CN111847517A - Ordered mesoporous carbon composite material directly introduced with tungsten trioxide by hard template method and preparation method thereof - Google Patents
Ordered mesoporous carbon composite material directly introduced with tungsten trioxide by hard template method and preparation method thereof Download PDFInfo
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- CN111847517A CN111847517A CN202010654426.4A CN202010654426A CN111847517A CN 111847517 A CN111847517 A CN 111847517A CN 202010654426 A CN202010654426 A CN 202010654426A CN 111847517 A CN111847517 A CN 111847517A
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- C01G41/00—Compounds of tungsten
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Abstract
The invention discloses a method for successfully preparing an ordered mesoporous carbon loaded tungsten trioxide composite material (WO) by taking a silicon dioxide loaded phosphotungstic acid composite material (HPW/OMS) as a hard template3OMC) characterized by the direct introduction of WO by means of a one-step synthesis technique3Active site, WO3The composite material is uniformly dispersed on the surface of OMC, the ordered structure of the hard template is reserved, and the preparation process flow is simple and direct.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an ordered mesoporous carbon composite material directly introducing tungsten trioxide by a hard template method and a preparation method thereof.
Background
In 1999, Ryoo et al and Hyeon et al almost simultaneously reported independently a method for synthesizing ordered mesoporous carbon using mesoporous templates. The synthesized carbon material was named CMK-1 by Ryoo et al. Thereafter, CMK series mesoporous carbons were developed, of which typical representatives are CMK-3 and CMK-5, which were synthesized using mesoporous silica SBA-15 as a template, and CMK-3 was obtained when the carbon source was completely filled in the pores of SBA-15. Because the micropores in the wall of the SBA-15 hole connect the parallel cylindrical pore channels into a three-dimensional communicated pore system, the parallel carbon nanorods copied from the main pore channel are connected with each other through the carbon nanorods copied from the micropores, so that the CMK-3 keeps the mesoporous structure with ordered hexagonal arrangement of the SBA-15.
If the carbon source is partially filled or only coated with a layer on the inner surface of the pore channel, then the obtained CMK-5 will be of nanotube type. Sucrose, glucose, ethylene, propylene, furfuryl alcohol, phenolic resin, resorcinol, formaldehyde resin, and nitrogen-containing substances (such as ethylenediamine and carbon tetrachloride, aniline, polyacrylonitrile, acetonitrile, etc.) can be used as carbon sources for synthesizing mesoporous carbon. We propose a load-type OMC. Unlike the conventional methods, one-step synthesis using a hard template method is proposed, and WO is directly introduced by one-step synthesis technology3An active site. WO3Converted from HPW by high temperature calcination. WO3Is a semiconductor having an n-type band gap of 2.4-2.8 eV. This is a promising candidate. The doping of the OMC material can further enrich the application field of the OMC material. And WO3Combined with OMC, the WO is reduced3The specific surface area of the composite material is also improved while the band gap energy is increased.
Research results show that the material retains a two-dimensional hexagonal ordered mesoporous structure, and has a large specific surface area, uniform pore diameter and the like by a one-step introduction method. Therefore, we propose a one-step synthesis method to design and prepare the mesoporous carbon loaded tungsten trioxide composite material and synthesize WO 3A/OMC composite material.
Disclosure of Invention
The invention aims to solve the technical problem of preparing an ordered mesoporous carbon loaded tungsten trioxide composite material by combining one-step synthesis with a hydrothermal treatment technology. Another object of the present invention is to provide a method for preparing the composite material.
The preparation method of the ordered mesoporous carbon loaded tungsten trioxide takes the HPW/OMS composite material as a hard template, and reduces the environmental pollution. The phosphotungstic acid not only provides a synthetic medium, but also can be converted into WO in the high-temperature calcination process3An active site. The preparation method simplifies the preparation process and reduces the production cost; the ordered mesoporous carbon loaded tungsten trioxide composite material synthesized by one step by the preparation method has a larger specific surface area.
The invention directly introduces active sites in one step to prepare the ordered mesoporous carbon loaded tungsten trioxideA composite material is prepared by taking a triblock copolymer P123 as a structure directing agent, Keggin type phosphotungstic acid as a catalytic active center, a phosphotungstic acid aqueous solution as a synthesis medium, Tetraethoxysilane (TEOS) as an inorganic silicon source precursor, hydrolyzing and condensing to synthesize a HPW/OMS composite material framework, sucrose as a carbon source, and adopting a one-step synthesis strategy to successfully prepare a series of mesoporous carbon loaded tungsten trioxide composite materials directly introducing active sites in one step, wherein the structure of the mesoporous carbon loaded tungsten trioxide composite materials is WO 3/OMC。
Preferably, the composite material is a mesoporous material, and the average pore diameter of the composite material is 3-5 nm.
The preparation method of the mesoporous carbon loaded tungsten trioxide composite material with the active sites directly introduced in one step comprises the following steps:
(1) 0.1 g phosphotungstic acid was dissolved in 30 mL deionized water and 1.0 g P123 was added. The mixture is stirred strongly for 4 hours at the temperature of 40 ℃ to obtain a clear solution containing the structure directing agent;
(2) then adding 0.05 g of KCl into the clear solution in the step (1), and continuing stirring for 1 h;
(3) adding 2 g of 98% tetraethoxysilane by mass into the solution, and heating and stirring the mixture for 24 hours at the temperature of 40 ℃;
(4) and transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal crystallization for 24 hours at 100 ℃. Filtering and washing the mixture, and drying the obtained white solid at 60 ℃ for 12 h;
(5) and finally, roasting the white solid substance in a muffle furnace at 350 ℃ for 10 h to obtain the HPW/OMS composite material.
(6) 0.625 g of sucrose and 0.07 g H g of the composite material obtained in (5) were added2SO4、2.5 mL H2O ultrasonic dissolution. The mixture was placed in a drying cabinet at 100 ℃ for 6 h, and then the temperature of the drying cabinet was raised to 160 ℃ and maintained there for 6 h. During the treatment in the drying oven, the sample turned dark brown or black, containing partially polymerized and carbonized sucrose in the present step;
(7) The sample obtained in (6) was dissolved in 0.4 g of sucrose, 0.045 g of sucrose by sonicationH2SO4And 2.5 mL of H2O, further treatment at 100 ℃ and 160 ℃ using the same drying oven;
(8) then, it was transferred to a tube furnace and heated in N2Carbonization was carried out at 800 ℃ under protection and maintained at this temperature for 4 h. The composite was stripped of the silica template with 5% HF at room temperature. The template-free carbon product thus obtained was washed with ethanol and dried at 120 ℃ to give WO3OMC, preferably, the carbonization in step (8) is complete.
Compared with the prior art, the invention has the following innovation: the invention uses HPW/OMS to directly introduce WO into a hard template in one step3The active site adopts phosphotungstic acid aqueous solution as a medium, P123 as a template agent, TEOS as a silicon source and sucrose as a carbon source, and phosphotungstic acid can be directly converted into a tungsten trioxide active site in the high-temperature calcination process. The production process is simplified. The synthesized ordered mesoporous carbon loaded tungsten trioxide composite material is a mesoporous material with an ordered structure, the aperture is uniform, and the average aperture is 3-5 nm.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only individual embodiments of the present invention, and other drawings can be obtained by those skilled in the art according to the idea of the present invention.
FIG. 1 is WO prepared in example 1 of the present invention3Transmission electron microscopy of the/OMC composite.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
WO3the/OMC composite material is prepared by the following steps:
(1) 0.1 g phosphotungstic acid was dissolved in 30 mL deionized water and 1.0 g P123 was added. The mixture is stirred strongly for 4 hours at the temperature of 40 ℃ to obtain a clear solution containing the structure directing agent;
(2) then adding 0.05 g of KCl into the clear solution in the step (1), and continuing stirring for 1 h;
(3) adding 2 g of 98% tetraethoxysilane by mass into the solution, and heating and stirring the mixture for 24 hours at the temperature of 40 ℃;
(4) and transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal crystallization for 24 hours at 100 ℃. Filtering and washing the mixture, and drying the obtained white solid at 60 ℃ for 12 h;
(5) and finally, roasting the white solid substance in a muffle furnace at 350 ℃ for 10 h to obtain the HPW/OMS composite material. The composite material has a typical two-dimensional hexagonal structure, and is a mesoporous material.
(6) Adding 0.5g of the HPW/OMS composite obtained in (5) to 0.625 g of sucrose, 0.07 g H 2SO4、2.5mL H2O ultrasonic dissolution. The mixture was placed in a drying cabinet at 100 ℃ for 6 h, and then the temperature of the drying cabinet was raised to 160 ℃ and maintained there for 6 h. During the treatment in the drying oven, the sample turned dark brown or black, containing partially polymerized and carbonized sucrose in the present step;
(7) the sample obtained in (6) was filled twice to be ultrasonically dissolved in 0.4 g of sucrose, 0.045 g H2SO4And 2.5 mLH2O, further treatment at 100 and 160 ℃ using the same drying oven;
(8) then, it was transferred to a tube furnace and heated in N2Carbonization was carried out at 800 ℃ under protection and maintained at this temperature for 4 h. The composite was stripped of the silica template with 5% HF at room temperature. The template-free carbon product thus obtained was washed with ethanol and dried at 120 ℃ to give WO3/OMC。
Example 2
WO3the/OMC composite material is prepared by the following steps:
(1) 0.3 g of phosphotungstic acid was dissolved in 30 mL of deionized water, and 1.0 g P123 was added. The mixture is stirred strongly for 4 hours at the temperature of 40 ℃ to obtain a clear solution containing the structure directing agent;
(2) then adding 0.05 g of KCl into the clear solution in the step (1), and continuing stirring for 1 h;
(3) Adding 2 g of 98% tetraethoxysilane by mass into the solution, and heating and stirring the mixture for 24 hours at the temperature of 40 ℃;
(4) and transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal crystallization for 24 hours at 100 ℃. Filtering and washing the mixture, and drying the obtained white solid at 60 ℃ for 12 h;
(5) and finally, roasting the white solid substance in a muffle furnace at 350 ℃ for 10 h to obtain the HPW/OMS composite material.
(6) Adding 0.5 g of the HPW/OMS composite obtained in (5) to 0.625 g of sucrose, 0.07 g H2SO4、2.5mL H2O ultrasonic dissolution. The mixture was placed in a drying cabinet at 100 ℃ for 6 h, and then the temperature of the drying cabinet was raised to 160 ℃ and maintained there for 6 h. During the treatment in the drying oven, the sample turned dark brown or black, containing partially polymerized and carbonized sucrose in the present step;
(7) the sample obtained in (6) was filled twice and dissolved in 0.4 g of sucrose, 0.045 g H by ultrasonic wave2SO4And 2.5mL of H2O, further treatment at 100 ℃ and 160 ℃ using the same drying oven;
(8) then, it was transferred to a tube furnace and heated in N2Carbonization was carried out at 800 ℃ under protection and maintained at this temperature for 4 h. The composite was stripped of the silica template with 5% HF at room temperature. The template-free carbon product thus obtained was washed with ethanol and dried at 120 ℃ to give WO 3/OMC。
The structure of the composite material is shown in figure 1, and is a typical two-dimensional hexagonal structure, and the composite material is a mesoporous material.
Comparative example 1
Referring to the preparation process of example 1, the traditional hydrochloric acid system synthesis method is adopted, and the preparation process is as follows:
(1) 1.0 g P123 was dissolved in 30 mL of 2M hydrochloric acid solution. Strongly stirring for 4 hours at 40 ℃ to obtain a clear solution containing the structure directing agent;
(2) adding 2 g of 98% tetraethoxysilane by mass into the solution, and heating and stirring the mixture for 24 hours at the temperature of 40 ℃;
(3) and transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal crystallization for 24 hours at 100 ℃. Filtering and washing the mixture, and drying the obtained white solid at 60 ℃ for 12 h;
(4) and finally, roasting the white solid substance in a muffle furnace at 500 ℃ for 10 h to obtain the OMS material.
(5) Adding 0.5 g of OMS material obtained in (4) to 0.625 g of sucrose, 0.07 g H2SO4、2.5 mL H2O ultrasonic dissolution. The mixture was placed in a drying cabinet at 100 ℃ for 6 h, and then the temperature of the drying cabinet was raised to 160 ℃ and maintained there for 6 h. During the treatment in the drying oven, the sample turned dark brown or black, containing partially polymerized and carbonized sucrose in the present step;
(6) The sample obtained in (5) was filled twice and dissolved in 0.4 g of sucrose, 0.045 g H by ultrasonic wave2SO4And 2.5mL of H2O, further treatment at 100 ℃ and 160 ℃ using the same drying oven;
(7) then, it was transferred to a tube furnace and heated in N2Carbonization was carried out at 800 ℃ under protection and maintained at this temperature for 4 h. The composite was stripped of the silica template with 5% HF at room temperature. The template-free carbon product thus obtained was washed with ethanol and dried at 120 ℃ to give pure OMC.
For WO prepared in examples 1 and 2 of the present invention3The OMC composite material and the OMC material prepared in the comparative example 1 are researched, and the phosphotungstic acid aqueous solution is adopted to replace the hydrochloric acid solution to be used as the medium for synthesizing the composite material, so that the process is simplified, the experimental period is shortened, the phosphotungstic acid not only provides the synthesized medium, but also can be converted into WO in the high-temperature calcination process3An active site. Direct guiding by hard template methodThe ordered mesoporous carbon composite material containing tungsten trioxide is a mesoporous material with an ordered structure, the pore diameter is uniform, and the average pore diameter is 3-5 nm.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (5)
1. Ordered mesoporous carbon loaded tungsten trioxide composite material with active sites directly introduced in one step (WO)3The preparation method of the/OMC) is characterized in that the preparation method uses ordered mesoporous silica supported phosphotungstic acid composite material (HPW/OMS) as a hard template, phosphotungstic acid can be directly converted into tungsten trioxide active sites in the high-temperature calcination process, the production process is simplified, the characterization shows that the mesoporous composite material has WO3Is present.
2. The ordered mesoporous carbon loaded tungsten trioxide composite material with active sites directly introduced in one step is characterized in that OMC is used as a carrier, and WO is loaded on the carrier3The structure of the composite material is WO3/OMC。
3. The ordered mesoporous carbon supported tungsten trioxide composite material with directly introduced active sites in one step according to claim 1, characterized in that WO is applied to the composite material3the/OMC composite material is a mesoporous material, and the average pore diameter of the/OMC composite material is 3-5 nm.
4. The preparation method of the ordered mesoporous carbon supported tungsten trioxide composite material directly introducing active sites according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) dissolving 0.1 g of phosphotungstic acid in 30 mL of deionized water, adding 1.0 g P123, and stirring the mixture strongly at 40 ℃ for 4 hours to obtain a clear solution containing a structure directing agent;
(2) Then adding 0.05 g of KCl into the clear solution in the step (1), and continuing stirring for 1 h;
(3) adding 2 g of 98% tetraethoxysilane by mass into the solution, and heating and stirring the mixture for 24 hours at the temperature of 40 ℃;
(4) transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization at 100 ℃ for 24 hours, filtering and washing the mixture, and drying the obtained white solid at 60 ℃ for 12 hours;
(5) finally, placing the white solid substance in a muffle furnace to be roasted for 10 hours at 350 ℃ to obtain the HPW/OMS composite material;
(6) adding 0.5 g of the composite material obtained in (5) to 0.625 g of sucrose and 0.07 g H2SO4、2.5 mL H2O ultrasonic dissolution, placing the mixture in a drying oven at 100 ℃ for 6 h, then raising the oven temperature to 160 ℃ and holding for 6 h, during the treatment in the oven, the sample turned dark brown or black, containing partially polymerized and carbonized sucrose in the present step;
(7) the sample obtained in (6) was filled twice and dissolved in 0.4 g of sucrose, 0.045 g H by ultrasonic wave2SO4And 2.5 mLH2O, further treatment at 100 ℃ and 160 ℃ using a drying oven;
(8) then, it was transferred to a tube furnace and heated in N 2Carbonizing at 800 deg.C under protection, maintaining at the temperature for 4h, removing silica template from the composite with 5% HF at room temperature, washing the obtained carbon product without template with ethanol, and drying at 120 deg.C to obtain WO3/OMC。
5. The preparation method of the ordered mesoporous carbon supported tungsten trioxide composite material with the active sites directly introduced in one step according to claim 4, wherein the carbonization in the step (8) is completed.
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