CN112194192B - C/CoS regulated and controlled by template2Method for preparing nanotube structure - Google Patents
C/CoS regulated and controlled by template2Method for preparing nanotube structure Download PDFInfo
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Abstract
The invention belongs to the technical field of nano photoelectronic materials, and discloses a C/CoS with a controllable structure2A method for preparing nanotubes. The invention adopts a one-step simple chemical vapor diffusion strategy and regulates and controls the reaction atmosphere, namely Ar/H2The gas ratio, thereby realizing the controllable growth from the nano rod to the nano tube, having the advantages of simple preparation process, stable product structure, high catalytic activity site and the like, and having high-efficiency catalytic activity. The problems of uncontrollable product structure, few active sites of the catalyst and the like in the traditional preparation method are solved. The invention has important engineering practical significance and has wide application prospect in the fields of military industry, aerospace, energy, electronics, environment and the like.
Description
Technical Field
The invention relates to a C/CoS with controllable structure2A nanotube preparation method belongs to the technical field of nano photoelectron materials.
Background
The global energy crisis has become a serious worldwide problem. Traditional energy sources such as petroleum, coal, natural gas and the like are primary energy sources and are non-renewable, and the search for sustainable, renewable and clean energy sources is particularly important. In the past decades, efforts have been made to develop new energy sources such as hydrogen fuel, solar cells, lithium sulfur cells, metal air cells, carbon dioxide electrochemical reduction, perovskite solar cells, sensors, etc., and among them, hydrogen energy has become the most focused research object of researchers. As is well known, hydrogen has long been recognized as a clean, earth-rich, environmentally friendly energy source. However, if sufficient hydrogen energy is developed, a large bias needs to be provided, which puts high demands on the plant power. Then, whether an improved way can be proposed to achieve the goal of high-efficiency catalysis starting from the reduction of power consumption. So far, numerous researchers are all seeking for a catalyst for efficiently producing hydrogen, for example, noble metals such as Pt and Pd are the first choice materials for researching the electrocatalysis performance. However, these noble metals are low in content and expensive, and are not suitable catalysts in the long term, so it is important to find a high-efficiency, pollution-free and low-cost catalyst to replace noble metals.
In recent years, transition metal chalcogenide MX2Wherein M is usually Mo, W, Co, etc.; x is usually S, Se, etc., which are considered to be most likely chalcogenides to replace noble metals due to their unique electrochemical properties. Wherein, MoS2Is one of the most typical catalysts, and has wide application in the field of electrocatalysis. However, purely prepared MoS2There are some disadvantages, such as low conductivity and few catalytically active sites, which limit its further development in the catalytic field. And MoS2In contrast, CoS2Also has ultrahigh conductivity and excellent catalytic performance, which is sought after by researchers. And the preparation process is simple, the product purity is high, the control is easy, and products with different shapes, such as nanotubes, nanowires, nanosheets, nano hollow cubes, nanoflowers, nanoparticles and the like, can be obtained. In addition, structural regulation is also an important factor for enhancing electrochemical performance, such as adding carbon-based conductive materials, constructing a core-shell composite structure, constructing a heterostructure and doping N, Se and nano materialsAnd the like. However, the above researches have some disadvantages, mainly including difficult preparation method, uncontrollable product structure, few active sites of the catalyst, etc., thereby affecting the electrochemical performance of the electrode material.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention provides a simple C/CoS self-template regulated and controlled2A method for preparing a nanotube structure, which aims to solve the problem of the existing CoS2Small specific surface area, few chemical active sites, low electrocatalytic performance and the like, and simultaneously improves the application of the electrode material in the aspects of electricity and photoelectrocatalysis.
The technical scheme adopted by the invention for solving the technical problems is as follows:
C/CoS regulated and controlled by template2The preparation method of the nanotube structure comprises the following steps:
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 80 to 180 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a low-temperature zone in a chemical vapor deposition system, wherein the temperature is set to 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out in Ar/H2Under the protection of gas, the reaction time is 1 hour, and C/CoS is obtained after the reaction is cooled2。
As the inventionIn the further improvement, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 100%: 0 percent.
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 99%: 1 percent.
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 95%: 5 percent.
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 90%: 10 percent.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is simple, and the product purity is high;
2. the product appearance is controllable. By controlling the reaction Ar/H2The gas ratio can obtain different appearances;
3. the prepared product has more active sites. The nanotube has large specific surface area and a plurality of catalytic active sites, which is beneficial to improving the catalytic performance;
4. the method has universality. The method is also suitable for the application of other chalcogen nano materials in the aspects of electric storage, electrocatalysis and the like.
Drawings
FIG. 1a is a process flow diagram for examples 1, 2, 3 and 4;
FIG. 1b is a chemical vapor process flow diagram for examples 1, 2, 3 and 4;
FIG. 2 is a scanning electron microscope image of the precursor Co (OH) Cl-urea at different temperatures;
FIGS. 2a-b are topographical views of the precursor Co (OH) Cl-urea at 80 ℃;
FIGS. 2c-d are topographical views of Co (OH) Cl-urea as a precursor at 100 deg.C;
FIGS. 2e-f are topographical views of Co (OH) Cl-urea precursor at 140 ℃;
FIG. 2g-h is a graph of the morphology of the precursor Co (OH) Cl-urea at 140 ℃;
FIGS. 2i-j are topographical views of the precursor Co (OH) Cl-urea at 180 ℃;
FIG. 3 is a diagram showing the formation mechanism of the samples of examples 1, 2, 3 and 4 and different Ar/H2Scanning electron microscopy images under contrast;
FIG. 4 is a scanning electron microscope photograph of the vulcanizate of examples 1, 2, 3, and 4 at different temperatures;
FIGS. 4a-c are scanning electron microscope images of the vulcanizate at 300 ℃;
FIGS. 4d-f are scanning electron micrographs of the vulcanizate at 350 ℃;
FIGS. 4g-i are scanning electron micrographs of the vulcanizate at 400 ℃;
FIGS. 4j-l are scanning electron micrographs of the vulcanizate at 600 ℃;
FIG. 4m-o is a scanning electron micrograph of the vulcanizate at 800 ℃;
FIGS. 5a-b are scanning electron microscopes of the sample of example 3;
FIGS. 5c-d are transmission electron microscopes of the samples of example 3;
FIGS. 5e-f are electron energy spectra of the samples of example 3;
FIGS. 6a-c are photoelectron spectra of the sample of example 3 according to the present invention;
FIG. 6d is a thermogravimetric analysis of a sample of example 3 in accordance with the present invention.
Detailed Description
The invention is further illustrated with reference to the following specific examples and figures without limiting the scope of the invention.
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 80 to 180 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a low-temperature zone in a chemical vapor deposition system, wherein the temperature is set to 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out in Ar/H2Under the protection of gas, the reaction time is 1 hour, and C/CoS is obtained after the reaction is cooled2。
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 100%: 0 percent.
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 99%: 1 percent.
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 95%: 5 percent.
As a further improvement of the invention, the reaction temperature in the step a is 140 ℃, and Ar/H in the step c2The ratio is 90%: 10 percent.
Example 1
This example prepares C/CoS as follows2Chain type nano-rod:
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 140 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a low-temperature zone in a chemical vapor deposition system, wherein the temperature is set to 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out in Ar/H2Under the protection of gas, wherein Ar/H2The ratio is 100%: 0 percent, the reaction time is 1 hour, and C/CoS is obtained after the reaction is cooled2。
Example 2
This example prepares C/CoS as follows2Mixed phase of nano-rod and nano-tube:
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 140 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a low-temperature zone in a chemical vapor deposition system, wherein the temperature is set to 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out in Ar/H2Under the protection of gas, wherein Ar/H2The ratio is 99%: 1 percent, the reaction time is 1 hour, and C/CoS is obtained after the reaction is cooled2。
Example 3
This example prepares C-CoS2Nanotube and method of manufacturing the same
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 140 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a low-temperature zone in a chemical vapor deposition system, wherein the temperature is set to 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out in Ar/H2Under the protection of gas, wherein Ar/H2The ratio is 95%: 5 percent, the reaction time is 1 hour, and C/CoS is obtained after the reaction is cooled2。
Example 4
This example prepares C/CoS as follows2Nanotube and method of manufacturing the same
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 140 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a low-temperature zone in a chemical vapor deposition system, wherein the temperature is set to 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out in Ar/H2Under the protection of gas, wherein Ar/H2The ratio is 90%: 10 percent, the reaction time is 1 hour, and C/CoS is obtained after the reaction is cooled2。
FIG. 1 is a process flow diagram of the products of examples 1, 2, 3 and 4. Wherein FIG. 1a is a process flow diagram of examples 1, 2, 3 and 4; FIG. 1b is a chemical vapor process flow diagram for examples 1, 2, 3 and 4. As is obvious in the figure, the first step adopts a low-temperature solvothermal method to prepare a precursor Co (OH) Cl-urea; the second step adopts a chemical vapor deposition method to prepare C @ CoS2Product by changing Ar/H2Different products can be obtained by gas ratio.
FIG. 2 is a scanning electron microscope image of the precursor Co (OH) Cl-urea at different temperatures. As can be seen from FIGS. 2a-b, the solvothermal reaction temperature was set at 80 ℃ and a small amount of nanorods appeared in the product; when the temperature is increased to 100 ℃, as shown in fig. 2c-d, the product has partially disordered nanorods and aggregation phenomenon; the temperature is further raised to 140 ℃, and as shown in the figure 2e-f, the appearance of the product is greatly changed, and an umbrella-shaped nanorod structure is formed; when the reaction temperature reaches 160 ℃, as shown in the graph of 2g-h, the appearance of the product presents an umbrella-shaped nanorod structure; the temperature is continuously increased to 180 ℃, as shown in fig. 2i-j, the morphology of the product is not changed.
FIG. 3 is a diagram showing the formation mechanism of the samples of examples 1, 2, 3 and 4 and different Ar/H2Scanning electron microscopy images of gas ratios; FIG. 3a is a diagram of the mechanism of product formation. FIG. 3b is the chemical vapor deposition product under pure Ar (100% Ar) atmosphere, exhibiting framework nanorods. When H is present2The addition was 1% (1% H)299% Ar), the product becomes a rod and tube mixed structure as shown in figure 3 c. With H2The dosage is further increased, and the product is tubularThe structure becomes more and more obvious. When H is present2The amount reaches 5% (5% H)295% Ar), most of the nanorods are converted into nanotubes, as shown in fig. 3 d. Continuously increasing H2Amount when Ar/H2The ratio exceeds 10% (10% H)290% Ar), the nanotube surface is rough, presenting a broken appearance, as shown in fig. 3 e. In summary, the gaseous environment plays a decisive role in the synthesis of nanorods or nanotubes. That is, when the hydrogen ion concentration is low, the electron transfer does not change the surface properties of the Co (OH) Cl-urea acicular nanorods and does not cause internal reaction. As the hydrogen concentration increases, its electron transfer is sufficient to change the Co (OH) Cl-urea surface properties, promoting reactions within it. With Co2+、OH-And urea molecules are diffused outwards, the reaction is further promoted, and the solid diffusion activation energy is far greater than the reaction activation energy, so that a hollow tubular structure is formed.
FIG. 4 is a scanning electron microscope photograph of the vulcanizate of examples 1, 2, 3, and 4 at different temperatures; FIGS. 4a-c are scanning electron micrographs of the vulcanizate at 300 ℃; FIGS. 4d-f are scanning electron micrographs of the vulcanizate at 400 ℃; FIGS. 4g-i are scanning electron micrographs of the vulcanizate at 500 ℃; FIGS. 4j-l are scanning electron micrographs of the vulcanizate at 600 ℃; FIG. 4m-o is a scanning electron micrograph of the vulcanizate at 800 ℃; as can be seen from the figure, the nanotube structure is most obvious for the product at a reaction temperature of 400 ℃, and therefore, the optimal reaction temperature is 400 ℃.
FIGS. 5a-b are scanning electron microscopes of the sample of example 3; it can be seen from the figure that the product exhibits a hollow structure. FIGS. 5c-d are transmission electron microscopes of the samples of example 3. As shown in FIG. 5c, which is a TEM image of the product, the structure is tubular, and as can be seen from a High Resolution TEM (HRTEM) image, the crystal has obvious lattice fringes and lattice spacing similar to that of CoS reported in the literature2The values of (a) are consistent, further demonstrating the presence of product. FIG. 5f Spectroscopy results show that the Co to S ratio is 1:2, further confirming that the product contains CoS2。
FIGS. 6a-c are photoelectron spectra of the sample of example 3 according to the present invention; FIG. 6d is a thermogravimetric analysis of a sample of example 3 in accordance with the present invention. The analysis in the figure canIt is known that peaks at 778.3eV and 780.5eV correspond to Co 2p3/2And Co 2p1/2This is in contrast to the literature reported CoS2The Co 2p values in (1) are quite consistent. Furthermore, the two XPS peaks at 785.9 and 802.5eV correspond to CoO respectivelyx Co 2p in (1)3/2And Co 2p1/2This result confirmed the CoOxIs present. Furthermore, it was found that S2 p XPS spectra, as shown in FIG. 6b, are at 162.7eV, and 164.2eV respectively correspond to S2 p3/2And S2 p1/2This means S2-Is present. At the same time, to further demonstrate the presence of carbon in the product, a C1s spectrum was also tested, as shown in FIG. 6C, from which it can be seen that there are two characteristic peaks for non-oxygenated carbon (C-C284.9 eV) and carbon (C-O287 eV), and the form of the presence of C may be amorphous. To further demonstrate the carbon content, the CoS was determined using thermogravimetric analysis (TGA) as shown in FIG. 6d2The medium carbon content. The amorphous carbon content was calculated to be about 22.3% (wt%).
Claims (1)
1. C/CoS regulated and controlled by template2The preparation method of the nanotube structure is characterized by comprising the following steps:
a. 0.58g of Co (NO) is weighed out3)2·6H2O or 0.47g CoCl2·6H2O、0.27g NH4Cl and 0.6g of urea are uniformly mixed and put into a 50ml beaker, 35ml of deionized water is added to be uniformly stirred, then the mixture is put into a 50ml reaction kettle and put into a drying oven to react for 6 to 12 hours, the reaction temperature is 80 to 180 ℃, and an initial product Co (OH) Cl-urea is obtained;
b. after the reaction is cooled, taking out an initial product Co (OH) Cl-urea, further carrying out ultrasonic treatment on the initial product Co (OH) Cl-urea to ensure the purity of the initial product Co (OH) Cl-urea, wherein the ultrasonic treatment time is 20 minutes, then washing the initial product Co (OH) Cl-urea for multiple times by using alcohol and deionized water, and finally placing the initial product Co (OH) Cl-urea in a vacuum drying oven to be dried for 12-24 hours, wherein the temperature of the oven is 60 ℃;
c. 0.01g of the initial product Co (OH) Cl-urea was weighed into the high temperature zone in the chemical vapor deposition system, the temperature was set at 400 ℃; placing 0.1g S powder in a chemical vapor deposition systemA low-temperature zone, wherein the temperature is set to be 240 ℃; the position between the initial product Co (OH) Cl-urea and S powder is kept between 15 and 20 cm; the whole chemical gas phase reaction is carried out at certain Ar/H2The reaction is carried out for 1 hour in a volume ratio, and C/CoS is obtained after the reaction is cooled2A nanotube structure; wherein, Ar/H2The volume ratio is 99%: 1% or 95%: 5% or 90%: 10 percent.
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