CN111268732B - Method for preparing molybdenum disulfide graphene aerogel by using low-temperature plasma and product thereof - Google Patents
Method for preparing molybdenum disulfide graphene aerogel by using low-temperature plasma and product thereof Download PDFInfo
- Publication number
- CN111268732B CN111268732B CN202010159520.2A CN202010159520A CN111268732B CN 111268732 B CN111268732 B CN 111268732B CN 202010159520 A CN202010159520 A CN 202010159520A CN 111268732 B CN111268732 B CN 111268732B
- Authority
- CN
- China
- Prior art keywords
- molybdenum disulfide
- graphene
- temperature plasma
- low
- slurry
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The invention discloses a method for preparing molybdenum disulfide graphene aerogel by utilizing low-temperature plasma, which comprises the following steps: mixing water and graphite powder, stirring, and simultaneously carrying out low-temperature plasma irradiation to obtain graphene slurry; dropwise adding sulfuric acid into the graphene slurry to obtain acidic graphene slurry; adding molybdenum trioxide into the acidic graphene slurry, stirring and simultaneously carrying out low-temperature plasma irradiation to obtain molybdenum disulfide graphene slurry; and centrifuging the molybdenum disulfide graphene slurry, carrying out solid-liquid separation, and then freeze-drying the solid part to obtain the molybdenum disulfide graphene aerogel. The invention also discloses molybdenum disulfide graphene aerogel. The invention realizes uniform dispersion and mixing of molybdenum disulfide and graphene based on ultraviolet radiation and microwave radiation generated in a low-temperature plasma system, and does not need to carry out additional ultrasonic dispersion. The adsorption performance and hydrogen evolution performance of the molybdenum disulfide graphene aerogel prepared by the method are higher than those of the molybdenum disulfide graphene aerogel prepared by the traditional method.
Description
Technical Field
The invention relates to the field of research and development of material preparation methods, in particular to a method for preparing molybdenum disulfide graphene aerogel by utilizing low-temperature plasma and a product thereof.
Background
Currently, molybdenum disulfide graphene aerogel is mainly prepared by a hydrothermal method, a chemical vapor deposition method, a solvothermal-heat treatment method, a physical doping method and the like. The chemical vapor deposition method is to form a composite coating nanomaterial by vaporizing a target material and sequentially depositing the target material on a substrate material. The preparation process is complex, target materials need to be purchased in advance, and the preparation process is difficult to popularize in a large scale in practical industrial application.
And when the hydrothermal method and the solvothermal-heat treatment method are used for preparing the molybdenum disulfide graphene aerogel, a reducing agent is required to be additionally added to reduce graphene oxide, and then a low-valence sulfur source is added to reduce high-valence molybdenum so as to generate molybdenum disulfide particles on the graphene particles. The physical doping rule is to introduce nitrides, carbides and phosphides into a molybdenum disulfide or graphene system, and the general preparation process is mainly a solvothermal-heat treatment method. In general, the molybdenum disulfide graphene aerogel prepared by the technology has the problems of complex preparation process, high dependence on reducing agents and low-valence sulfur sources, poor adsorption performance of the prepared composite material and the like.
In the prior art, the graphene-based nano molybdenum disulfide composite aerogel is prepared by mixing high-valence molybdenum salt and graphene oxide to preload or cover the surface of the graphene oxide with high-valence titanium molybdenum, and then reducing the high-valence titanium molybdenum and the graphene oxide by adding a thiocyanate reducing agent. In general, graphene oxide and a thiocyanide reducing agent are directly used as a carbon source and a sulfur source, so that the relative preparation cost is high. The thiocyanide reducing agent is a high-toxicity substance, which is easy to cause operator poisoning and the synthesis residual liquid still needs to be deeply disposed. Meanwhile, molybdenum disulfide in the prepared graphene-based nano molybdenum sulfide composite aerogel is unevenly distributed, and the composite aerogel is poor in adsorption and hydrogen evolution performance.
Therefore, based on the above discussion, developing a preparation technology with simple process, no need of adding reducing agent and low-valence sulfur source in the process and better finished product performance is a key to solving the bottleneck problem of the molybdenum disulfide graphene aerogel.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for preparing molybdenum disulfide graphene aerogel by utilizing low-temperature plasma.
The invention also solves the technical problem of providing the molybdenum disulfide graphene aerogel.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention provides a method for preparing molybdenum disulfide graphene aerogel by utilizing low-temperature plasma, which comprises the following steps:
1) Mixing water and graphite powder, stirring at a rotating speed of 60-180 rpm, and simultaneously carrying out low-temperature plasma irradiation for 0.5-1.5 hours to obtain graphene slurry;
2) Dropwise adding sulfuric acid into the graphene slurry to obtain acidic graphene slurry;
3) Adding molybdenum trioxide into the acidic graphene slurry, stirring at a rotating speed of 60-180 rpm, and simultaneously carrying out low-temperature plasma irradiation for 0.5-1.5 hours to obtain molybdenum disulfide graphene slurry;
4) And centrifuging the molybdenum disulfide graphene slurry, carrying out solid-liquid separation, and then carrying out vacuum freeze drying on the solid part to obtain the molybdenum disulfide graphene aerogel.
Wherein, the liquid-solid ratio of the water and the graphite powder in the step 1) is 1-3:1 mL/mg.
Wherein the action voltage of the low-temperature plasma irradiation in the step 1) is 20-50 KV, and the action atmosphere is oxygen.
Wherein the concentration of sulfuric acid in the step 2) is 1-2M.
Wherein, the mass ratio of the molybdenum trioxide to the acidic graphene slurry in the step 3) is 5-15:100.
Wherein, the action voltage of the low-temperature plasma irradiation in the step 3) is 20KV to 50KV, and the action atmosphere is argon.
Wherein, the vacuum freeze drying temperature in the step 4) is between-90 ℃ and-10 ℃, and the vacuum freeze drying time is between 6 and 18 hours.
The invention further discloses the molybdenum disulfide graphene aerogel obtained by the preparation method.
Reaction mechanism: in the low-temperature plasma action process, high-energy electrons released by the high-voltage electrode collide with oxygen to generate oxygen free radicals, and react with water molecules to generate hydrogen free radicals, hydroxyl free radicals and hydrated electrons. Simultaneously ultraviolet radiation and microwave radiation are generated along with the energy level transition of excited particles in the low-temperature plasma action process. Oxygen radicals and hydroxyl radicals can convert graphite to graphene oxide. While hydrogen radicals, ultraviolet radiation, and microwave radiation can convert graphene oxide to reduced graphene through a thermal reduction mechanism. Mixing molybdenum trioxide into acidic graphene slurry, stirring to obtain low-temperature plasma irradiation, and forming a dominant free radical in the slurry by combining hydrated electrons and hydrogen ions in the slurry because the action atmosphere is argon and the acted slurry is strong acid. The hydrogen radicals react with sulfate to produce hydrogen sulfide. The hydrogen sulfide combines with the molybdenum trioxide to produce molybdenum disulfide and hydrogen ions. Under the stirring effect and the ultraviolet radiation and microwave radiation effect, the molybdenum disulfide and the graphene are uniformly mixed together to form molybdenum disulfide graphene. Under the freeze drying effect, the molybdenum disulfide graphene is converted into molybdenum disulfide graphene aerogel.
The beneficial effects are that: according to the method, graphite powder is directly adopted as a raw material, so that the price is low, the graphene preparation process is directly realized through low-temperature plasma, the traditional toxic reducing agent of thiocyanide is avoided, only the freeze-drying part of the traditional graphene aerogel preparation method is reserved, and the early-stage graphene and molybdenum disulfide forming and mixing processes are all carried out in a low-temperature plasma environment. According to the invention, only graphite powder and sulfuric acid are used as carbon sources and sulfur sources to prepare graphene and molybdenum disulfide, so that the production and reduction processes of the traditional graphene oxide are simplified, and the production of reduced graphene is realized in only one system. The invention realizes uniform dispersion and mixing of molybdenum disulfide and graphene based on ultraviolet radiation and microwave radiation generated in a low-temperature plasma system, and does not need to carry out additional ultrasonic dispersion. The adsorption performance and hydrogen evolution performance of the molybdenum disulfide graphene aerogel prepared by the method are higher than those of the molybdenum disulfide graphene aerogel prepared by the traditional method.
Drawings
FIG. 1 is a flow chart of the processing method of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1 influence of the concentration of sulfuric acid added to graphene slurry on the adsorption and Hydrogen evolution properties of the prepared molybdenum disulfide graphene aerogel
Mixing water and graphite powder according to a liquid-solid ratio of 1:1 mL/mg, stirring at a rotating speed of 60rpm, and simultaneously carrying out low-temperature plasma irradiation for 0.5 hour to obtain graphene slurry, wherein the action voltage of the low-temperature plasma irradiation is 20KV, and the action atmosphere is oxygen. And (3) dropwise adding sulfuric acid into the graphene slurry to ensure that the sulfuric acid concentration in the slurry is respectively 0.5M, 0.7M, 0.9M, 1M, 1.5M, 2M, 2.1M, 2.3M and 2.5M, thereby obtaining nine groups of acidic graphene slurry. Adding molybdenum trioxide into nine groups of acidic graphene slurries according to the mass ratio of the molybdenum trioxide to the acidic graphene slurries of 5:100, stirring at a rotating speed of 60rpm, and simultaneously carrying out low-temperature plasma irradiation for 0.5 hour to obtain nine groups of molybdenum disulfide graphene slurries, wherein the action voltage of the low-temperature plasma irradiation is 20KV, and the action atmosphere is argon. And centrifuging the nine groups of molybdenum disulfide graphene slurries, performing solid-liquid separation, and then keeping the solid part at the temperature of minus 10 ℃ for 6 hours in vacuum freeze drying to obtain nine groups of molybdenum disulfide graphene aerogel.
Adsorption test and adsorption capacity calculation: 40mg of molybdenum disulfide graphene aerogel is added into 80mL of methylene blue organic solution with the concentration of 250mg/L, stirred for 30 minutes under the condition of 360rpm, and kept stand, and supernatant is taken for detection. The methylene blue concentration in the liquid was measured according to the standard method for determination of methylene blue adsorption value for woody activated carbon test method (GB-T12496.10-1999). The adsorption capacity of the molybdenum disulfide graphene aerogel to methylene blue is calculated according to formula (1), wherein Q t Adsorption capacity (mg/g) of molybdenum disulfide graphene aerogel on methylene blue, c 0 And c t The methylene blue concentration (mg/L) in the liquid before and after the adsorption test is carried out, m is the mass (g) of the added molybdenum disulfide graphene aerogel, and V is the volume (L) of the test solution.
Current density and electric double layer powerAnd (3) calculating the capacity: current Density (268.5 mA/cm) 2 ) And electric double layer capacitance (mF/cm) 2 ) The calculation (overpotential=300 mV) is carried out by referring to the method in the construction of graphene-based nano molybdenum sulfide composite aerogel and the research on the adsorption and hydrogen evolution performances of the graphene-based nano molybdenum sulfide composite aerogel.
The test results of this example are shown in Table 1.
TABLE 1 influence of added sulfuric acid concentration in graphene slurry on adsorption property and hydrogen evolution property of prepared molybdenum disulfide graphene aerogel
As can be seen from Table 1, when the concentration of sulfuric acid added to the graphene slurry is less than 1M (as in Table 1, when the concentration of sulfuric acid added to the graphene slurry=0.9, 0.7, 0.5 and lower values not listed in Table 1), the sulfuric acid is less, the corresponding generated hydrogen radicals and hydrogen sulfide are reduced, the molybdenum disulfide which is formed successively after the combination of hydrogen sulfide and molybdenum trioxide is reduced, the molybdenum disulfide and graphene are insufficiently mixed, so that the active area, defect structure and active site density formation conditions of the composite aerogel are all poor, the adsorption capacity of the prepared composite aerogel is all lower than 282mg/g, and the current density is all lower than 264mA/cm 2 The electric double layer capacitance is lower than 203mF/cm 2 . When the concentration of sulfuric acid added to the graphene slurry is equal to 1-2M (as in table 1, when the concentration of sulfuric acid added to the graphene slurry=1, 1.5, 2), the acting atmosphere is argon, and the acted slurry is strong acid at the same time, the hydrated electrons and the hydrogen ions combine to generate hydrogen radicals, and the hydrogen radicals become dominant radicals in the slurry. The hydrogen radicals react with sulfate to produce hydrogen sulfide. The hydrogen sulfide combines with the molybdenum trioxide to produce molybdenum disulfide and hydrogen ions. Under the stirring effect and the ultraviolet radiation and microwave radiation effect, the molybdenum disulfide and the graphene are uniformly mixed together to form molybdenum disulfide graphene. The final composite aerogel has good active area, defect structure and active site density formation conditions, so that the adsorption capacity of the prepared composite aerogel is larger than 292mg/g, and the current density is larger than 271mA/cm 2 Electric double layerThe capacitance is larger than 211mF/cm 2 . When the concentration of sulfuric acid added to the graphene slurry is greater than 2M (as in table 1, when the concentration of sulfuric acid added to the graphene slurry=2.1, 2.3, 2.5, and higher values not listed in table 1), the generated hydrogen sulfide is excessive, and the hydrogen sulfide is loaded on the surfaces of molybdenum disulfide and graphene, so that the mixing uniformity of molybdenum disulfide and graphene is poor, the active area, defect structure and active site density formation condition of the composite aerogel are poor, and the adsorption capacity, current density and electric double layer capacitance of the composite aerogel are remarkably reduced along with the further increase of the concentration of sulfuric acid added to the graphene slurry. Therefore, in combination, the benefits and the cost are combined, and when the concentration of sulfuric acid added into the graphene slurry is equal to 1-2M, the adsorption performance and the hydrogen evolution performance of the prepared molybdenum disulfide graphene aerogel are improved most favorably.
Example 2 influence of the mass ratio of molybdenum trioxide and acidic graphene slurry on the adsorption Performance and Hydrogen evolution Performance of the prepared molybdenum disulfide graphene aerogel
Mixing water and graphite powder according to a liquid-solid ratio of 2:1 mL/mg, stirring at a rotating speed of 120rpm, and simultaneously carrying out low-temperature plasma irradiation for 1 hour to obtain graphene slurry, wherein the action voltage of the low-temperature plasma irradiation is 35KV, and the action atmosphere is oxygen. And (3) dropwise adding sulfuric acid into the graphene slurry to enable the concentration of the sulfuric acid in the slurry to be 2M, so as to obtain the acidic graphene slurry. Adding molybdenum trioxide into the acidic graphene slurry according to the mass ratio of 2.5:100, 3.5:100, 4.5:100, 5:100, 10:100, 15:100, 15.5:100, 16.5:100 and 17.5:100, stirring at the rotating speed of 120rpm, and simultaneously carrying out low-temperature plasma irradiation for 1 hour to obtain nine groups of molybdenum disulfide graphene slurry, wherein the action voltage of the low-temperature plasma irradiation is 35KV, and the action atmosphere is argon. And centrifuging the nine groups of molybdenum disulfide graphene slurries, performing solid-liquid separation, and then keeping the solid part at the temperature of 50 ℃ below zero, and performing vacuum freeze drying for 12 hours to obtain nine groups of molybdenum disulfide graphene aerogel.
Adsorption test and adsorption capacity, current density and electric double layer capacitance calculation were the same as in example 1.
The test results of this example are shown in Table 2.
TABLE 2 influence of mass ratio of molybdenum trioxide to acidic graphene slurry on adsorption performance and hydrogen evolution performance of prepared molybdenum disulfide graphene aerogel
As can be seen from Table 2, when the mass ratio of molybdenum trioxide to acidic graphene slurry is less than 5:100 (as in Table 2, the mass ratio of molybdenum trioxide to acidic graphene slurry=4.5:100, 3.5:100, 2.5:100, and lower values not listed in Table 2), less molybdenum disulfide is formed by combining hydrogen sulfide with molybdenum trioxide, and the molybdenum disulfide and graphene are uniformly mixed, so that the active area, defect structure, and active site density formation conditions of the composite aerogel are all poor, the adsorption capacity of the prepared composite aerogel is lower than 292mg/g, and the current density is lower than 265mA/cm 2 The electric double layer capacitance is lower than 207mF/cm 2 . When the mass ratio of molybdenum trioxide to acidic graphene slurry is equal to 5-15:100 (as in table 2, when the mass ratio of molybdenum trioxide to acidic graphene slurry=5:100, 10:100, 15:100), hydrogen sulfide is combined with molybdenum trioxide to generate a proper amount of molybdenum disulfide. Under the stirring effect and the ultraviolet radiation and microwave radiation effect, the molybdenum disulfide and the graphene are uniformly mixed together to form molybdenum disulfide graphene. The final composite aerogel has good active area, defect structure and active site density formation conditions, so that the adsorption capacity of the prepared composite aerogel is larger than 304mg/g, and the current density is larger than 279mA/cm 2 The electric double layer capacitance is larger than 215mF/cm 2 . When the mass ratio of molybdenum trioxide to acidic graphene slurry is greater than 15:100 (as in table 2, the mass ratio of molybdenum trioxide to acidic graphene slurry = 15.5:100, 16.5:100, 17.5:100, and higher values not listed in table 2), the hydrogen sulfide is combined with the molybdenum trioxide to produce an excess of molybdenum disulfide such that the uniformity of mixing of molybdenum disulfide and grapheneThe composite aerogel is poor in active area, defect structure and active site density formation condition, so that the adsorption capacity, current density and double-electric-layer capacitance of the composite aerogel are obviously reduced along with the further increase of the mass ratio of molybdenum trioxide to acidic graphene slurry. Therefore, when the mass ratio of the molybdenum trioxide to the acidic graphene slurry is equal to 5-15:100, the adsorption performance and the hydrogen evolution performance of the prepared molybdenum disulfide graphene aerogel are improved most.
Example 3 influence of the action voltage of Low temperature plasma irradiation on the adsorption Performance and Hydrogen evolution Performance of the prepared molybdenum disulfide graphene aerogel
Mixing water and graphite powder according to a liquid-solid ratio of 3:1mL/mg, stirring at a rotating speed of 180rpm, and simultaneously carrying out low-temperature plasma irradiation for 1.5 hours to obtain graphene slurry, wherein the action voltage of the low-temperature plasma irradiation is 50KV, and the action atmosphere is oxygen. And (3) dropwise adding sulfuric acid into the graphene slurry to enable the concentration of the sulfuric acid in the slurry to be 2M, so as to obtain the acidic graphene slurry. Adding molybdenum trioxide into acid graphene slurry according to the mass ratio of the molybdenum trioxide to the acid graphene slurry of 15:100, stirring at a rotating speed of 180rpm, and simultaneously carrying out low-temperature plasma irradiation for 1.5 hours to obtain molybdenum disulfide graphene slurry, wherein the action voltages of the low-temperature plasma irradiation are respectively 10KV, 15KV, 18KV, 20KV, 35KV, 50KV, 52KV, 55KV and 60KV, and the action atmosphere is argon. And centrifuging the molybdenum disulfide graphene slurry, carrying out solid-liquid separation, and then keeping the solid part at-90 ℃ for 18 hours in vacuum freeze drying to obtain nine groups of molybdenum disulfide graphene aerogel.
Adsorption test and adsorption capacity, current density and electric double layer capacitance calculation were the same as in example 1.
The test results of this example are shown in Table 3.
TABLE 3 influence of the action voltage of Low temperature plasma irradiation on the adsorption and Hydrogen evolution properties of the prepared molybdenum disulfide graphene aerogel
As can be seen from Table 3, when the operating voltage of the low temperature plasma irradiation is lower than 20KV (as in Table 3, the operating voltage of the low temperature plasma irradiation=18 KV, 15KV, 10KV and lower values not listed in Table 3), the hydrated electron yield and the operating effect are deteriorated, the hydrogen radical and the hydrogen sulfide generation amount are correspondingly reduced, the molybdenum disulfide generated by combining the hydrogen sulfide with the molybdenum trioxide is reduced, the mixing uniformity of the molybdenum disulfide and the graphene is reduced, the active area, the defect structure and the active site density formation condition of the composite aerogel are deteriorated, the adsorption capacity of the prepared composite aerogel is lower than 293mg/g, and the current density is lower than 276mA/cm 2 The electric double layer capacitance is lower than 213mF/cm 2 . When the operating voltage of the low-temperature plasma irradiation is equal to 20-50 KV (as in table 3, when the operating voltage of the low-temperature plasma irradiation=20 KV, 35KV, 50 KV), the hydrated electrons combine with the hydrogen ions to generate hydrogen radicals, which become dominant radicals in the slurry. The hydrogen radicals react with sulfate to produce hydrogen sulfide. The hydrogen sulfide combines with the molybdenum trioxide to produce molybdenum disulfide and hydrogen ions. Under the stirring effect and the ultraviolet radiation and microwave radiation effect, the molybdenum disulfide and the graphene are uniformly mixed together to form molybdenum disulfide graphene. The final composite aerogel has good active area, defect structure and active site density formation conditions, so that the adsorption capacity of the prepared composite aerogel is more than 316mg/g, and the current density is more than 286mA/cm 2 The electric double layer capacitance is larger than 221mF/cm 2 . When the action voltage of the low-temperature plasma irradiation is higher than 50KV (as in table 3, the action voltage of the low-temperature plasma irradiation=52 KV, 55KV, 60KV and higher values not listed in table 3), the generated hydrogen radicals and hydrogen sulfide are excessive, so that molybdenum disulfide generated by combining the hydrogen sulfide and molybdenum trioxide is excessive, the mixing uniformity of the molybdenum disulfide and graphene is poor, the active area, the defect structure and the active site density formation condition of the composite aerogel are poor, and the adsorption capacity, the current density and the electric double layer capacitance of the composite aerogel are obviously reduced along with the further increase of the action voltage of the low-temperature plasma irradiation. Thus, in combination, the benefits and costs are combined when the low temperature plasma irradiates the active electricityAnd when the pressure is equal to 20-50 KV, the adsorption performance and hydrogen evolution performance of the prepared molybdenum disulfide graphene aerogel are improved most.
Comparative example the molybdenum disulfide graphene aerogel prepared by the invention is compared with the existing composite gas in terms of gelation adsorption performance and hydrogen evolution performance
The preparation method of the molybdenum disulfide graphene aerogel comprises the following steps: mixing water and graphite powder according to a liquid-solid ratio of 3:1mL/mg, stirring at a rotating speed of 180rpm, and simultaneously carrying out low-temperature plasma irradiation for 1.5 hours to obtain graphene slurry, wherein the action voltage of the low-temperature plasma irradiation is 50KV, and the action atmosphere is oxygen. And (3) dropwise adding sulfuric acid into the graphene slurry to enable the concentration of the sulfuric acid in the slurry to be 2M, so as to obtain the acidic graphene slurry. Adding molybdenum trioxide into the acidic graphene slurry according to the mass ratio of the molybdenum trioxide to the acidic graphene slurry of 15:100, stirring at a rotating speed of 180rpm, and simultaneously carrying out low-temperature plasma irradiation for 1.5 hours while stirring to obtain the molybdenum disulfide graphene slurry, wherein the action voltage of the low-temperature plasma irradiation is 50KV, and the action atmosphere is argon. And centrifuging the molybdenum disulfide graphene slurry, carrying out solid-liquid separation, and then keeping the solid part at-50 ℃ for 12 hours in vacuum freeze drying to obtain the molybdenum disulfide graphene aerogel.
The existing composite aerogel is prepared by the following steps: the composite aerogel is prepared according to the preparation method of the graphene-based nano molybdenum sulfide composite aerogel construction and adsorption and hydrogen evolution performance research. The specific method comprises the following steps: (1) First, 3mmol MoO was taken 3 Adding 30mL of deionized water into Graphene Oxide (GO) with a certain mass, magnetically stirring for 10 minutes, uniformly dispersing, and performing ultrasonic treatment for 1 hour to obtain uniformly dispersed suspension; (2) 8mmol KSCN is dissolved in 10mL deionized water, and then gradually added into MoO dropwise under the condition of magnetic stirring 3 And GO, continuing magnetic stirring for 30 minutes, and further performing ultrasonic dispersion for 30 minutes; (3) Maintaining magnetic stirring, slowly adding ammonia water into the mixed suspension solution in the step (2) dropwise to adjust the pH value to 10, and ensuring uniform dispersion of the suspension; (4) Finally, transferring the mixed suspension with the regulated pH value into a 50mL polytetrafluoroethylene high-pressure reaction kettle, and placing the mixed suspension into a blast drying oven to be heated for 24 hours at a constant temperature; (5) Take out the reverseAfter the autoclave had cooled naturally to room temperature, the sample was removed from the autoclave and rinsed with deionized water (3 cycles). And then placing the sample in a liquid nitrogen solution, rapidly freezing and maintaining for 5 minutes, and vacuum freeze-drying at the temperature of-54 ℃ for 24 hours to obtain the graphene-based molybdenum disulfide composite aerogel.
Adsorption test and adsorption capacity, current density and electric double layer capacitance calculation were the same as in example 1.
The test results of this example are shown in Table 4.
TABLE 4 comparison of the gel adsorption performance and Hydrogen evolution performance of the molybdenum disulfide graphene aerogel prepared by the invention with the existing composite gas
As can be seen from Table 4, the adsorption capacity, the current density and the double-layer capacitance of the molybdenum disulfide graphene aerogel prepared by the method are higher than those of the prior reported composite gas gelation. According to the invention, no additional reducing agent is required in the process of preparing the molybdenum disulfide graphene aerogel, and the prepared aerogel has better adsorption performance and hydrogen evolution performance than those of the reported composite gas gelation.
Claims (6)
1. The method for preparing the molybdenum disulfide graphene aerogel by utilizing the low-temperature plasma is characterized by comprising the following steps of:
1) Mixing water and graphite powder, stirring at a rotating speed of 60-180 rpm, and simultaneously carrying out low-temperature plasma irradiation for 0.5-1.5 hours to obtain graphene slurry;
2) Dropwise adding sulfuric acid into the graphene slurry to obtain acidic graphene slurry;
3) Adding molybdenum trioxide into the acidic graphene slurry, stirring at a rotating speed of 60-180 rpm, and simultaneously carrying out low-temperature plasma irradiation for 0.5-1.5 hours to obtain molybdenum disulfide graphene slurry;
4) Centrifuging the molybdenum disulfide graphene slurry, carrying out solid-liquid separation, and then carrying out vacuum freeze drying on a solid part to obtain molybdenum disulfide graphene aerogel;
the action voltage of the low-temperature plasma irradiation in the step 1) is 20-50 KV, and the action atmosphere is oxygen;
and 3) the action voltage of the low-temperature plasma irradiation in the step is 20-50 KV, and the action atmosphere is argon.
2. The method for preparing the molybdenum disulfide graphene aerogel by utilizing the low-temperature plasma according to claim 1, wherein the liquid-solid ratio of water to graphite powder in the step 1) is 1-3:1 mL/mg.
3. The method for preparing the molybdenum disulfide graphene aerogel by utilizing the low-temperature plasma according to claim 1, wherein the concentration of sulfuric acid in the step 2) is 1-2M.
4. The method for preparing the molybdenum disulfide graphene aerogel by utilizing the low-temperature plasma, which is disclosed in claim 1, is characterized in that the mass ratio of the molybdenum trioxide to the acidic graphene slurry in the step 3) is 5-15:100.
5. The method for preparing the molybdenum disulfide graphene aerogel by utilizing the low-temperature plasma according to claim 1, wherein the vacuum freeze-drying temperature in the step 4) is-90 to-10 ℃, and the vacuum freeze-drying time is 6-18 hours.
6. The molybdenum disulfide graphene aerogel obtained by the preparation method of any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010159520.2A CN111268732B (en) | 2020-03-09 | 2020-03-09 | Method for preparing molybdenum disulfide graphene aerogel by using low-temperature plasma and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010159520.2A CN111268732B (en) | 2020-03-09 | 2020-03-09 | Method for preparing molybdenum disulfide graphene aerogel by using low-temperature plasma and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111268732A CN111268732A (en) | 2020-06-12 |
| CN111268732B true CN111268732B (en) | 2023-04-25 |
Family
ID=70994576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010159520.2A Active CN111268732B (en) | 2020-03-09 | 2020-03-09 | Method for preparing molybdenum disulfide graphene aerogel by using low-temperature plasma and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111268732B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112569914B (en) * | 2020-12-11 | 2023-02-28 | 常熟理工学院 | Method for preparing uranium adsorbent by using ammonia water and acrylonitrile wastewater of coking plant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807212A (en) * | 2012-08-28 | 2012-12-05 | 武汉大学 | Method for preparing graphene at low temperature |
| CN104658764A (en) * | 2015-02-06 | 2015-05-27 | 浙江大学 | Graphene aerogel three-component compound electrode material of supercapacitor as well as preparation and application |
| CN104773725A (en) * | 2015-04-09 | 2015-07-15 | 厦门大学 | Method for preparing graphene by using low-temperature plasmas |
| CN107394127A (en) * | 2017-06-13 | 2017-11-24 | 陕西科技大学 | A kind of molybdenum disulfide graphene aerogel electrode material preparation method |
| CN110655066A (en) * | 2019-09-30 | 2020-01-07 | 中科院合肥技术创新工程院 | Method for preparing platinum-graphene-molybdenum sulfide composite material by low-temperature plasma |
-
2020
- 2020-03-09 CN CN202010159520.2A patent/CN111268732B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807212A (en) * | 2012-08-28 | 2012-12-05 | 武汉大学 | Method for preparing graphene at low temperature |
| CN104658764A (en) * | 2015-02-06 | 2015-05-27 | 浙江大学 | Graphene aerogel three-component compound electrode material of supercapacitor as well as preparation and application |
| CN104773725A (en) * | 2015-04-09 | 2015-07-15 | 厦门大学 | Method for preparing graphene by using low-temperature plasmas |
| CN107394127A (en) * | 2017-06-13 | 2017-11-24 | 陕西科技大学 | A kind of molybdenum disulfide graphene aerogel electrode material preparation method |
| CN110655066A (en) * | 2019-09-30 | 2020-01-07 | 中科院合肥技术创新工程院 | Method for preparing platinum-graphene-molybdenum sulfide composite material by low-temperature plasma |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111268732A (en) | 2020-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kondratowicz et al. | Tailoring properties of reduced graphene oxide by oxygen plasma treatment | |
| CN109830659B (en) | Te-doped MXene material and preparation method thereof | |
| Liu et al. | (0D/3D) MoS2 on porous graphene as catalysts for enhanced electrochemical hydrogen evolution | |
| CN107399729A (en) | A kind of bimetallic MOFs nitrogenous graphitized carbon material | |
| Liu et al. | Direct synthesis of FeS/N-doped carbon composite for high-performance sodium-ion batteries | |
| Chen et al. | A facile self-catalyzed CVD method to synthesize Fe3C/N-doped carbon nanofibers as lithium storage anode with improved rate capability and cyclability | |
| CN104103821B (en) | The preparation method of silicon-carbon cathode material | |
| CN111477891B (en) | Preparation method of nitrogen-doped porous hollow carbon sphere compound with low platinum loading capacity, product and application thereof | |
| CN105366664A (en) | Production method for sulfur-doped graphene | |
| CN109390561A (en) | A kind of lead negative and preparation method thereof of graphene lead carbon battery | |
| CN112479199A (en) | Preparation method of nitrogen, phosphorus and oxygen co-doped porous graphitized carbon nanosheet | |
| Xu et al. | A highly efficient and free-standing copper single atoms anchored nitrogen-doped carbon nanofiber cathode toward reliable Li–CO2 batteries | |
| CN111276684A (en) | Preparation method and application of carbon-coated composite material | |
| CN111268732B (en) | Method for preparing molybdenum disulfide graphene aerogel by using low-temperature plasma and product thereof | |
| CN103451670A (en) | Electrochemical preparation method of graphene | |
| Wang et al. | Surface modification of hollow capsule by Dawson-type polyoxometalate as sulfur hosts for ultralong-life lithium-sulfur batteries | |
| Dai et al. | Si@ SnS2–Reduced Graphene Oxide Composite Anodes for High‐Capacity Lithium‐Ion Batteries | |
| CN108840679A (en) | A kind of preparation method of atomic crystal boron doping carbon material | |
| Li et al. | Fabrication of Core‐Shell Ni2P@ N, P− Co‐Doped Carbon/Reduced Graphene Oxide Composite as Anode Material for Lithium‐and Sodium‐Ion Batteries | |
| CN112010279A (en) | Preparation method of three-dimensional porous carbon aerogel material and application of three-dimensional porous carbon aerogel material in lithium-sulfur battery | |
| Ma et al. | One-step ultrafast laser induced synthesis of strongly coupled 1T-2H MoS2/N-rGO quantum-dot heterostructures for enhanced hydrogen evolution | |
| Ding et al. | Atomically dispersed Fe–N x species within a porous carbon framework: an efficient catalyst for Li–CO 2 batteries | |
| Yuan et al. | Hybrid Sub‐1 nm Nanosheets of Co‐assembled MnZnCuOx and Polyoxometalate Clusters as Anodes for Li‐ion Batteries | |
| Wan et al. | Bioprocess-inspired preparation of silica with varied morphologies and potential in lithium storage | |
| CN113104835B (en) | Two-dimensional silicon carbon nano sheet negative electrode material and preparation method thereof |
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 |