CN110634684B - Preparation of flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction - Google Patents
Preparation of flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction Download PDFInfo
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- CN110634684B CN110634684B CN201910920710.9A CN201910920710A CN110634684B CN 110634684 B CN110634684 B CN 110634684B CN 201910920710 A CN201910920710 A CN 201910920710A CN 110634684 B CN110634684 B CN 110634684B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a preparation method of a flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction, which comprises the following steps: the paper sheet jointly modified by the cerium dioxide nanowire and the metal organic framework heterojunction is prepared by taking filter paper as a substrate, activating the surface of the filter paper, growing a metal organic framework material in situ and carrying out electrodeposition. The invention is characterized in that the filter paper is selected as a heterojunction growth substrate, so that the water absorption of the surface of the paper fiber can be increased, the growth of a metal organic framework material is promoted, meanwhile, the existence of the heterojunction can greatly improve the photoelectrochemical response of the paper base material and increase the capacitance performance of the paper base material, and a good foundation is laid for the preparation of novel multifunctional flexible biosensing platforms and flexible supercapacitors.
Description
Technical Field
The invention relates to a preparation method of a paper-based cerium dioxide nanowire-metal organic framework heterojunction, and belongs to the field of preparation of organic-inorganic hybrid nano materials.
Background
The cerium dioxide is used as the most stable metal oxide in the rare earth compound, and has good photo-electrochemical properties, so that the cerium dioxide has a unique application prospect in the fields of photo-catalytic hydrogen production, photo-catalytic degradation of organic pollutants such as methylene blue and methyl orange and active black, super capacitors and the like. However, the stability of the single ceria nano-material is poor, which is not favorable for the use of the ceria nano-material in optoelectronic devices and the integration of multifunctional devices.
The metal organic framework material is a regular crystal structure formed by supporting metal nodes and organic ligands, and has various topological structures, large specific surface area, ultrahigh porosity, low density and good biocompatibility due to designability of ligand molecules and central metal nodes. Meanwhile, by doping, forming a heterojunction compound and regulating and controlling the particle size, the precise regulation and control of the energy band structure, the capacitance performance, the multiplying power performance, the energy density and the like of the metal organic framework material can be realized. Nowadays, the metal organic frame material mainly adopts a strategy of firstly synthesizing and then using, so that the metal organic frame material is not beneficial to forming a stable structure between the frame material and a substrate, and the use of the metal organic frame material in electronic devices, particularly flexible electronic products, is limited.
Paper, which is a sheet made of plant fibers, each consisting of many small fibers. Each sheet is about 100 microns thick and contains a rich hierarchical structure and a large number of hydrogen bonds within it. Therefore, the paper has the characteristics of low price, portability, green degradability and good flexibility, and simultaneously has huge three-dimensional space active sites, so that convenience is provided for in-situ modification of the nano material, and simultaneously, the mutually crosslinked and criss-cross fiber structures provide a multi-dimensional information 'communication' platform for the nano material. Therefore, the paper chip is used as a load substrate, the flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction is grown in situ by adopting a simple and efficient hydrothermal method and an electrodeposition technology, and the prepared paper chip not only bears the unique flexibility of the paper chip, but also effectively inhibits the agglomeration of the nano material and improves the stability of the cerium dioxide and metal organic framework nano material. In addition, the existence of the paper fiber greatly increases the load of the nano material, forms a huge three-dimensional lighting active interface, improves the progress of the optical and electrochemical reaction of the heterojunction interface, and accelerates the charge transfer dynamics between the electrolyte and the paper electrode. The method develops a new development direction for the preparation of novel and multifunctional portable photoelectric chemical biosensors, flexible supercapacitors, flexible electronic skins and the like.
Disclosure of Invention
The invention aims to solve the technical problem of manufacturing a flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction composite material so as to realize the construction of a high-efficiency super capacitor and a novel photoelectric biosensing platform.
In order to solve the technical problem, the invention is realized by the following measures: a preparation method of a flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction is characterized by comprising the following steps:
(1) selecting filter paper as a paper substrate, and cutting the paper sheet into 4 cm multiplied by 4 cm;
(2) activating the paper substrate;
activation of the paper substrate comprising the steps of: putting the paper with the size of 4 cm multiplied by 4 cm into 20 mL of water/ethanol/isopropanol mixed solution, wherein the volume ratio of the water/ethanol/isopropanol solution is 2:1: 1; carrying out ultrasonic treatment on the paper sheet for 2 hours, then taking out the paper sheet, putting the paper sheet into a mixed solution of water and ethanol with the volume ratio of 1:1, and carrying out ultrasonic treatment for 1 hour to remove organic matters remained on the surface of the paper sheet; subsequently, the sheet was placed in an oven and dried at 150 ℃ for 48 h;
(3) growing a metal organic framework material on the surface of the paper sheet:
the growth of the metal organic framework material on the surface of the paper sheet comprises the following steps: dripping a chitosan solution with the volume concentration of 1% on the surface of the paper sheet activated in the step (2), and then drying the paper sheet at room temperature; repeating the step of dripping the chitosan for three times, then cleaning the surface of the paper sheet by using secondary water, and drying for 1 hour at room temperature; then, 8 mL of dimethylformamide aqueous solution is added into the glass dish, wherein the volume ratio of water to dimethylformamide is 1: 1; then adding 0.05 g of copper acetate and 40 mg of triphenylene-2, 3,6,7,10, 11-hexaol hydrate into the solution, stirring and mixing uniformly, putting the chitosan functionalized paper sheet into a glass dish, and reacting for 120 min at 85 ℃; taking out the paper sheet, washing the surface of the paper sheet with deionized water for 5 times, and then freeze-drying the paper sheet for 12 hours to finish the in-situ growth of the organic framework material on the surface of the paper fiber;
(4) preparing a paper-based cerium dioxide nanowire-metal organic framework heterojunction:
the preparation method of the paper-based cerium dioxide nanowire-metal organic framework heterojunction comprises the following steps: and (4) taking the paper sheet obtained in the step (3) as a substrate, preheating the paper sheet at 60 ℃ for 30 min in 50 mL of 20 mM cerium nitrate and 20 mM hexamethylenetetramine reaction liquid, heating the reaction liquid to 80 ℃, and performing electrodeposition for 20 min by adopting an electrodeposition technology under a potential of-0.8V to complete the preparation of the paper-based cerium dioxide nanowire-metal organic framework heterojunction.
The invention has the advantages of
(1) The preparation method is simple by adopting an in-situ growth process.
(2) The filter paper is selected as the growth substrate of the nano material, so that the cost of the paper sheet is reduced, and meanwhile, the filter paper has good water absorption performance, so that ions are favorably adsorbed on the surface of the fiber, and further the in-situ growth reaction kinetics of the metal organic framework is promoted.
(3) The prepared flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction has a large specific surface area, good conductivity and photoelectrochemical response performance, and meanwhile, has excellent specific capacitance performance.
Detailed Description
In order to better understand the present invention, the following examples further illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
A simple and efficient preparation method of a flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction comprises the following specific preparation processes:
(1) selecting filter paper as a paper substrate, and cutting the paper sheet into 4 cm multiplied by 4 cm;
(2) activating the paper substrate;
activation of the paper substrate comprising the steps of: putting the paper with the size of 4 cm multiplied by 4 cm into 20 mL of water/ethanol/isopropanol mixed solution, wherein the volume ratio of the water/ethanol/isopropanol solution is 2:1: 1; carrying out ultrasonic treatment on the paper sheet for 2 hours, then taking out the paper sheet, putting the paper sheet into a mixed solution of water and ethanol with the volume ratio of 1:1, and carrying out ultrasonic treatment for 1 hour to remove organic matters remained on the surface of the paper sheet; subsequently, the sheet was placed in an oven and dried at 150 ℃ for 48 h;
(3) growing a metal organic framework material on the surface of the paper sheet:
the growth of the metal organic framework material on the surface of the paper sheet comprises the following steps: dripping a chitosan solution with the volume concentration of 1% on the surface of the paper sheet activated in the step (2), and then drying the paper sheet at room temperature; repeating the step of dripping the chitosan for three times, then cleaning the surface of the paper sheet by using secondary water, and drying for 1 hour at room temperature; then, 8 mL of dimethylformamide aqueous solution is added into the glass dish, wherein the volume ratio of water to dimethylformamide is 1: 1; then adding 0.05 g of copper acetate and 40 mg of triphenylene-2, 3,6,7,10, 11-hexaol hydrate into the solution, stirring and mixing uniformly, putting the chitosan functionalized paper sheet into a glass dish, and reacting for 120 min at 85 ℃; taking out the paper sheet, washing the surface of the paper sheet with deionized water for 5 times, and then freeze-drying the paper sheet for 12 hours to finish the in-situ growth of the organic framework material on the surface of the paper fiber;
(4) preparing a paper-based cerium dioxide nanowire-metal organic framework heterojunction:
the preparation method of the paper-based cerium dioxide nanowire-metal organic framework heterojunction comprises the following steps: and (4) taking the paper sheet obtained in the step (3) as a substrate, preheating the paper sheet at 60 ℃ for 30 min in 50 mL of 20 mM cerium nitrate and 20 mM hexamethylenetetramine reaction liquid, heating the reaction liquid to 80 ℃, and performing electrodeposition for 20 min by adopting an electrodeposition technology under a potential of-0.8V to complete the preparation of the paper-based cerium dioxide nanowire-metal organic framework heterojunction.
Claims (1)
1. A preparation method of a flexible paper-based cerium dioxide nanowire-metal organic framework heterojunction is characterized by comprising the following preparation steps:
(1) selecting filter paper as a paper substrate, and cutting the paper sheet into 4 cm multiplied by 4 cm;
(2) activating the paper substrate;
activation of the paper substrate comprising the steps of: putting the paper with the size of 4 cm multiplied by 4 cm into 20 mL of water/ethanol/isopropanol mixed solution, wherein the volume ratio of the water/ethanol/isopropanol solution is 2:1: 1; carrying out ultrasonic treatment on the paper sheet for 2 hours, then taking out the paper sheet, putting the paper sheet into a mixed solution of water and ethanol with the volume ratio of 1:1, and carrying out ultrasonic treatment for 1 hour to remove organic matters remained on the surface of the paper sheet; subsequently, the sheet was placed in an oven and dried at 150 ℃ for 48 h;
(3) growing a metal organic framework material on the surface of the paper sheet:
the growth of the metal organic framework material on the surface of the paper sheet comprises the following steps: dripping a chitosan solution with the volume concentration of 1% on the surface of the paper sheet activated in the step (2), and then drying the paper sheet at room temperature; repeating the step of dripping the chitosan for three times, then cleaning the surface of the paper sheet by using secondary water, and drying for 1 hour at room temperature; then, 8 mL of dimethylformamide aqueous solution is added into the glass dish, wherein the volume ratio of water to dimethylformamide is 1: 1; then adding 0.05 g of copper acetate and 40 mg of triphenylene-2, 3,6,7,10, 11-hexaol hydrate into the solution, stirring and mixing uniformly, putting the chitosan functionalized paper sheet into a glass dish, and reacting for 120 min at 85 ℃; taking out the paper sheet, washing the surface of the paper sheet with deionized water for 5 times, and then freeze-drying the paper sheet for 12 hours to finish the in-situ growth of the organic framework material on the surface of the paper fiber;
(4) preparing a paper-based cerium dioxide nanowire-metal organic framework heterojunction:
the preparation method of the paper-based cerium dioxide nanowire-metal organic framework heterojunction comprises the following steps: and (4) taking the paper sheet obtained in the step (3) as a substrate, preheating the paper sheet at 60 ℃ for 30 min in 50 mL of 20 mM cerium nitrate and 20 mM hexamethylenetetramine reaction liquid, heating the reaction liquid to 80 ℃, and performing electrodeposition for 20 min by adopting an electrodeposition technology under a potential of-0.8V to complete the preparation of the paper-based cerium dioxide nanowire-metal organic framework heterojunction.
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| CN109289856A (en) * | 2018-09-03 | 2019-02-01 | 中国矿业大学 | A kind of polyhedron hollow core-shell structure MxM′3-xO4@CeO2Composite material and preparation method |
| CN109364936A (en) * | 2018-09-03 | 2019-02-22 | 中国矿业大学 | A kind of M of more shell hollow core-shell cubic structures1.8M′1.2O4@CeO2Composite material and preparation method |
| CN110136997A (en) * | 2019-05-16 | 2019-08-16 | 武汉工程大学 | A kind of preparation method of high flexibility composite electrode |
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| KR101787190B1 (en) * | 2015-07-02 | 2017-10-18 | 한국과학기술원 | Gas sensor and member using porous metal oxide semiconductor composite nanofibers including nanoparticle catalyst functionalized by nano-catalyst included within metal-organic framework, and manufacturing method thereof |
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| CN109289856A (en) * | 2018-09-03 | 2019-02-01 | 中国矿业大学 | A kind of polyhedron hollow core-shell structure MxM′3-xO4@CeO2Composite material and preparation method |
| CN109364936A (en) * | 2018-09-03 | 2019-02-22 | 中国矿业大学 | A kind of M of more shell hollow core-shell cubic structures1.8M′1.2O4@CeO2Composite material and preparation method |
| CN110136997A (en) * | 2019-05-16 | 2019-08-16 | 武汉工程大学 | A kind of preparation method of high flexibility composite electrode |
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| 滤纸增强壳聚糖膜的拉伸性能;黎明庆, 周长忍;《暨南大学学报 ( 自然科学版) 》;20041031;全文 * |
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