CN110512232B - Self-supporting transition metal sulfide film electro-catalytic electrode and preparation method thereof - Google Patents
Self-supporting transition metal sulfide film electro-catalytic electrode and preparation method thereof Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 100
- -1 transition metal sulfide Chemical class 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011888 foil Substances 0.000 claims abstract description 60
- 239000010408 film Substances 0.000 claims abstract description 51
- 239000010409 thin film Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000003624 transition metals Chemical class 0.000 claims abstract description 35
- 239000010453 quartz Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910004211 TaS2 Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
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- 238000003491 array Methods 0.000 description 2
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- 241000446313 Lamella Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 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
-
- 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
-
- 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
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
-
- 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
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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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 self-supporting transition metal sulfide film electrocatalysis electrode and a preparation method thereof, belonging to the technical field of electrocatalysis electrode materials. The electrode comprises an active material and a metal substrate, wherein the active material is a transition metal sulfide thin film, the metal substrate is a transition metal foil, and the active material grows on the metal substrate in situ. The invention also discloses a preparation method of the self-supporting transition metal sulfide thin film electro-catalysis electrode, which is a surface-assisted chemical vapor transport method: and sealing the transition metal foil and the sulfur powder in a quartz tube in vacuum to perform one-step reaction, and growing a transition metal sulfide film on the surface of the metal foil in situ. The method has the following technical effects: the transition metal foil not only provides a metal source, but also is a substrate for growing the nucleation of the film, and the in-situ growth ensures that the transition metal foil and the film are tightly combined; the film is uniform and pure and has good crystallinity by reaction in vacuum. The obtained self-supporting electro-catalytic electrode has the advantages of high catalytic activity, good conductivity, strong stability and simple preparation.
Description
Technical Field
The invention relates to the field of electrocatalytic electrode materials, in particular to a self-supporting transition metal sulfide thin film electrocatalytic electrode and a preparation method thereof.
Background
The hydrogen energy is a renewable and pollution-free green energy source, has the advantages of high combustion value, wide application range, safety, environmental protection and the like, and the development and the application of the hydrogen energy have important social significance and profound influence on solving the problems of energy shortage and environmental deterioration at present. Among various hydrogen production methods, electrocatalytic water decomposition is an efficient and sustainable hydrogen production technology, has the advantages of low carbon emission, high product purity, simple process and the like, and is the most suitable for the current hydrogen production methodsThe most well-established electrocatalysts with high efficiency are platinum-based noble metal materials, but the high cost and scarcity severely limit the wide application of such electrode materials. The industrial hydrogen production urgently needs to find the electrocatalytic material with rich content on the earth to replace the platinum-based noble metal material, so that the cost is reduced, and simultaneously, the high catalytic activity and the high stability are maintained. At present, those skilled in the art have sought various substitutes with high catalytic activity and low price, such as transition metal sulfide, transition metal selenide, transition metal carbide, etc., for the problem. Wherein the transition metal sulfide (e.g. WS)2、MoS2、TaS2Or NbS2) The material has a unique laminated structure, adjustable electronic performance and abundant active sites at the edges or the center of a lamella, can be used as a catalytic center, and is an electro-catalytic material with great potential.
However, the application of the transition metal sulfide in the field of electrocatalysis still has some problems. On one hand, most of the existing transition metal sulfide electrode materials are powder, and are prepared by methods such as solvothermal, chemical vapor deposition, chemical stripping and the like, and a conductive agent and a polymer binder are required to be additionally added in the preparation process of the transition metal sulfide powder, so that the cost is increased, the complexity of the preparation process of the electrode is improved, and a plurality of adverse factors such as resistance improvement, electrode conductivity reduction, active site covering, mass transfer inhibiting and the like can be generated due to the introduction of the binder. In the reaction process, the problems of weak bonding force between the active material and the substrate, easy shedding, limitation of the load capacity of the active material and the like exist, so that the catalytic performance of the electrode material is difficult to give full play. On the other hand, the preparation of the transition metal sulfide into the self-supporting electrocatalytic electrode has the obvious advantages of effectively reducing the falling of the active material and avoiding the introduction of the conductive agent and the binder, but the preparation method of the transition metal sulfide self-supporting electrocatalytic electrode reported at present is still less, and the carbon material is mostly adopted as the conductive substrate, so that the bonding force with the active material is lower. Most of the preparation methods are two-step methods, such as dip coating, annealing treatment, hydrothermal treatment and vulcanization treatment, and the product is poor in purity, complex and time-consuming.
Therefore, in the field of using transition metal sulfide as an electrocatalyst, there is a need to provide a simple surface-assisted method for preparing a novel transition metal sulfide self-supporting electrode, which has the advantages of low cost, simple preparation, pure product, close bonding of active materials and a substrate, and high and stable electrocatalytic performance.
Disclosure of Invention
One of the purposes of the invention is to provide a self-supporting transition metal sulfide thin film electrocatalytic electrode, which can ensure that transition metal sulfide grows in situ on a metal substrate and is tightly combined with the substrate, thereby reducing contact resistance and improving the conductivity and the use stability of the electrode; the full exposure of the active sites of the transition metal sulfide can be ensured, and the contact area of the active material and the electrolyte is increased, so that the electrocatalytic activity of the electrode is obviously improved.
Another object of the present invention is to provide a method for preparing an electrocatalytic electrode of a self-supporting transition metal sulfide thin film, which can simplify the preparation process of the electrocatalytic electrode and effectively reduce the cost; and the transition metal sulfide film can be ensured to grow on the surface of the transition metal foil in situ and can be directly used as a self-supporting electrode for electrocatalytic reaction.
The technical scheme of the invention is as follows:
a self-supporting transition metal sulfide thin film electrocatalytic electrode, characterized by: the electrode comprises an active material and a metal substrate, wherein the active material is a transition metal sulfide thin film, and the metal substrate is a transition metal foil; the active material grows on the surface of the metal substrate in situ, and the active material and the metal substrate are tightly combined to form a self-supporting structure.
Preferably, the active material is WS2、MoS2、TaS2Or NbS2The film is 1-40 mu m thick and consists of nanosheets 30-1000 nm in transverse dimension.
Preferably, the metal substrate is tungsten foil, molybdenum foil, tantalum foil or niobium foil, and the thickness of the substrate is 0.1-0.2 mm.
The invention provides a preparation method of the self-supporting transition metal sulfide thin film electro-catalysis electrode, which is characterized by comprising the following steps:
1) vacuum sealing a transition metal foil and sulfur powder in a quartz tube, wherein the mass ratio of the transition metal foil to the sulfur powder is 1: 0.001 to 0.05, vacuum degree of 10-2～10-6Pa；
2) And placing the quartz tube in a tubular furnace which is preheated for reaction, wherein the reaction temperature is 500-1100 ℃, the reaction time is 2-50 min, and after the reaction is finished, quickly pushing the quartz tube out of the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting transition metal sulfide thin film electro-catalytic electrode.
Preferably, the transition metal foil in step 1) is a tungsten foil, a molybdenum foil, a tantalum foil or a niobium foil; the mass ratio of the transition metal foil to the sulfur powder is 1: 0.002-0.02; the vacuum degree is 10-4～10-5Pa。
Preferably, the reaction temperature in the step 2) is 600-1000 ℃, and the reaction time is 10-20 min.
The invention has the following advantages and prominent technical effects: firstly, the transition metal sulfide thin film grows on the surface of the transition metal foil in situ and can be directly used as a self-supporting electrode for electrocatalytic reaction, the preparation process of the electrode is simplified, and a conductive agent and a binder do not need to be additionally introduced. The in-situ growth can ensure the close combination of the active material and the metal substrate, reduce the contact resistance, and thus obviously improve the conductivity and the use stability of the electrode. The transition metal sulfide thin film prepared by the invention is composed of uniform nanosheets, so that the unique structure can ensure that the active sites of the transition metal sulfide are fully exposed, and the contact area of the active material and the electrolyte is increased, thereby remarkably improving the electrocatalytic activity of the electrode. The preparation method adopted by the invention is a one-step surface-assisted chemical vapor transport method, and the transition metal foil is adopted to provide a metal source for synthesizing the transition metal sulfide and also used as a substrate for nucleation and growth of the transition metal sulfide, so that the method is a foundation and a precondition for obtaining the self-supporting electrode. The reaction is carried out under the vacuum condition, the transition metal sulfide thin film is uniform and clean, has good crystallinity, and completely covers the surface of the metal foil, and the uniform large-area batch production can be realized.
Drawings
FIG. 1 is a diagram of a self-supporting MoS as described in example 1 of the present invention2Microstructural characterization of thin film electrocatalytic electrodes.
FIG. 2 shows a self-supporting TaS according to embodiment 5 of the present invention2Microstructural characterization of thin film electrocatalytic electrodes.
FIG. 3 is the self-supporting NbS in embodiment 6 of the invention2Microstructural characterization of thin film electrocatalytic electrodes.
FIG. 4 is a diagram of a self-supporting WS according to embodiment 13 of the present invention2Microstructural characterization of thin film electrocatalytic electrodes.
FIG. 5 is a schematic view of a self-supporting WS according to embodiment 13 of the present invention2The electro-catalysis hydrogen production performance diagram of the thin film electro-catalysis electrode.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, but the embodiments of the present invention are not limited thereto.
The invention provides a self-supporting transition metal sulfide film electro-catalytic electrode, which takes a transition metal sulfide film as an active material and a transition metal foil as a metal substrate, wherein the active material is uniformly covered on the surface of the metal substrate and is tightly combined to form a self-supporting structure.
The active material is a transition metal sulfide thin film, preferably WS2、MoS2、TaS2Or NbS2The film is 1-40 mu m in thickness and is composed of nanosheets 30-1000 nm in transverse dimension, and microstructure representation diagrams are shown in figures 1-4. The thickness of the transition metal sulfide film is mainly regulated and controlled by changing the mass ratio of the transition metal foil to the sulfur powder. Preferably, the film thickness is 5 to 20 μm. Too small a thickness results in too small an amount of active material, a decrease in the number of active sites, which is manifested as a decrease in electrocatalytic properties; if the thickness is too large, the loading amount increases, resulting in a decrease in the binding force of the active material to the substrate, a thin film may be peeled off from the substrate when the loading amount is too large,is not favorable for the stability of the electrocatalytic electrode in the test; the moderate thickness can ensure the use stability of the electrode and provide excellent electrocatalytic activity. The size of the nanosheet in the transition metal sulfide thin film can be regulated and controlled by coordinating various reaction conditions, and the smaller the size of the nanosheet is, the better the electrocatalytic performance is improved.
The metal substrate is a transition metal foil, a tungsten foil, a molybdenum foil, a tantalum foil or a niobium foil, and the thickness of the substrate is preferably 0.1-0.2 mm. The transition metal sulfide film grows in situ on the surface of the metal substrate to realize the tight combination of the transition metal sulfide film and the metal substrate, and can be integrally used as a self-supporting electrocatalytic electrode. The self-supporting structure can not only improve the conductivity and the use stability of the electrode, but also increase the loading amount of the active material.
The invention also provides a preparation method of the self-supporting transition metal sulfide thin film electro-catalysis electrode, a surface-assisted chemical vapor transport method, which specifically comprises the following steps:
step 1: and (6) sealing the tube in vacuum. And sealing the transition metal foil and the sulfur powder in a certain mass ratio in a quartz tube in vacuum. The transition metal foil is tungsten foil, molybdenum foil, tantalum foil or niobium foil, and the mass ratio of the transition metal foil to the sulfur powder is 1: 0.001 to 0.05, and a degree of vacuum after sealing of 10-2～10-6Pa. Step 2: preparing the transition metal sulfide film. And quickly placing the quartz tube sealed in vacuum into a tubular furnace preheated to a specific temperature, wherein the reaction temperature is 500-1100 ℃, and the reaction time is 2-50 min. And after the reaction is finished, quickly pushing the quartz tube out of the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting transition metal sulfide thin film electro-catalytic electrode.
In the step 1, the sulfur powder provides a sulfur source for synthesizing the transition metal sulfide, the transition metal foil provides a metal source for synthesizing the transition metal sulfide on one hand, and is also a substrate for nucleation and growth of the transition metal sulfide on the other hand, and the use of the metal foil is a basis and a precondition for obtaining the self-supporting transition metal sulfide thin film electro-catalysis electrode. The appearance and thickness of the transition metal sulfide film can be regulated and controlled by regulating the mass ratio of the transition metal foil to the sulfur powder. The smaller the mass ratio of the transition metal foil to the sulfur powder is, namely the more the sulfur powder is added, the higher the amount of the obtained transition metal sulfide film is, and the larger the thickness and the size of the nanosheet are; the larger the mass ratio of the transition metal foil to the sulfur powder is, i.e., the smaller the amount of the sulfur powder added, the lower the amount of the transition metal sulfide film obtained, and the smaller the thickness and the size of the nanosheet. Preferably, the mass ratio of the transition metal foil to the sulfur powder is 1: 0.002 to 0.02. The length and width of the metal foil are not limited in the present invention, and those skilled in the art can appropriately adjust the length and width according to the desired size and the size of the reaction apparatus.
In the step 1, it is preferable that the degree of vacuum of the quartz tube is in the range of 10-4～10-5Pa, the purity of the product can be ensured and is easy to achieve in actual operation.
In the step 2, the transition metal sulfide thin film is prepared by a surface-assisted chemical vapor transport method. The main reaction parameters involved are reaction temperature and reaction time, both of which have a great influence on the morphology and electrocatalytic performance of the transition metal sulfide thin film. The reaction temperature is too low, the reaction is slowly carried out, the amount of the obtained active material is too small, and the reaction cannot be fully carried out; if the reaction temperature is too high, the reaction is very fast, the size of the generated transition metal sulfide structure is obviously increased, the active surface area of the film is reduced, and the full exposure of active sites is not facilitated. The reaction time is too short, the reaction cannot be carried out completely, the sulfur powder cannot fully react with the transition metal foil, and the quartz tube has the residue of the sulfur powder; the reaction time is too long, and sufficient progress of the reaction can be ensured, but the transition metal sulfide also has a problem of an increase in the structural size and a decrease in the active surface area. In particular, three main reaction parameters, namely the element mass ratio, the reaction temperature and the reaction time, have a synergistic effect on the influence of the morphology and the performance of the product. Preferably, the transition metal sulfide thin film is preferably prepared under the following conditions: the vacuum degree of the quartz tube is within 10-4～10-5Pa, the mass ratio of the transition metal foil to the sulfur powder is 1: 0.002-0.02 deg.c, reaction temperature of 600-1000 deg.c and reaction time of 10-20 min. The transition metalThe sulfide thin film has the most appropriate structure, the electrocatalytic activity surface area of the structure is the largest, active sites of materials can be exposed as much as possible, the contact area with electrolyte is increased, and the electrocatalytic activity of the electrocatalytic electrode is further remarkably improved.
Several specific examples are given below:
example 1
(1) And (6) sealing the tube in vacuum. And sealing the molybdenum foil and the sulfur powder in a quartz tube in vacuum, wherein the thickness of the molybdenum foil is 0.1mm, and the mass ratio of the molybdenum foil to the sulfur powder is 1: 0.005 and 10 degrees of vacuum-4Pa。
(2) Preparation of MoS2A film. Quickly placing the quartz tube sealed in vacuum in a tubular furnace preheated to 1000 ℃, reacting for 10min, quickly pushing out the quartz tube from the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting MoS2A thin film electro-catalytic electrode.
Self-supporting MoS in this example2The microstructure of the thin film electro-catalytic electrode is characterized as shown in FIG. 1, MoS2The thickness of the film is about 5 mu m, the film is uniformly covered on the surface of the molybdenum foil and consists of nanosheets with uniform sizes, the transverse size of the nanosheets is about 100nm, the exposure of active sites of the nanosheets can be promoted, and the electrocatalytic performance of the nanosheets is greatly improved.
Example 2
The only difference from example 1 is that the degree of vacuum of the quartz tube is 10-2Pa. Self-supporting MoS in this example2The surface of the thin film electro-catalytic electrode still consists of the nanosheets, but is less uniform than in example 1, and a higher vacuum level will help to improve the uniformity and cleanliness of the product.
Example 3
The only difference from example 1 is that the degree of vacuum of the quartz tube is 10-6Pa. Self-supporting MoS in this example2The thin film electro-catalytic electrode is covered on the surface of the substrate very uniformly, and the high vacuum degree is beneficial to preparing products with uniform purity and high crystallinity, but the vacuum degree which is too high is not easy to realize in practical operation.
Example 4
(1) And (6) sealing the tube in vacuum. And (2) vacuum-sealing tantalum foil and sulfur powder in a quartz tube, wherein the thickness of the tantalum foil is 0.2mm, and the mass ratio of the tantalum foil to the sulfur powder is 1: 0.05 and a vacuum degree of 10-5Pa。
(2) Preparation of TaS2A film. Quickly placing the quartz tube sealed in vacuum in a tubular furnace preheated to 1000 ℃, reacting for 20min, quickly pushing out the quartz tube from the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting TaS2A thin film electro-catalytic electrode.
Self-supporting TaS in this example2The thickness of the film is about 40 mu m, the film is composed of nano-sheet arrays with larger sizes, and the film is not beneficial to self-supporting TaS2The film fully exposes the active sites, thereby limiting the performance of the electrocatalytic hydrogen production performance. The produced TaS is generated due to the large addition of the sulfur element2The film is thick, the reaction is not completely carried out, and a small amount of sulfur remains in the quartz tube after the reaction is finished.
Example 5
The difference from the example 4 is only that the mass ratio of the tantalum foil to the sulfur powder is 1: 0.002. self-supporting TaS in this example2The microstructure of the thin film electro-catalytic electrode is shown in FIG. 2, TaS2The film is composed of nanosheet arrays with uniform sizes and vertical orientations, and the thickness of the film is about 4 micrometers. Compared with example 4, the addition amount of sulfur powder is reduced in this example, so that TaS2The thickness of the film is reduced, and the size of the nano-sheet is obviously reduced.
Example 6
(1) And (6) sealing the tube in vacuum. And sealing the niobium foil and the sulfur powder in a quartz tube in vacuum, wherein the thickness of the niobium foil is 0.1mm, and the mass ratio of the niobium foil to the sulfur powder is 1: 0.02 and 10 degrees of vacuum-5Pa。
(2) Preparation of NbS2A film. Quickly placing the quartz tube sealed in vacuum in a tubular furnace preheated to 1000 ℃, reacting for 10min, quickly pushing out the quartz tube from the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting NbS2A thin film electro-catalytic electrode.
Self-supporting NbS in this example2The microstructure of the thin film electro-catalytic electrode is characterized asShown in FIG. 3, NbS2The thin film is uniformly covered on the surface of the niobium foil, has the thickness of about 20 mu m, and is formed by stacking nanosheets with the transverse dimension of about 100 nm.
Example 7
(1) And (6) sealing the tube in vacuum. And (2) sealing tungsten foil and sulfur powder in a quartz tube in vacuum, wherein the thickness of the tungsten foil is 0.1mm, and the mass ratio of the tungsten foil to the sulfur powder is 1: 0.005 and 10 degrees of vacuum-5Pa。
(2) Preparation of WS2A film. Quickly placing the quartz tube sealed in vacuum in a tubular furnace preheated to 600 ℃, reacting for 10min, quickly pushing out the quartz tube from the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting WS2A thin film electro-catalytic electrode.
Self-supporting WS in this embodiment2The thin film is uniformly covered on the surface of the tungsten foil, the thickness of the thin film is about 10 mu m, the thin film consists of nanoclusters, each nanocluster is formed by stacking thinner nanosheets, and the obtained WS2The film has a unique multilevel structure.
Example 8
The only difference from example 7 is that the reaction temperature is 500 ℃. Self-supporting WS in this embodiment2The film is still composed of nanoclusters, each of which is in turn formed by stacking of fine nanosheets. In this example, the size of the obtained nanoclusters was reduced to about 30nm due to the reduction in reaction temperature, as compared to example 7.
Example 9
The only difference from example 7 is that the reaction temperature is 1100 ℃. In this example, the size of the obtained nanoclusters becomes large due to the high reaction temperature, and the obvious adhesion phenomenon occurs between clusters, which is disadvantageous to WS in comparison with example 72The exposure of the active sites of the membrane, in turn, reduces its electrocatalytic properties.
Example 10
The only difference from example 7 is that the reaction time is 2 min. Compared with example 7, in this example, the size of the obtained nanoclusters is significantly reduced and the film thickness is reduced to 3 μm due to the shortened reaction time, but sulfur powder remains in the quartz tube and the reaction cannot be completely performed.
Example 11
The only difference from example 7 is that the reaction time was 50 min. Self-supporting WS in this embodiment2The film thickness is about 10 μm, and still consists of uniform nanoclusters, each nanocluster being formed by stacking fine nanosheets. The nanoclusters obtained in this example tend to have a larger size than in example 7.
Example 12
The difference from example 7 is only that the mass ratio of the tungsten foil to the sulfur powder is 1: 0.001. in contrast to example 7, the self-supporting WS obtained in this example2The nanocluster size of the thin film is obviously reduced, the amount of the obtained active material is also obviously reduced due to the reduction of the addition amount of the sulfur powder, and the thickness of the thin film is only 3 microns. On one hand, the reduction of the size of the nano structure can increase the number of active sites; on the other hand, a decrease in the amount of active material significantly decreases the number of active sites, and thus compared to the self-supporting WS of example 72Thin film electrodes, ultimately exhibiting a decrease in electrocatalytic performance.
Example 13
(1) And (6) sealing the tube in vacuum. And (2) sealing tungsten foil and sulfur powder in a quartz tube in vacuum, wherein the thickness of the tungsten foil is 0.1mm, and the mass ratio of the tungsten foil to the sulfur powder is 1: 0.01, vacuum degree of 10-5Pa。
(2) Preparation of WS2A film. Quickly placing the quartz tube sealed in vacuum in a tubular furnace preheated to 600 ℃, reacting for 10min, quickly pushing out the quartz tube from the tubular furnace, and naturally cooling to room temperature to obtain the self-supporting WS2A thin film electro-catalytic electrode.
Self-supporting WS in this embodiment2A microstructure characterization of the thin film electro-catalytic electrode is shown in FIG. 4, WS2The film has a thickness of about 20 μm and consists of clusters of about 50nm each of which consists of WS of finer size2And the nano sheets are stacked. In comparison with example 7, the amount of sulfur added in this example was increased, and the sizes of the nanoclusters and nanosheets were increased, but WS was also increased2The thickness of the film increases.
Self-supporting WS in this embodiment2The film electro-catalysis electrode is used as a working electrode for testing hydrogen produced by electro-catalysis decomposition, a three-electrode system is adopted in the test, a Pt sheet is used as a counter electrode, a saturated Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.5M H2SO4And the experimental temperature is about 25 ℃, and high-purity argon is continuously introduced and magnetic stirring is carried out in the testing process. Resulting self-supporting WS2The linear sweep voltammogram of the thin film electro-catalytic electrode is shown in FIG. 5, self-supporting WS2When the film electro-catalytic electrode is used for electrolyzing water to produce hydrogen, the water concentration reaches-50 mA/cm2The current density and the overpotential of the high-voltage direct current are only-0.23V, and the high-voltage direct current has excellent performance of producing hydrogen by electrocatalytic decomposition of water.
With reference to examples 1 to 13, the following conclusions can be drawn: the transition metal sulfide thin film is prepared by adopting a surface-assisted chemical vapor transport method, the difference of reaction conditions and the type of the transition metal foil brings about larger difference in product appearance, but the obtained product transition metal sulfide is a thin film uniformly covering the surface of the transition metal foil, consists of uniform and consistent nano structures, grows on the transition metal foil in situ and is tightly combined with a substrate.
In combination with examples 1, 2 and 3, the following conclusions can be drawn: the vacuum degree of the quartz tube mainly affects the uniformity and cleanliness of the transition metal sulfide film. The moderate vacuum degree can ensure the uniformity and the cleanliness of the product and is easy to realize in the actual operation.
In combination with examples 4 and 5, 7, 12 and 13, the following conclusions can be drawn: with the increase of the addition amount of the sulfur powder, the thickness of the film is increased, and the size of the transition metal sulfide nanosheet also tends to be larger.
In combination with examples 7, 8 and 9, the following conclusions can be drawn: the shape of the transition metal sulfide film can be regulated and controlled by adjusting the reaction temperature, and the nanostructure with smaller size can be obtained at lower reaction temperature, so that the bonding among the nanostructures is reduced.
In combination with examples 7, 10 and 11, the following conclusions can be drawn: the reaction time also has great influence on the product, the reaction time is short, the reaction can not be completely carried out, and the problems of large structure size of the transition metal sulfide and reduced active surface area can be caused if the reaction time is too long.
Therefore, when the surface-assisted chemical vapor transport method is adopted to prepare the self-supporting transition metal sulfide film electro-catalytic electrode, the vacuum degree of the quartz tube mainly influences the uniformity and cleanliness of the product, three main reaction parameters, namely the element mass ratio, the reaction temperature and the reaction time, have a synergistic effect on the appearance and performance of the product, and the preparation of the self-supporting electrode with high catalytic performance can be realized through proper reaction parameters. In practical operation, the transition metal foil species are combined to determine specific reaction parameters. Finally, the prepared electro-catalytic electrode can be used for electro-catalytic hydrogen production, super capacitors and batteries.
The above is a self-supporting transition metal sulfide thin film electrocatalytic electrode and a preparation method thereof provided by the present invention, and the present invention is explained in detail by specific examples. It should be noted that the above-mentioned embodiments are not intended to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope covered by the present invention.
Claims (5)
1. A method of making a self-supporting transition metal sulfide thin film electrocatalytic electrode, characterized in that the method comprises the steps of:
1) vacuum sealing a transition metal foil and sulfur powder in a quartz tube, wherein the transition metal foil is a tungsten foil, a molybdenum foil, a tantalum foil or a niobium foil, and the thickness of the transition metal foil is 0.1-0.2 mm; the mass ratio of the transition metal foil to the sulfur powder is 1: 0.001 to 0.05, vacuum degree of 10-2～10-6Pa；
2) Placing the quartz tube in a tubular furnace which is preheated for reaction, wherein the reaction temperature is 500-1100 ℃, the reaction time is 2-50 min, after the reaction is finished, rapidly pushing the quartz tube out of the tubular furnace, and naturally cooling to room temperature to obtain a self-supporting transition metal sulfide film electro-catalytic electrode, wherein the electro-catalytic electrode is formed by in-situ growth of a transition metal sulfide film on the surface of a metal substrate; sulfiding of the transition metalThe object film is WS2、MoS2、TaS2Or NbS2The film is 1-40 mu m thick and consists of nanosheets 30-1000 nm in transverse dimension.
2. The preparation method according to claim 1, wherein the mass ratio of the transition metal foil to the sulfur powder is 1: 0.002 to 0.02.
3. The method according to claim 1, wherein the degree of vacuum in the step 1) is 10-4～10- 5Pa。
4. The method according to claim 1, wherein the reaction temperature in the step 2) is 600 to 1000 ℃.
5. The preparation method according to claim 1, wherein the reaction time in the step 2) is 10 to 20 min.
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