CN108636427B - Molybdenum disulfide-nitrogen sulfur doped graphite foil composite nanomaterial and preparation method thereof - Google Patents
Molybdenum disulfide-nitrogen sulfur doped graphite foil composite nanomaterial and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011888 foil Substances 0.000 title claims abstract description 50
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 47
- 239000010439 graphite Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- TZPQFOBHHGBRNC-UHFFFAOYSA-N [S].[N].[Mo](=S)=S Chemical compound [S].[N].[Mo](=S)=S TZPQFOBHHGBRNC-UHFFFAOYSA-N 0.000 title abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004108 freeze drying Methods 0.000 claims description 22
- 229910052961 molybdenite Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101100008048 Caenorhabditis elegans cut-4 gene Proteins 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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- B01J35/33—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A process for preparing the Mo disulfide-N-S doped graphite foil as the composite nano material of Mo disulfide, N-S and N-S includes such steps as preparing graphite foil, HNO3、H2SO4The method comprises the following steps of taking ammonium tetrathiomolybdate, thiourea, oxalic acid and ultrapure water as raw materials, and respectively carrying out the steps of preparation of a nitrogen and sulfur atom doped graphite oxide foil, hydrothermal synthesis reaction, cleaning, drying and the like. The raw materials are simple and easy to obtain, the composite material is obtained through oxidation and hydrothermal processes, the whole experimental process is simple, the operation is convenient, the large-scale production of the product is easy to realize, the product can be recovered by 100% in the using process, the obtained molybdenum disulfide-nitrogen-sulfur doped graphite oxide foil has excellent flexibility, the molybdenum disulfide grows on the graphite foil in an epitaxial growth mode, the product uniformity is good, and the composite material has a good catalytic effect on the electrocatalytic hydrogen evolution. In addition, the material is expected to have good application in the aspects of flexible batteries, flexible sensors and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic nano materials and energy development and storage, and particularly relates to an electrocatalytic hydrogen evolution composite nano material and a preparation method thereof.
Background
With the rapid expansion of the population and the rapid development of the industry, energy problems have become the first problems affecting human production and life. In order to solve the global energy shortage problem, people pay more and more attention to hydrogen production by electrochemically decomposing water. Noble metals such as platinum (Pt) and its alloys are currently the most commonly used electrocatalytic hydrogen production catalysts due to low potential and high electrochemical stability in acidic solutions. However, it has disadvantages of high cost and scarce resources, so that its practical application is hindered. Therefore, the research of non-noble metal catalysts with high performance and high cost performance attracts the attention of the majority of scientific researchers.
In recent years, nanostructured molybdenum disulfide, both theoretical and experimental studies, has proven its usefulness as HER electrocatalyst with large specific surface area, complex structure and many edge unsaturation. But its poor conductivity and stability limit the catalytic efficiency. To combine the superior properties of some materials, researchers have included MoS2Complexation with Carbon Nanotubes (CNTs) and graphene to improve MoS2The composite material becomes a catalyst with effective HER as the problems of poor conductivity and poor stability of the electro-catalytic hydrogen evolution catalyst. Doping with nitrogen, sulfur, boron and oxygen has also been reported, since the doped catalyst is more active than the conventional catalyst. Where nitrogen and sulfur doping would enhance HER activity significantly because atomic doping can modulate the electronic energy levels to enhance chemical activity. The epitaxial growth can ensure the formation of atomic-level bonds between materials, effectively promote the transfer of charges and improve the electrocatalytic performance of the materials.
Up to now, molybdenum disulfide has been improved by preparing various molybdenum disulfide nanocomposites, such as carbon fiber-molybdenum disulfide composite, graphene-molybdenum disulfide composite, etc. Although the method is many, the method still has some defects, which mainly comprise that the experimental process is complex and large-scale production is not easy to form; in order to obtain high electrochemical performance, the obtained product is usually nano powder, so that the recovery rate of a sample in the use process is low, and the requirement of a large-area flexible electrochemical device is difficult to meet; however, if the nano material is loaded on a substrate such as nickel foam, etc., although the electrode requirement of large area can be realized, the product has poor flexibility, poor catalytic effect on the electrocatalytic hydrogen evolution, poor stability of the catalytic process, and easy shedding of the catalyst from the substrate, the currently obtained molybdenum disulfide composite material still needs to improve the electrocatalytic hydrogen evolution performance, and the search for the electrocatalytic material which is cheap, environment-friendly and has high catalytic activity is the key of the electrocatalytic technology development.
Disclosure of Invention
The first purpose of the invention is to provide a MoS2the/NSGF electrocatalytic hydrogen evolution composite nano material.
The invention aims to provide a MoS2A preparation method of a/NSGF electrocatalytic hydrogen evolution composite nano material.
The purpose of the invention is realized by the following technical scheme:
MoS2the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized by comprising the following substances: MoS2(iv)/N, S-Graphene Foil, wherein the MoS2The weight percentage of the N is 5% -15%, the weight percentage of the N is 0.1% -1%, the weight percentage of the S is 0.1% -1%, and the weight percentage of the Graphene Foil is 84.8% -94.8%.
MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized in that the material is graphite foil and HNO3、H2SO4The method comprises the following steps of taking ammonium tetrathiomolybdate, thiourea, oxalic acid and ultrapure water as raw materials, and respectively carrying out the steps of preparation of a nitrogen and sulfur atom doped graphite oxide foil, hydrothermal synthesis reaction, cleaning, drying and the like.
Further, a MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized in that the preparation step of the graphite foil doped with nitrogen and sulfur atoms is to put the graphite foil into a container filled with HNO3And H2SO4The mixed solution of (1) is soaked and then washed with deionized water and ethanol.
Further, a MoS2NSGF electrocatalytic hydrogen evolution complexThe preparation method of the composite nano material is characterized in that in the preparation step of the graphite oxide foil doped with nitrogen and sulfur atoms, low-temperature freeze drying is needed after cleaning.
Further, a MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized in that the mass ratio of the graphite foil, the ammonium tetrathiomolybdate, the thiourea, the oxalic acid and the purified water is 0.2:0.35:0.5:0.189: 40.
Further, a MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized in that the hydrothermal synthesis reaction is carried out under the condition of introducing nitrogen.
Specifically, a MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized by comprising the following steps:
1. preparation of nitrogen and sulfur atom doped graphite oxide foil
Placing graphite foil in a container filled with HNO3And H2SO4Soaking in the mixed solution, heating by microwave, reacting while keeping the temperature, taking out the soaked graphite foil sample after the reaction is finished, respectively washing with more than 100ml of deionized water and absolute ethyl alcohol for 3-4 times, and then putting into a freeze drying oven for drying to obtain a nitrogen and sulfur doped graphite oxide foil sample; the HNO3And H2SO4The mixed solution is prepared by taking 65-68% of HNO by mass fraction3Solution and 96-98% of H by mass fraction2SO4Solution, according to volume ratio of 1: 3, mixing, wherein the reaction time is 12-48 hours; the microwave heating temperature is 80-85 ℃, and the microwave power is 300W; the freeze drying temperature is set to be-55 to-45 ℃, the vacuum degree is 10 to 50Pa, and the drying time is 24 to 48 hours;
2. hydrothermal synthesis reaction
Putting the nitrogen and sulfur atom graphite oxide foil sample obtained in the step 1, ammonium tetrathiomolybdate, thiourea, oxalic acid and ultrapure water into a reaction kettle, and carrying out hydrothermal synthesis under the condition of introducing nitrogen gas for reaction; the nitrogen pressure is 2-3 MPa, stirring is required in the reaction process, the stirring speed is 450-550 r/min, the temperature of the hydrothermal synthesis reaction is 210-230 ℃, and the reaction time is 12-48 h;
3. cleaning and drying
Cooling to 20-25 ℃, taking out, cleaning, and freeze-drying to obtain a sample; the cleaning is to lightly clamp the sample by using a pair of tweezers, then wash the sample by using more than 100ml of deionized water and absolute ethyl alcohol for 3-4 times respectively, after the cleaning is finished, put the sample into a freeze drying box for drying, wherein the freezing temperature is set to be-55 to-45 ℃, the vacuum degree is 10 to 50Pa, and the drying time is 24 to 48 hours.
The invention has the following beneficial effects:
the invention relates to a MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nanomaterial adopts a hydrothermal method as a preparation process, raw materials are simple and easy to obtain, the composite material is obtained through oxidation and hydrothermal processes, the whole experimental process is simple, the operation is convenient, the large-scale production of products is easy to realize, the products can be recovered by 100% in the using process, the obtained molybdenum disulfide-nitrogen-sulfur doped graphite oxide foil has excellent flexibility, the molybdenum disulfide grows on the graphite foil in an epitaxial growth mode, the product uniformity is good, and the preparation method has a good catalytic effect on electrocatalytic hydrogen evolution. In addition, the material is expected to have good application in the aspects of flexible batteries, flexible sensors and the like.
Drawings
Figure 1 is an XRD pattern of epitaxially grown molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Figure 2 is an SEM image (low magnification) of epitaxially grown molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Figure 3 is an SEM image (high magnification) of epitaxially grown molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Figure 4 is an SEM image (side) of a molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Figure 5 is a TEM image (front) of an epitaxially grown molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Figure 6 is a TEM image (side) of an epitaxially grown molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Figure 7 is a selected area diffraction pattern of epitaxially grown molybdenum disulfide-nitrogen sulfur doped graphite oxide foil prepared in example 1.
Fig. 8 is a graph of bending (flexibility) performance of example 1.
FIG. 9 is a distribution diagram of elements of example 1.
FIG. 10 is a graph of the electrocatalytic hydrogen production performance of example 1 (linear voltammetric scan).
FIG. 11 is a graph showing the electrocatalytic hydrogen production stability (constant voltage) of example 1.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure.
Example 1
Using a ruler to cut 4 pieces of GF (3 cm x 5 cm) (weight about 0.6 g) into pieces containing 15ml of 65% HNO3And 45mL98% H2SO4 Soaking the mixed solution for 24 hours, heating the mixed solution to 80 ℃ by using microwaves, wherein the microwave power is 300W, taking out the soaked graphite oxide foil after reaction, respectively washing the graphite oxide foil for 3 times by using 100ml of deionized water and absolute ethyl alcohol, and then putting the graphite oxide foil into a freeze drying box for drying, wherein the freeze drying temperature is-52 ℃, the vacuum degree is 10Pa, and the drying time is 36 hours.
Weighing 0.35g of ammonium tetrathiomolybdate, 0.5g of thiourea and 0.189g of oxalic acid, dissolving in 40ml of deionized water, stirring for 30min to obtain a uniform and transparent solution, pouring the mixed solution into a 60ml reaction kettle, adding 0.2g of graphite oxide foil, setting the stirring speed of the reaction kettle at 450 revolutions per minute, introducing nitrogen for protection (the nitrogen pressure is 3 MPa), and keeping the temperature at 210 ℃ for 48 h. And after the reaction is finished, taking out the reaction kettle, naturally cooling the reaction kettle to 25 ℃, respectively washing the obtained product with 100ml of deionized water and absolute ethyl alcohol for 4 times, then putting the product into a freeze drying box for drying, wherein the freeze drying temperature is-48 ℃, the vacuum degree is 10Pa, the drying time is 36 hours, and the sample is obtained after the drying is finished.
The characterization of the sample by the energy spectrum accessory of the spherical aberration transmission electron microscope shows that the elements of the sample are distributed very uniformly. The sample can be bent by more than 270 degrees and has good flexibility.
Experiment one: electrocatalytic performance testing of materials
The electrochemical test adopts a three-electrode system, and is tested by an AUTOLAB PGSTAT302N workstation, a sample prepared in the experiment is directly used as a working electrode after being cut into 0.5cm by 2cm, the area of the soaked electrolyte is 0.5cm by 1cm, a Pt sheet electrode is used as a counter electrode, and a silver/silver chloride electrode (Ag/AgCl) is used as a reference electrode. Electrochemical test electrolyte was 0.5M H2SO4And introducing nitrogen into the solution for 30min before the solution test to remove air in the electrolyte, wherein each electrode is kept in a static state during the test so as to be beneficial to obtaining accurate experimental data. The experimental results show that: the electrocatalytic hydrogen evolution initial voltage of the sample is 6 mVvs RHE, and the current density can reach 10 mA/cm when the overpotential is 30mV2Tafel is 66mVdec-1,
experiment two: hydrogen evolution stability test
The test was continued using the three-electrode system, and the measurement was carried out in the constant voltage mode, using 100,200 and 180mV voltages for examples 1-3, respectively, and a test time of 40000 seconds. The experimental result shows that the stability of the sample is tested for 40000 seconds under the constant voltage of 100mV, and the hydrogen evolution performance is only reduced by 2-3%.
Example 2
Using a ruler to cut 4 pieces of GF (3 cm x 5 cm) (weight about 0.6 g) into pieces containing 15ml of 68% HNO3And 45mL98% H2SO4 The mixed solution is soaked for 48 hours, the temperature is heated to 85 ℃ by microwaves, the microwave power is 300W, the soaked graphite oxide foil is taken out after reaction, the graphite oxide foil is respectively washed for 4 times by 100ml of deionized water and absolute ethyl alcohol and then is put into a freeze drying oven for drying, the freeze drying temperature is-48 ℃, the vacuum degree is 50Pa, and the drying time is 24 hours.
Weighing 0.35g of ammonium tetrathiomolybdate, 0.5g of thiourea and 0.189g of oxalic acid, dissolving in 40ml of deionized water, stirring for 30min to obtain a uniform and transparent solution, pouring the mixed solution into a 60ml reaction kettle, adding 0.2g of graphite oxide foil, setting the stirring speed of the reaction kettle at 500 r/min, introducing nitrogen for protection (the nitrogen pressure is 2 MPa), and keeping the temperature at 220 ℃ for 12 h. And after the reaction is finished, taking out the reaction kettle, naturally cooling the reaction kettle to 20 ℃, respectively washing the obtained product with 100ml of deionized water and absolute ethyl alcohol for 3 times, then putting the product into a freeze drying box for drying, wherein the freeze drying temperature is-52 ℃, the vacuum degree is 50Pa, the drying time is 24 hours, and the sample is obtained after the drying is finished.
The characterization of the sample by the energy spectrum accessory of the spherical aberration transmission electron microscope shows that the elements of the sample are distributed very uniformly. The sample can be bent by more than 270 degrees and has good flexibility. The electrocatalytic hydrogen evolution initial voltage of the sample is 10mVvs RHE, and the current density can reach 10 mA/cm when the overpotential is 39mV2And Tafel is 69 mVdec-1. The stability of the sample is tested at 100mV constant voltage for 40000 seconds, and the hydrogen evolution performance is reduced by 3-4%.
Example 3
Using a ruler to cut 4 pieces of GF (3 cm x 5 cm) (weight about 0.6 g) into pieces containing 15ml of 65% HNO3And 45mL98% H2SO4 Soaking the mixed solution for 36 hours, heating the mixed solution to 82 ℃ by using microwaves, wherein the microwave power is 300W, taking out the soaked graphite oxide foil after reaction, respectively washing the graphite oxide foil for 4 times by using 100ml of deionized water and absolute ethyl alcohol, and then putting the graphite oxide foil into a freeze drying box for drying, wherein the freeze drying temperature is-50 ℃, the vacuum degree is 30Pa, and the drying time is 36 hours.
Weighing 0.35g of ammonium tetrathiomolybdate, 0.5g of thiourea and 0.189g of oxalic acid, dissolving in 40ml of deionized water, stirring for 30min to obtain a uniform and transparent solution, pouring the mixed solution into a 60ml reaction kettle, adding 0.2g of graphite oxide foil, setting the stirring speed of the reaction kettle at 500 r/min, introducing nitrogen for protection (the nitrogen pressure is 3 MPa), and keeping the temperature at 230 ℃ for 36 h. And after the reaction is finished, taking out the reaction kettle, naturally cooling the reaction kettle to 25 ℃, respectively washing the obtained product with 100ml of deionized water and absolute ethyl alcohol for 4 times, then putting the product into a freeze drying oven for drying, wherein the freeze drying temperature is-50 ℃, the vacuum degree is 30Pa, the drying time is 36 hours, and the sample is obtained after the drying is finished.
The characterization of the sample by the energy spectrum accessory of the spherical aberration transmission electron microscope shows that the elements of the sample are distributed very uniformly. The sample can be bent by more than 270 degrees and has good flexibility. Electrocatalysis of samplesThe hydrogen evolution initial voltage is 19mVvs RHE, and the current density can reach 10 mA/cm when the overpotential is 48mV2And Tafel is 72 mVdec-1. The stability test of 40000 seconds is carried out on the sample under the constant voltage of 100mV, and the hydrogen evolution performance is reduced by 4-5%.
Claims (2)
1. MoS2The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized by comprising the following steps: it is made of graphite foil and HNO3、H2SO4The method comprises the following steps of taking ammonium tetrathiomolybdate, thiourea, oxalic acid and ultrapure water as raw materials, and respectively carrying out preparation, hydrothermal synthesis reaction, cleaning and drying of nitrogen and sulfur atom doped graphite oxide foil;
the method specifically comprises the following steps:
(1) preparation of nitrogen and sulfur atom doped graphite oxide foil
Placing graphite foil in a container filled with HNO3And H2SO4Soaking in the mixed solution, heating by microwave, reacting while keeping the temperature, taking out the soaked graphite foil sample after the reaction is finished, respectively washing with more than 100ml of deionized water and absolute ethyl alcohol for 3-4 times, and then putting into a freeze drying oven for low-temperature freeze drying to obtain a nitrogen and sulfur doped graphite oxide foil sample; the HNO3And H2SO4The mixed solution is prepared by taking 65-68 percent of HNO by mass fraction3Solution and 96-98% of H by mass fraction2SO4Solution, according to volume ratio of 1: 3, mixing, wherein the reaction time is 12-48 hours; the microwave heating temperature is 80-85 ℃, and the microwave power is 300W; the freeze drying temperature is set to be-55 to-45 ℃, the vacuum degree is 10 to 50Pa, and the drying time is 24 to 48 hours;
(2) hydrothermal synthesis reaction
Putting the nitrogen and sulfur atom graphite oxide foil sample in the step (1), ammonium tetrathiomolybdate, thiourea, oxalic acid and ultrapure water into a reaction kettle, and carrying out hydrothermal synthesis under the condition of introducing nitrogen gas for reaction; the nitrogen pressure is 2-3 MPa, stirring is required in the reaction process, the stirring speed is 450-550 r/min, the temperature of the hydrothermal synthesis reaction is 210-230 ℃, and the reaction time is 12-48 h;
(3) cleaning and drying
Cooling to 20-25 ℃, taking out, cleaning, and freeze-drying to obtain a sample; the cleaning is to lightly clamp the sample by using a pair of tweezers, then wash the sample for 3 to 4 times by using more than 100ml of deionized water and absolute ethyl alcohol respectively, and after the cleaning is finished, put the sample into a freeze drying oven for drying, wherein the freezing temperature is set to be-55 to-45 ℃, the vacuum degree is 10 to 50Pa, and the drying time is 24 to 48 hours;
the composite nano material consists of the following substances: wherein the MoS2The mass percentage content is 5-15%; the NSGF is a nitrogen-sulfur doped graphite Foil, the mass percentage of N is 0.1-1%, the mass percentage of S is 0.1-1%, and the mass percentage of Graphene Foil is 84.8-94.8%.
2. A MoS according to claim 12The preparation method of the/NSGF electrocatalytic hydrogen evolution composite nano material is characterized by comprising the following steps: the mass ratio of the graphite foil to the ammonium tetrathiomolybdate to the thiourea to the oxalic acid to the ultrapure water is 0.2:0.35:0.5:0.189: 40.
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