CN117069118A - Preparation method of silicon dioxide nanotube with cellulose structure - Google Patents

Preparation method of silicon dioxide nanotube with cellulose structure Download PDF

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Publication number
CN117069118A
CN117069118A CN202311038378.6A CN202311038378A CN117069118A CN 117069118 A CN117069118 A CN 117069118A CN 202311038378 A CN202311038378 A CN 202311038378A CN 117069118 A CN117069118 A CN 117069118A
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filter paper
silica
hours
nanotube
template
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Inventor
张恒硕
宿海
尚德兴
董文瑞
刘楠楠
马德齐
房满义
金亚飞
王永和
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Bengbu Zhongheng New Materials Scientific And Technological Co ltd
Anhui Kaisheng Applied Materials Co ltd
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Bengbu Zhongheng New Materials Scientific And Technological Co ltd
Anhui Kaisheng Applied Materials Co ltd
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Priority to CN202311038378.6A priority Critical patent/CN117069118A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Abstract

The invention discloses a preparation method of a silicon dioxide nanotube with a cellulose structure, which comprises the steps of mixing and stirring organosilane, low-carbon alcohol and hydrochloric acid to form a mixed solution, and stirring for 3-5 h to form transparent silica sol; and (3) putting quantitative filter paper serving as a template into silica sol for soaking, depositing silane oligomer on the surface of the filter paper, washing the filter paper, drying, and calcining to remove the filter paper template to obtain the silica nanotube. The method avoids using an organic template agent, has the advantages of small environmental pollution, wide raw material sources and low cost, and the prepared silicon dioxide nanotube has high specific surface area, can meet various compounding and doping requirements, can form a composite material with various metal oxides, and has wide application in the fields of photocatalysis and super capacitor electrode materials.

Description

Preparation method of silicon dioxide nanotube with cellulose structure
Technical Field
The invention belongs to a silicon dioxide preparation technology, in particular to a preparation method of a silicon dioxide nanotube with a cellulose structure.
Background
Silica is a common composite filler with high heat conductivity, low thermal expansion coefficient and excellent photoelectric property, and the morphology of the composite filler has great influence on various physical and chemical properties of the composite. With the development of the technology level and the gradual maturity of the research on the mechanism of the nano material, the research on the morphology of the silicon dioxide becomes one of hot spots. Among them, the excellent performance of silica nanotubes in the field of composite material preparation and photocatalysis and supercapacitor electrode materials has attracted attention from researchers.
The natural world is a magic big factory, a few special microstructures with organisms are created, natural substances are taken as templates, the structures and the shapes of the natural substances are copied, so that the prepared material can keep the original characteristics of the natural substances, natural cellulose is the most widely-sourced substance of biological template families, and the natural cellulose is low in price and degradable, and therefore, the natural cellulose is taken as a template to design a nano material with a special shape, which is a feasible way. Cellulose substances such as filter paper gauze are composed of a large number of coarse fibers (micron-sized) arranged in a three-dimensional network structure, and the coarse fibers are built up of tens of thousands of nano-sized fibers. Because of the existence of hydrogen bonds between the structures, cellulose can exist stably in conventional solvents such as water, ethanol and dilute acid alkali solution, and the method is a novel way for preparing special structural materials with high efficiency, stability, convenience and economy.
Since 1968 Stober invention sol-gel method for preparing silicon dioxide, the morphology control of the silicon dioxide has become one of research hot spots, such as silicon dioxide mesoporous nanospheres, nanorods, nanotubes and the like. At present, a sol-gel method is mostly used for preparing the silicon dioxide nanotube, and organic template agents such as ammonium citrate, CTAC (cetyltrimethylammonium chloride), CTAB (bromohexadecyltrimethylamine) and the like are utilized for preparing the silicon dioxide nanotube. Zheng et al used a sol-gel method to prepare silica nanotubes with ethyl orthosilicate as the silicon source, ethanol as the solvent, tartaric acid as the ammonia template precursor, and ammonia as the catalyst, however, the organic template is highly contaminated, not friendly to the environment, and its high price also limits its industrial applications. The silica prepared by using cellulose templates such as filter paper, cotton and the like through a sol-gel method not only effectively inherits the microstructure of the cellulose templates, but also has simple preparation process and is easy for industrial production. Zhang Yanhua et al use methyl orthosilicate as a silicon source, methanol as a solvent, filter paper as a template, and utilize a surface sol-gel method to deposit sol on filter paper fibers step by step to prepare silica nanotubes, and the prepared silica nanotubes have the microscopic morphology and structure of the filter paper fibers due to mild reaction conditions, but the preparation process of the method has a complex deposition process and low yield, so how to perfect and simplify the operation process becomes a key point of future industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the silicon dioxide nanotube with the cellulose structure, which has the advantages of simple process, mild condition, no use of an organic template agent, small environmental pollution, wide raw material source and low cost, and the prepared silicon dioxide nanotube has high specific surface area, can meet various compounding and doping requirements, can form a composite material with various metal oxides, and has wide application in the fields of photocatalysis and super capacitor electrode materials.
In order to solve the technical problems, the invention provides a preparation method of a silicon dioxide nanotube with a cellulose structure, which comprises the following steps:
(1) Adding 7-9 parts by mass of organosilane into 100-120 parts by mass of low-carbon alcohol, regulating the pH value to 2-3 by using hydrochloric acid with the concentration of 10-12 mol/L, and stirring for 3-5 hours at the speed of 200-300 rpm to form transparent silica sol;
(2) Cutting 10 parts by mass of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 3-5 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 60-80 ℃ for 4-6 hours for standby;
(3) Calcining the filter paper dried in the step (2) at 600-700 ℃ for 4-6 hours, burning off a filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
Specifically, the organosilane is methyl orthosilicate or methyl orthosilicate, and the lower alcohol is methanol, ethanol or isopropanol.
The invention uses biomass cellulose as a template, does not need to add a template agent, has mild reaction conditions and simple steps, and the prepared silica nanotube highly reduces the microstructure of the filter paper fiber, and has the advantages of large specific surface area, more active sites, capability of being used as a composite material filler and the like.
Drawings
FIG. 1 is a scanning electron microscope picture of a filter paper used in the present invention.
Fig. 2 is a scanning electron microscope image of a silica nanotube of a cellulose structure synthesized in example 1 of the present invention.
Fig. 3 is a scanning electron microscope image of a silica nanotube of a cellulose structure synthesized in example 2 of the present invention.
Fig. 4 is a scanning electron microscope image of a silica nanotube of a cellulose structure synthesized in example 3 of the present invention.
Fig. 5 is a scanning electron microscope image of a silica nanotube of a cellulose structure synthesized in example 4 of the present invention.
Fig. 6 is a scanning electron microscope image of a silica nanotube of a cellulose structure synthesized in example 5 of the present invention.
FIG. 7 is a scanning electron microscope image of a silica nanotube of cellulose structure synthesized in example 6 of the present invention.
Detailed Description
The invention will be further apparent from the examples given below, which are not intended to be limiting.
Example 1
A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) Adding 9g of ethyl orthosilicate into 100g of absolute ethyl alcohol, adding 5g of hydrochloric acid with the concentration of 10mol/L to adjust the pH value to 2, slowly hydrolyzing the ethyl orthosilicate, and stirring the mixed solution at the speed of 200rpm for 5 hours to form transparent silica sol;
(2) Cutting 10g of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 3 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 80 ℃ for 4 hours for standby;
(3) And (3) placing the dried filter paper in the step (2) into a muffle furnace, calcining at 650 ℃ for 5 hours to burn out a filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
SEM photographs of the synthesized silica nanotubes having a cellulose structure are shown in fig. 2, showing a structure similar to that of the filter paper template (fig. 1).
Example 2
A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) Adding 9g of ethyl orthosilicate into 120g of absolute methanol, adding 4g of hydrochloric acid with the concentration of 12mol/L to adjust the pH value to 2.5, slowly hydrolyzing the ethyl orthosilicate, and stirring the mixed solution at the speed of 300rpm for 3 hours to form transparent silica sol;
(2) Cutting 10g of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 5 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 60 ℃ for 5 hours for later use;
(3) And (3) placing the dried filter paper in the step (2) into a muffle furnace, calcining at 650 ℃ for 5 hours to burn out a filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
SEM photographs of the synthesized silica nanotubes having a cellulose structure are shown in fig. 3, showing a structure similar to that of the filter paper template (fig. 1).
Example 3
A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) 7g of methyl orthosilicate is added into 110g of absolute methanol, then 5g of hydrochloric acid with the concentration of 12mol/L is added to adjust the pH value to 2, so that the ethyl orthosilicate is slowly hydrolyzed, and the mixed solution is stirred for 4 hours at the speed of 300rpm to form transparent silica sol;
(2) Cutting 10g of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 3 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 60 ℃ for 6 hours for standby;
(3) And (3) placing the dried filter paper in the step (2) into a muffle furnace, calcining for 4 hours at the temperature of 700 ℃ to burn out the filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
SEM photographs of the synthesized silica nanotubes having a cellulose structure are shown in fig. 4, showing a structure similar to that of the filter paper template (fig. 1).
Example 4
A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) 7g of methyl orthosilicate is added into 110g of absolute ethyl alcohol, then 5g of hydrochloric acid with the concentration of 10mol/L is added to adjust the pH value to 3, so that the ethyl orthosilicate is slowly hydrolyzed, and the mixed solution is stirred for 4 hours at the speed of 300rpm to form transparent silica sol;
(2) Cutting 10g of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 3.5 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 70 ℃ for 4 hours for standby;
(3) And (3) placing the dried filter paper in the step (2) into a muffle furnace, calcining for 4 hours at the temperature of 700 ℃ to burn out the filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
An SEM photograph of the synthesized silica nanotubes having a cellulose structure is shown in fig. 5, showing a structure similar to that of the filter paper template (fig. 1).
Example 5
A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) Adding 7g of methyl orthosilicate into 100g of isopropanol, adding 5g of hydrochloric acid with the concentration of 12mol/L to adjust the pH value to 2, slowly hydrolyzing the ethyl orthosilicate, and stirring the mixed solution at the speed of 200rpm for 5 hours to form transparent silica sol;
(2) Cutting 10g of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 4 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 80 ℃ for 4 hours for standby;
(3) And (3) placing the dried filter paper in the step (2) into a muffle furnace, calcining for 4 hours at 600 ℃ to burn out a filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
An SEM photograph of the synthesized silica nanotubes having a cellulose structure is shown in fig. 6, showing a structure similar to that of the filter paper template (fig. 1).
Example 6
A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) Adding 9g of ethyl orthosilicate into 110g of isopropanol, adding 5g of hydrochloric acid with the concentration of 10mol/L to adjust the pH value to 2.5, slowly hydrolyzing the ethyl orthosilicate, and stirring the mixed solution at the speed of 200rpm for 4 hours to form transparent silica sol;
(2) Cutting 10g of low ash quantitative filter paper into blocks, adding the blocks into transparent sol, soaking for 5 hours to enable silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 80 ℃ for 4 hours for standby;
(3) And (3) placing the dried filter paper in the step (2) into a muffle furnace, calcining at 600 ℃ for 6 hours to burn out a filter paper template, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
An SEM photograph of the synthesized silica nanotubes having a cellulose structure is shown in fig. 7, showing a structure similar to that of the filter paper template (fig. 1).
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention in any way; any person skilled in the art can make possible variations and modifications to the technical solution of the present invention, or modifications to equivalent embodiments, using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention, unless departing from the technical solution of the present invention.

Claims (3)

1. A method for preparing a silica nanotube with a cellulose structure, comprising the steps of:
(1) Adding 7-9 parts by mass of organosilane into 100-120 parts by mass of low-carbon alcohol, regulating the pH value to 2-3 by using hydrochloric acid with the concentration of 10-12 mol/L, and stirring for 3-5 hours at the speed of 200-300 rpm to form transparent silica sol;
(2) Cutting 10 parts by mass of low ash quantitative filter paper into blocks, adding the blocks into transparent silica sol, soaking for 3-5 hours to enable the silica sol to be fully deposited on filter paper fibers, taking out the filter paper, cleaning the filter paper by deionized water, and drying at 60-80 ℃ for 4-6 hours for standby;
(3) Calcining the filter paper dried in the step (2) at 600-700 ℃ for 4-6 hours, and cooling to room temperature to obtain the silica nanotube with the filter paper fiber structure.
2. The method for preparing silica nanotubes having a cellulose structure according to claim 1, wherein: the organosilane is methyl orthosilicate or methyl orthosilicate.
3. The method for preparing silica nanotubes having a cellulose structure according to claim 1 or 2, characterized in that: the lower alcohol is methanol, ethanol or isopropanol.
CN202311038378.6A 2023-08-17 2023-08-17 Preparation method of silicon dioxide nanotube with cellulose structure Pending CN117069118A (en)

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