials, biosensors, tissue engineering, sewage treatment, food Science and the like [ Progress in Polymer Science,2012,37:106-]。
In recent years, the electrodeposition technology of natural polymers has the advantages of simple operation, mild preparation conditions, time and space selectivity and controllability, and the like, and functional film materials can be obtained on the surface of conductive metal materials by applying electric signals, so that attention of researchers is paid to the technology. The current methods for the electrodeposition of alginic acid generally use an anode electrode stationPartially hydrolyzed to generate hydrogen ions, alginic acid near the anode is combined with the hydrogen ions to form gel on the Surface of the electrode, and Cheong et al deposit alginic acid/hydroxyapatite nano material film [ Colloids and Surface A,2008,328: 73-78: 78-78 on the anode]. In addition, alginic acid can be obtained by reacting with Ca2+Forming calcium alginate gel to generate electro-deposition, applying the electro-deposition of the alginic acid to the fixation of cells, and constructing biocompatible scaffold Materials [ Advanced Functional Materials,2012,22:519-]。
In recent decades, quantum dot nanomaterials have attracted extensive research interest in the scientific community due to their unique physical and chemical properties. It is noted that co-deposition of quantum dots and natural polymers can be achieved by electrodeposition [ ACS Applied Materials & Interfaces,2014,6:15510-15515 ]. However, the electrodeposition work of quantum dots and natural polymers carried out at present all adopts a codeposition mode, and no relevant patent and literature report exists for the research on the in-situ preparation of the quantum dot and natural polymer composite material by using the electrodeposition technology.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for preparing the zinc sulfide quantum dot/alginic acid nano composite membrane in situ by the electrodeposition technology has the advantages of simple operation, simple equipment, easy control and low cost.
The technical scheme adopted by the invention is as follows: a method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology is characterized in that a mixed solution of sodium sulfide and alginic acid is adopted as electrodeposition solution, and a metal zinc sheet is adopted as an anode metal electrode material for electrodeposition to carry out electrodeposition; in the electrodeposition process, zinc ions are generated by utilizing an electrochemical reaction on a metal zinc sheet (anode metal electrode material), and then the coordination effect of alginic acid and the zinc ions and the reaction between sulfur ions and the zinc ions are utilized, so that the zinc sulfide quantum dot/alginic acid nano composite membrane is prepared in situ on an electrode.
The method for in-situ preparation of the zinc sulfide quantum dot/alginic acid nano composite membrane by the electrodeposition technology is characterized by comprising the following specific steps of:
1) preparing a sodium sulfide solution: weighing 0.48-2.4 g of sodium sulfide solid particles, adding the sodium sulfide solid particles into a beaker filled with 100-200 mL of distilled water, and magnetically stirring for 1-2 hours at room temperature until the sodium sulfide solid particles are completely dissolved to prepare a sodium sulfide solution with the molar concentration of 0.02-0.05M;
2) preparing a alginic acid solution: weighing 1-4 g of sodium alginate solid powder, adding the sodium alginate solid powder into a beaker filled with 100-200 mL of distilled water, and magnetically stirring for 4-8 hours at room temperature until the sodium alginate is fully dissolved to prepare an alginic acid solution with the mass percentage concentration of 1.0-2.0%;
3) preparing an electrodeposition solution of sodium sulfide and alginic acid: taking 20-50 ml of the sodium sulfide solution prepared in the step 1), adding the sodium sulfide solution into a beaker containing 20-50 ml of the alginic acid solution prepared in the step 2), magnetically stirring the solution at room temperature for 5-15 minutes to fully mix the solution, and ultrasonically dispersing the solution by using an ultrasonic instrument for 5-15 minutes to uniformly mix the solution to prepare an electrodeposition solution of sodium sulfide and alginic acid;
4) preparation of anode and cathode metal electrode materials: the method comprises the following steps of (1) taking a metal zinc sheet as an anode metal electrode material for electrodeposition, firstly making the metal zinc sheet into the electrode material with the required size and shape, carefully polishing the metal zinc sheet by using abrasive paper before use to enable the surface of the metal zinc sheet to be flat and smooth, and then sequentially immersing the metal zinc sheet into acetone, absolute ethyl alcohol and distilled water to respectively perform ultrasonic cleaning for 3-5 minutes for later use; a platinum sheet is used as a cathode electrode material for electrodeposition, and the platinum sheet is sequentially immersed in acetone, absolute ethyl alcohol and distilled water and respectively ultrasonically cleaned for 3-5 minutes for later use;
5) preparing a zinc sulfide quantum dot/alginic acid nano composite membrane in situ by electrodeposition: ultrasonically removing bubbles from the sodium sulfide and alginic acid electrodeposition solution prepared in the step 3) for 3-5 minutes, taking a metal zinc sheet prepared in the step 4) as an anode and a platinum sheet as a cathode, respectively connecting the anode and the cathode with a high-precision direct-current power supply, then simultaneously placing the two electrodes into the sodium sulfide and alginic acid electrodeposition solution, wherein the distance between the anode and the cathode is 1-2 cm, and then applying a constant voltage of 1.0-1.5V by using the direct-current power supply for electrodeposition, wherein the deposition time is 5-15 minutes; and immediately closing the direct current power supply after the electrodeposition is finished, taking out the anode (namely the metal zinc sheet), repeatedly cleaning the anode for 3-6 times by using distilled water, and preparing the zinc sulfide quantum dot/alginic acid nano composite film on the surface of the metal zinc sheet in situ.
The power of the ultrasonic instrument is 40-50W.
The zinc sulfide quantum dot/alginic acid nano composite membrane prepared in situ on the electrode material by utilizing the electrodeposition technology has good application value in the biomedical fields and functional materials such as fluorescence labeling, biological imaging, controlled release, fluorescent functional materials and the like.
The technical principle of the invention is as follows: in the electrodeposition process, the electrochemical reaction on the anode metal electrode material (metal zinc sheet) can generate metal zinc ions, and the metal zinc ions can generate coordination with alginic acid molecules, so that the alginic acid molecules can deposit on the surface of the anode metal electrode material to form a gel film; on the other hand, sulfur ions in the system can react with zinc ions generated on an anode metal electrode material (metal zinc sheet), and the formed alginate gel film can also be used as a dispersing agent and a stabilizing agent for generating quantum dots by the reaction of the sulfur ions and the zinc ions in the system, so that the zinc sulfide quantum dot/alginic acid nano composite film material is prepared in situ by utilizing an electrodeposition technology.
The method for in-situ preparation of the zinc sulfide quantum dot/alginic acid nano composite membrane by the electrodeposition technology has the characteristics and advantages that: the method is easy to control, simple in equipment, convenient to operate, mild in preparation conditions, and has the characteristics of time and space selectivity, controllability and the like. Meanwhile, the method does not use an organic solvent, is environment-friendly and pollution-free, directly prepares the zinc sulfide quantum dot/alginic acid nano composite membrane on the electrode material in situ, and can control the thickness of the zinc sulfide quantum dot/alginic acid nano composite membrane by changing electrodeposition conditions (such as electrodeposition time and deposition voltage). In addition, the zinc sulfide quantum dot/alginic acid nano composite membrane prepared in situ on the anode metal electrode material (metal zinc sheet) by the method has the advantages of uniform surface, no bubbles, flatness and smoothness, and easy peeling from the surface of the electrode material to obtain the complete zinc sulfide quantum dot/alginic acid nano composite membrane, and is favorable for direct subsequent application and independent use of the quantum dot/natural polymer nano composite membrane. The technology adopts natural high molecular alginic acid as an electrodeposition solution, and prepares the quantum dot/alginic acid nano composite membrane in situ by utilizing the electrodeposition technology, and the nano composite membrane has good biocompatibility, nontoxicity and biodegradability, so that the nano composite membrane has good application prospect in the aspects of biomedical functional materials, bioelectronic devices, biosensors, detectors and the like.
The invention has the beneficial effects that:
1) the invention relates to a method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology.
2) The method for in-situ preparation of the zinc sulfide quantum dot/alginic acid nano composite membrane by the electrodeposition technology has the characteristics and advantages of simple operation, simple equipment, easy control, low cost, time and space selectivity, controllability and the like. Meanwhile, the method does not use an organic solvent, is environment-friendly and pollution-free, and has mild preparation conditions; the thickness of the zinc sulfide quantum dot/alginic acid nano composite film can be regulated and controlled by changing electrodeposition control conditions (such as electrodeposition time and deposition voltage).
3) The invention relates to a method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite film by an electrodeposition technology, wherein the zinc sulfide quantum dot in the nano composite film prepared by the method does not contain toxic heavy metal elements, and alginic acid also has good biocompatibility and biodegradability, so that the prepared zinc sulfide quantum dot/alginic acid nano composite film material has the performance characteristics and advantages of good biocompatibility, nontoxicity, biodegradability and the like, and has good application prospects in the fields of biomedical materials, bioelectronic devices, biosensors, detectors and the like.
4) The invention relates to a method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology.
5) The zinc sulfide quantum dot/alginic acid nano composite membrane prepared by the invention has fluorescence property and has good application value in biomedical fields and functional materials such as fluorescence labeling, biological imaging, controlled release and fluorescent functional materials.
Drawings
Fig. 1 is a photograph of a zinc sulfide quantum dot/alginic acid nanocomposite film prepared in situ on a metal zinc sheet by an electrodeposition technique in example 1 of the present invention.
Fig. 2 is a transmission electron microscope photograph of the zinc sulfide quantum dot/alginic acid nano composite film prepared in example 2 of the present invention.
FIG. 3 is a fluorescent photograph of the zinc sulfide quantum dot/alginic acid nano-composite film prepared in example 3 of the present invention under a 302nm ultraviolet lamp.
Detailed Description
The invention is further described below with reference to the following figures and examples, which should not be construed as limiting the invention.
The invention provides a method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology, and the technology of the invention is further described by combining specific examples, but the invention is not limited by the following examples.
Example 1
A method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology comprises the following specific steps:
1) preparation of sodium sulfide solution: weighing 0.48g of sodium sulfide solid particles, adding the sodium sulfide solid particles into a beaker filled with 100mL of distilled water, and magnetically stirring the mixture at room temperature for 1 hour until the sodium sulfide solid particles are completely dissolved to prepare a sodium sulfide solution with the molar concentration of 0.02M;
2) preparation of alginic acid solution: weighing 1g of sodium alginate solid powder, adding the sodium alginate solid powder into a beaker filled with 100mL of distilled water, and magnetically stirring the mixture at room temperature for 4 hours until the sodium alginate is fully dissolved to prepare a sodium alginate solution with the mass percentage concentration of 1.0%;
3) preparing an electrodeposition solution of sodium sulfide and alginic acid: taking 20ml of the sodium sulfide solution prepared in the step 1), adding the sodium sulfide solution into a beaker containing 20ml of the alginic acid solution prepared in the step 2), magnetically stirring the mixture at room temperature for 5 minutes to fully mix the mixture, and then ultrasonically dispersing the mixture for 5 minutes by using an ultrasonic instrument to uniformly mix the solution, thereby preparing an electrodeposition solution of sodium sulfide and alginic acid;
4) preparation of anode and cathode metal electrode materials: adopting a metal zinc sheet as an anode metal electrode material for electrodeposition, firstly making the anode metal electrode material into metal sheets with different sizes and shapes, carefully polishing the anode metal electrode material (the metal zinc sheet) by using sand paper before use to ensure that the surface of the anode metal electrode material is smooth, and then sequentially immersing the anode metal electrode material into acetone, absolute ethyl alcohol and distilled water to respectively perform ultrasonic cleaning for 3 minutes for later use; a platinum sheet is taken as a cathode electrode material for electrodeposition, and is sequentially immersed in acetone, absolute ethyl alcohol and distilled water for ultrasonic cleaning for 3 minutes respectively for later use;
5) preparing a zinc sulfide quantum dot/alginic acid nano composite membrane in situ by electrodeposition: ultrasonically removing bubbles from the sodium sulfide and alginic acid electrodeposition solution prepared in the step 3) for 3 minutes, respectively connecting an anode and a cathode with a direct current power supply (high-precision direct current power supply) by taking a metal zinc sheet prepared in the step 4) as the anode and a platinum sheet as the cathode, and then simultaneously placing the two electrodes into the sodium sulfide and alginic acid electrodeposition solution, wherein the distance between the two electrodes is 1 cm; applying a constant voltage of 1.0V by adopting a high-precision programmable direct-current power supply to carry out electrodeposition, wherein the deposition time is 5 minutes; and immediately turning off the power supply after the electrodeposition is finished, taking out the metal zinc sheet, and carefully cleaning the metal zinc sheet for 3 times by using distilled water to obtain the zinc sulfide quantum dot/sodium alginate nano composite film prepared on the surface of the anode metal zinc sheet in situ by electrodeposition.
Fig. 1 is a photograph of a zinc sulfide quantum dot/alginic acid nanocomposite film prepared in situ on a metal zinc sheet by an electrodeposition technique in example 1 of the present invention. As can be seen from fig. 1, when sodium sulfide and alginic acid are used as electrodeposition liquid and a zinc sheet is used as an anode metal electrode material, a gel film is formed on the surface of the metal zinc sheet after electrodeposition, and the gel film is transparent and uniform, has a flat and smooth surface, is free of bubbles, and has a certain thickness, which indicates that the zinc sulfide quantum dot/alginic acid nano composite film can be prepared in situ on the surface of the metal zinc sheet electrode by using an electrodeposition technology.
Example 2
A method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology comprises the following specific steps:
1) preparation of sodium sulfide solution: weighing 0.96g of sodium sulfide solid particles, adding the sodium sulfide solid particles into a beaker filled with 100mL of distilled water, and magnetically stirring the mixture at room temperature for 2 hours until the sodium sulfide solid particles are completely dissolved to prepare a sodium sulfide solution with the molar concentration of 0.04M;
2) preparation of alginic acid solution: weighing 2g of sodium alginate solid powder, adding the sodium alginate solid powder into a beaker filled with 100mL of distilled water, and magnetically stirring the mixture at room temperature for 6 hours until the sodium alginate is fully dissolved to prepare a sodium alginate solution with the mass percentage concentration of 2.0%;
3) preparing an electrodeposition solution of sodium sulfide and alginic acid: adding 30ml of the sodium sulfide solution prepared in the step 1) into a beaker containing 30ml of the alginic acid solution prepared in the step 2), magnetically stirring for 10 minutes at room temperature for fully mixing, and then ultrasonically dispersing for 10 minutes by using an ultrasonic instrument to uniformly mix the solutions, thereby preparing an electrodeposition solution of sodium sulfide and alginic acid;
4) preparation of anode and cathode metal electrode materials: adopting a metal zinc sheet as an anode metal electrode material for electrodeposition, firstly making the anode metal electrode material into metal sheets with different sizes and shapes, carefully polishing the anode metal electrode material (the metal zinc sheet) by using sand paper before use to ensure that the surface of the anode metal electrode material is smooth, and then sequentially immersing the anode metal electrode material into acetone, absolute ethyl alcohol and distilled water to respectively perform ultrasonic cleaning for 5 minutes for later use; a platinum sheet is taken as a cathode electrode material for electrodeposition, and is sequentially immersed in acetone, absolute ethyl alcohol and distilled water for ultrasonic cleaning for 5 minutes respectively for later use;
5) preparing a zinc sulfide quantum dot/alginic acid nano composite membrane in situ by electrodeposition: and 3) ultrasonically removing bubbles from the sodium sulfide and alginic acid electrodeposition solution prepared in the step 3) for 5 minutes, respectively connecting the anode and the cathode with a direct current power supply (high-precision direct current power supply) by taking the metal zinc sheet prepared in the step 4) as the anode and the platinum sheet as the cathode, and then simultaneously placing the two electrodes into the sodium sulfide and alginic acid electrodeposition solution, wherein the distance between the two electrodes is 1 cm. And applying a constant voltage of 1.2V by adopting a high-precision programmable direct-current power supply to carry out electrodeposition, wherein the deposition time is 10 minutes. And immediately turning off the power supply after the electrodeposition is finished, taking out the metal zinc sheet, carefully cleaning the metal zinc sheet for 3 times by using distilled water to obtain the zinc sulfide quantum dot/alginic acid nano composite membrane prepared on the surface of the anode metal zinc sheet in situ by electrodeposition, and observing the fluorescence property of the zinc sulfide quantum dot/alginic acid nano composite membrane by using a 302nm ultraviolet lamp.
Fig. 2 is a transmission electron microscope photograph of the zinc sulfide quantum dot/alginic acid nano composite film prepared in example 2 of the present invention. The specific testing steps are as follows: firstly, drying the prepared zinc sulfide quantum dot/alginic acid nano composite film at normal temperature, grinding the dried zinc sulfide quantum dot/alginic acid nano composite film into powder to prepare a sample, then ultrasonically dispersing the sample in PBS (pH 7.0), then dripping the sample on the surface of a clean copper mesh special for a transmission electron microscope, drying the copper mesh, and then detecting by using a high-resolution transmission electron microscope (HRTEM, JEM-2100F STEM/EDS, JP). From fig. 2, it can be found that the particle size of the nanoparticles is relatively uniform, the nanoparticles are well dispersed in the system, and the average particle size is about 5nm, which indicates the existence of the zinc sulfide quantum dots in the prepared zinc sulfide quantum dot/alginic acid nano composite film.
Example 3
A method for in-situ preparation of a zinc sulfide quantum dot/alginic acid nano composite membrane by an electrodeposition technology comprises the following specific steps:
1) preparation of sodium sulfide solution: weighing 2.4g of sodium sulfide solid particles, adding the sodium sulfide solid particles into a beaker filled with 200mL of distilled water, and magnetically stirring the mixture at room temperature for 2 hours until the sodium sulfide solid particles are completely dissolved to prepare a sodium sulfide solution with the molar concentration of 0.05M;
2) preparation of alginic acid solution: weighing 4g of sodium alginate solid powder, adding the sodium alginate solid powder into a beaker filled with 200mL of distilled water, and magnetically stirring the mixture at room temperature for 8 hours until the sodium alginate is fully dissolved to prepare a sodium alginate solution with the mass percentage concentration of 2.0%;
3) preparing sodium sulfide and alginic acid electrodeposition liquid: taking 50ml of the sodium sulfide solution prepared in the step 1), adding the sodium sulfide solution into a beaker containing 50ml of the alginic acid solution prepared in the step 2), magnetically stirring the mixture at room temperature for 15 minutes to fully mix the mixture, and then ultrasonically dispersing the mixture for 15 minutes by using an ultrasonic instrument to uniformly mix the solution, thereby preparing an electrodeposition solution of sodium sulfide and alginic acid;
4) preparation of anode and cathode metal electrode materials: adopting a metal zinc sheet as an anode metal electrode material for electrodeposition, firstly making the anode metal electrode material into metal sheets with different sizes and shapes, carefully polishing the anode metal electrode material (the metal zinc sheet) by using sand paper before use to ensure that the surface of the anode metal electrode material is smooth, and then sequentially immersing the anode metal electrode material into acetone, absolute ethyl alcohol and distilled water to respectively perform ultrasonic cleaning for 5 minutes for later use; a platinum sheet is taken as a cathode electrode material for electrodeposition, and is sequentially immersed in acetone, absolute ethyl alcohol and distilled water for ultrasonic cleaning for 5 minutes respectively for later use;
5) preparing a zinc sulfide quantum dot/alginic acid nano composite membrane in situ by electrodeposition: and 3) ultrasonically removing bubbles from the sodium sulfide and alginic acid electrodeposition solution prepared in the step 3) for 5 minutes, respectively connecting the anode and the cathode with a direct current power supply (high-precision direct current power supply) by taking the metal zinc sheet prepared in the step 4) as the anode and the platinum sheet as the cathode, and then simultaneously placing the two electrodes into the sodium sulfide and alginic acid electrodeposition solution, wherein the distance between the two electrodes is 2 cm. And applying a constant voltage of 1.5V by adopting a high-precision programmable direct-current power supply to perform electrodeposition, wherein the deposition time is 15 minutes. And immediately turning off the power supply after the electrodeposition is finished, taking out the metal zinc sheet, carefully cleaning for 6 times by using distilled water to obtain the zinc sulfide quantum dot/alginic acid nano composite membrane prepared on the surface of the metal zinc sheet in situ by electrodeposition, and observing the fluorescence property of the zinc sulfide quantum dot/alginic acid nano composite membrane by using a 302nm ultraviolet lamp.
FIG. 3 is a fluorescent photograph of the zinc sulfide quantum dot/alginic acid nano-composite film prepared in example 3 of the present invention under a 302nm ultraviolet lamp. As can be found from FIG. 3, the prepared zinc sulfide quantum dot/alginic acid nano composite membrane shows very obvious blue fluorescence under the irradiation of a 302nm ultraviolet lamp, which also indicates the existence of the zinc sulfide quantum dot in the composite membrane.
It should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is to be covered by the appended claims.
Claims (2)
1. A method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology is characterized in that a mixed solution of sodium sulfide and alginic acid is adopted as electrodeposition solution, and a metal zinc sheet is adopted as an anode metal electrode material for electrodeposition to carry out electrodeposition; in the electrodeposition process, zinc ions are generated by utilizing the electrochemical reaction generated on the metal zinc sheet, and then the coordination effect of alginic acid and the zinc ions and the reaction between sulfur ions and the zinc ions are utilized, so that the zinc sulfide quantum dot/alginic acid nano composite membrane is prepared in situ on the electrode.
2. The method for in-situ preparation of the zinc sulfide quantum dot/alginic acid nano composite membrane by the electrodeposition technology as claimed in claim 1, characterized by comprising the following specific steps:
1) preparing a sodium sulfide solution: weighing 0.48-2.4 g of sodium sulfide solid particles, adding the sodium sulfide solid particles into a beaker filled with 100-200 mL of distilled water, and magnetically stirring for 1-2 hours at room temperature until the sodium sulfide solid particles are completely dissolved to prepare a sodium sulfide solution with the molar concentration of 0.02-0.05M;
2) preparing a alginic acid solution: weighing 1-4 g of sodium alginate solid powder, adding the sodium alginate solid powder into a beaker filled with 100-200 mL of distilled water, and magnetically stirring for 4-8 hours at room temperature until the sodium alginate is fully dissolved to prepare an alginic acid solution with the mass percentage concentration of 1.0-2.0%;
3) preparing an electrodeposition solution of sodium sulfide and alginic acid: taking 20-50 ml of the sodium sulfide solution prepared in the step 1), adding the sodium sulfide solution into a beaker containing 20-50 ml of the alginic acid solution prepared in the step 2), magnetically stirring the solution at room temperature for 5-15 minutes to fully mix the solution, and ultrasonically dispersing the solution by using an ultrasonic instrument for 5-15 minutes to uniformly mix the solution to prepare an electrodeposition solution of sodium sulfide and alginic acid;
4) preparation of anode and cathode metal electrode materials: the method comprises the following steps of (1) taking a metal zinc sheet as an anode metal electrode material for electrodeposition, firstly making the metal zinc sheet into the electrode material with the required size and shape, polishing the metal zinc sheet by using abrasive paper before use to enable the surface of the metal zinc sheet to be flat and smooth, and then sequentially immersing the metal zinc sheet into acetone, absolute ethyl alcohol and distilled water to respectively perform ultrasonic cleaning for 3-5 minutes for later use; a platinum sheet is used as a cathode electrode material for electrodeposition, and the platinum sheet is sequentially immersed in acetone, absolute ethyl alcohol and distilled water and respectively ultrasonically cleaned for 3-5 minutes for later use;
5) preparing a zinc sulfide quantum dot/alginic acid nano composite membrane in situ by electrodeposition: ultrasonically removing bubbles from the sodium sulfide and alginic acid electrodeposition solution prepared in the step 3) for 3-5 minutes, taking a metal zinc sheet prepared in the step 4) as an anode and a platinum sheet as a cathode, respectively connecting the anode and the cathode with a direct current power supply, then simultaneously placing the two electrodes into the sodium sulfide and alginic acid electrodeposition solution, wherein the distance between the anode and the cathode is 1-2 cm, and then applying a constant voltage of 1.0-1.5V by using the direct current power supply for electrodeposition, wherein the deposition time is 5-15 minutes; and immediately closing the direct current power supply after the electrodeposition is finished, taking out the anode, washing the anode for 3-6 times by using distilled water, and preparing the zinc sulfide quantum dot/alginic acid nano composite film on the surface of the metal zinc sheet in situ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810767639.0A CN108998008B (en) | 2018-07-13 | 2018-07-13 | Method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810767639.0A CN108998008B (en) | 2018-07-13 | 2018-07-13 | Method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108998008A CN108998008A (en) | 2018-12-14 |
| CN108998008B true CN108998008B (en) | 2020-08-25 |
Family
ID=64600264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810767639.0A Active CN108998008B (en) | 2018-07-13 | 2018-07-13 | Method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108998008B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110596220B (en) * | 2019-09-25 | 2022-05-03 | 武汉理工大学 | Preparation method of quantum dot electrode for simultaneously carrying out fluorescence and electrochemical detection on metal ions |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241648A (en) * | 1999-07-29 | 2000-01-19 | 石油大学(北京) | Preparation of zinc sulfide and hydrogen from hydrogen sulfide |
| CN102644088A (en) * | 2012-04-25 | 2012-08-22 | 宁波大学 | Preparation method of zinc sulfide quantum dots |
| CN102964608A (en) * | 2012-11-15 | 2013-03-13 | 中北大学 | Preparation method of carbon quantum dot containing calcium alginate gel for detecting copper ions |
| CN103204634A (en) * | 2013-03-15 | 2013-07-17 | 北京科技大学 | Method for manufacturing semiconductor sulfide biopolymer nano-composite film |
| CN104356430A (en) * | 2014-11-17 | 2015-02-18 | 武汉理工大学 | Preparation method of carbon dot/chitosan in-situ composite material |
| CN104562074A (en) * | 2015-01-09 | 2015-04-29 | 武汉理工大学 | Preparation method of anodic-electrodeposition chitosan gel on basis of coordination action |
-
2018
- 2018-07-13 CN CN201810767639.0A patent/CN108998008B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241648A (en) * | 1999-07-29 | 2000-01-19 | 石油大学(北京) | Preparation of zinc sulfide and hydrogen from hydrogen sulfide |
| CN102644088A (en) * | 2012-04-25 | 2012-08-22 | 宁波大学 | Preparation method of zinc sulfide quantum dots |
| CN102964608A (en) * | 2012-11-15 | 2013-03-13 | 中北大学 | Preparation method of carbon quantum dot containing calcium alginate gel for detecting copper ions |
| CN103204634A (en) * | 2013-03-15 | 2013-07-17 | 北京科技大学 | Method for manufacturing semiconductor sulfide biopolymer nano-composite film |
| CN104356430A (en) * | 2014-11-17 | 2015-02-18 | 武汉理工大学 | Preparation method of carbon dot/chitosan in-situ composite material |
| CN104562074A (en) * | 2015-01-09 | 2015-04-29 | 武汉理工大学 | Preparation method of anodic-electrodeposition chitosan gel on basis of coordination action |
Non-Patent Citations (2)
| Title |
|---|
| Electrodeposition of alginic acid and composite films;M. Cheong et al.;《Colloids and Surfaces A: Physicochemical and Engineering Aspects》;20080618;第328卷;第73-78页 * |
| 壳聚糖与量子点及配位金属离子的电沉积技术研究;耿增华;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180115(第1期);第B015-214页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108998008A (en) | 2018-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lv et al. | A highly flexible self-powered biosensor for glucose detection by epitaxial deposition of gold nanoparticles on conductive bacterial cellulose | |
| Jerome et al. | Hydrothermal synthesis of boron nitride quantum dots/poly (luminol) nanocomposite for selective detection of ascorbic acid | |
| Zhang et al. | Photoelectrochemical response of carbon dots (CDs) derived from chitosan and their use in electrochemical imaging | |
| Martinez-Perinan et al. | Insulin sensor based on nanoparticle-decorated multiwalled carbon nanotubes modified electrodes | |
| CN104356430B (en) | The preparation method of a kind of carbon point/chitosan in situ matrix material | |
| CN108318568A (en) | A kind of electrochemical sensor and preparation method for Sensitive Detection heavy metal cadmium ion | |
| CN107576704B (en) | microcystin-LR molecular imprinting photoelectric chemical sensor and preparation and application thereof | |
| CN105499596B (en) | The method of autonomous growth Au nanoparticles on Electrodeposited CdSe films | |
| CN106467744B (en) | A kind of preparation method of the carbon quantum dot with adjustable photo-electro-luminescence and photoluminescence performance | |
| WO2018214430A1 (en) | Nano-cone structure composite material for capturing cancer cells, preparation method therefor, and application thereof | |
| CN106222718B (en) | A kind of electro-deposition method of carboxymethyl cellulose | |
| CN108998008B (en) | Method for in-situ preparation of zinc sulfide quantum dot/alginic acid nano composite membrane by electrodeposition technology | |
| CN110596220B (en) | Preparation method of quantum dot electrode for simultaneously carrying out fluorescence and electrochemical detection on metal ions | |
| Jiang et al. | Trifunctional modification of individual bacterial cells for magnet-assisted bioanodes with high performance in microbial fuel cells | |
| Wang et al. | Dendritic CdO nanomaterials prepared by electrochemical deposition and their electrogenerated chemiluminescence behaviors in aqueous systems | |
| CN107121418B (en) | Carbon dot/chitosan detector with double detection functions and preparation method thereof | |
| CN109518246A (en) | Nano silver/carboxyl chitosan composite membrane method is prepared in situ using electro-deposition techniques | |
| CN111463441A (en) | Aminated Fe3O4@SiO2Nanoparticle and application thereof in polypyrrole-modified microbial fuel cell anode | |
| CN102644089B (en) | Preparation method for cadmium sulfide quantum dots | |
| CN106637332B (en) | One kind prepares cathode material AgCuO by anodic oxidation electro-deposition2Method | |
| CN110186965A (en) | CuO- polylysine/Graphene electrodes and its preparation method and application | |
| CN114134553A (en) | Preparation method of stainless steel net for separating oil-in-water emulsion | |
| CN104084597B (en) | Method for manufacturing fractal tree branch pattern aggregation including gold nanoparticles | |
| Pandit et al. | Electrochemical deposition toward thin films | |
| CN105906828A (en) | Method for spontaneous deposition of natural polymer gel film on surface of metal substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |