CN108325540B - Tungsten disulfide/niobium disulfide heterojunction nanosheet - Google Patents
Tungsten disulfide/niobium disulfide heterojunction nanosheet Download PDFInfo
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- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- VRSMQRZDMZDXAU-UHFFFAOYSA-N bis(sulfanylidene)niobium Chemical compound S=[Nb]=S VRSMQRZDMZDXAU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002135 nanosheet Substances 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 229910020042 NbS2 Inorganic materials 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002356 single layer Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 19
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 16
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 229910052594 sapphire Inorganic materials 0.000 claims description 11
- 239000010980 sapphire Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000002064 nanoplatelet Substances 0.000 claims description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000002674 ointment Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000010955 niobium Substances 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 description 8
- -1 transition metal sulfides Chemical class 0.000 description 8
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002055 nanoplate Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000690622 Decma Species 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
The invention provides a tungsten disulfide/niobium disulfide heterojunction nanosheet which grows on the surface of a substrate, wherein the first layer from the substrate to the top is a single-layer tungsten disulfide layer, at least part of the upper part of the tungsten disulfide layer is covered with a niobium disulfide layer, and the thickness of the niobium disulfide layer is 4-6 nm. The invention also provides a preparation method and application of the tungsten disulfide/niobium disulfide heterojunction nanosheet. The invention provides NbS2/WS2The heterojunction has the advantages of stable chemical property, good crystallinity, high electrochemical active area and the like, and the Nb isS2/WS2The heterojunction electrochemical hydrogen evolution performance is good, the stability is good, and the method can be used in the related field of hydrogen production by water electrolysis.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a catalytic material for electrochemical hydrogen evolution, and preparation and application thereof.
Background
The use of fossil fuels such as coal, oil and natural gas poses serious environmental problems, and the reserves of coal, oil and natural gas are limited and difficult to regenerate, and the shortage of energy is a major challenge facing the current society. Therefore, the vigorous development of clean and renewable energy is an important subject in front of people. The hydrogen has higher combustion heat value, and the combustion product only contains water, so the hydrogen is an important clean energy source. However, to realize the practical utilization of hydrogen energy, many problems need to be solved, and one of the bottleneck problems is how to efficiently prepare fuel hydrogen.
Compared with the hydrogen production by petroleum reforming and cracking, the hydrogen production by water electrolysis is environment-friendly and renewable, and the product purity is high. However, the energy consumption is high, the price is high, and the catalyst for hydrogen production by electrolysis mostly uses noble metals (such as Pt and Pd), so that the development of a high-efficiency hydrogen-evolution catalytic material with low cost and rich resources becomes one of the current research focuses. Recent studies have found that transition metal sulfides (e.g., MoS)2And WS2) And hydrogen have a binding energy close to that of noble metals,the catalyst has good catalytic activity, low price and abundant reserves, and is an ideal low-cost hydrogen evolution catalytic material.
The hydrogen production catalyzed by transition metal sulfide is actually used as an electrode to electrolyze water, so the structure of the catalyst has great influence on catalytic activity. Obtaining transition metal sulfide catalytic materials with good catalytic performance at a low cost is a great challenge for researchers in the field. The metallic transition metal sulfide is another important member in a transition metal sulfide family, can be used as a good electrode contact based on the metallic characteristics of the metallic transition metal sulfide, and has important significance in promoting the application prospect of the transition metal sulfide in the fields of electrocatalysis, devices and the like.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a tungsten disulfide/niobium disulfide heterojunction nanosheet.
The second purpose of the invention is to provide a preparation method of the tungsten disulfide/niobium disulfide heterojunction nanosheet.
The third purpose of the invention is to provide the application of the tungsten disulfide/niobium disulfide heterojunction nanosheet.
The technical scheme for realizing the above purpose of the invention is as follows:
a tungsten disulfide/niobium disulfide heterojunction nanosheet grows on the surface of a substrate, and the first layer from the substrate upwards is a single-layer tungsten disulfide (WS)2) A layer of tungsten disulfide at least partially covered with niobium disulfide (NbS)2) The thickness of the layer and the niobium disulfide layer is 4-6 nm.
Preferably, the niobium disulfide sheet is a single crystal, and the size of a niobium disulfide domain of the single crystal is 1-10 mu mm; the substrate is one of sapphire, mica and silicon dioxide.
The preparation method of the tungsten disulfide/niobium disulfide heterojunction nanosheet comprises the following steps:
(1) synthesizing single-layer WS on substrate by using tungsten oxide powder and sulfur powder as raw materials and utilizing low-pressure chemical vapor deposition method2，
(2) Niobium chloride and sulfur powder are used as raw materials,WS obtained in step (1) by means of atmospheric pressure chemical vapor deposition2Surface-synthesized thin layer NbS2Thereby obtaining the tungsten disulfide/niobium disulfide heterojunction nanosheet.
Further, the step (1) is carried out in a three-temperature-zone tube furnace, the air pressure in the tube furnace is 0.5-10 Pa, and the temperatures of the tungsten oxide powder, the sulfur powder and the substrate are respectively 90-120 ℃, 800-900 ℃ and 800-900 ℃.
In the step (1), argon and/or hydrogen is introduced into the tubular furnace, the flow rate of the argon is 10-100 sccm, the flow rate of the hydrogen is 1-10 sccm, and the sulfur powder, the tungsten oxide powder and the substrate are respectively arranged at the upstream, the midstream and the downstream in the furnace tube.
Wherein the step (2) is carried out in a three-temperature-zone tube furnace, and sulfur powder and NbCl are adopted5The powder and the substrate with tungsten disulfide are respectively arranged at the upstream, the midstream and the downstream of a furnace tube and are heated for carrying out a vulcanization reaction;
wherein the furnace temperature at the substrate is 650-800 ℃ and NbCl5The furnace temperature is 150-300 ℃, and the furnace temperature is 100-250 ℃ at the sulfur powder.
Introducing argon and/or hydrogen into the reaction equipment in the step (2), wherein the flow of the argon is 70-120 sccm, and the flow of the hydrogen is 1-10 sccm;
in the step (2), the pressure in the tube of the three-temperature-zone tube furnace is normal pressure.
Wherein the time of the synthesis reaction in the step (2) is 5-30 min, preferably 15 min.
The preparation method, more preferably, comprises the steps of:
(1) and (3) placing the sulfur powder, the tungsten oxide powder and the substrate in a furnace tube of a three-temperature-zone tube furnace, and cleaning the whole growth system by using argon gas before the reaction is carried out, wherein the flow of the argon gas is 400-600 sccm, and the cleaning time is 10-30 min. The temperatures of the tungsten oxide powder, the sulfur powder and the substrate are respectively 95-110 ℃, 860-900 ℃ and 860-900 ℃, the temperature rise time is 30-40 minutes, and the temperature is maintained for 20-40 minutes;
(2) mixing sulfur powder and NbCl5The powder and the substrate with tungsten disulfide are respectively arranged on the furnace tubeCleaning the furnace tube by argon gas at the midstream, the downstream and the midstream, then heating, controlling the furnace temperature at the substrate to 700-800 ℃, and NbCl5The furnace temperature is 160-210 ℃, the furnace temperature of the sulfur powder is 120-180 ℃, the heating time is 15-50min, the temperature is maintained for 5-15 min, and then the furnace is naturally cooled.
Preferably, in the preparation method of the thin niobium disulfide, the Ar gas flow in the gas washing treatment in the step (1) is 400-600 sccm, preferably 500 sccm;
the tungsten disulfide/niobium disulfide heterojunction nanosheet is applied to catalyzing electrochemical hydrogen evolution.
Compared with the prior art, the invention has the following advantages:
the invention provides NbS2/WS2The heterojunction has the advantages of stable chemical property, good crystallinity, high electrochemical active area and the like, and the Nb isS2/WS2The heterojunction electrochemical hydrogen evolution performance is good, the stability is good, and the method can be used in the related field of hydrogen production by water electrolysis.
The invention utilizes the chemical vapor deposition method to prepare NbS by a two-step method2/WS2An interlayer heterojunction. The method has the advantages of simple synthesis steps, low cost, high repeatability and good controllability; prepared NbS2/WS2The heterojunction sheet has good crystallinity and chemical stability, and simultaneously NbS2The heterojunction is a metallic transition metal sulfide, is a metal-semiconductor heterojunction, has very good performance when applied to electrochemical hydrogen evolution, has a Tafel slope of 85V/decade, has enhanced performance compared with the performance of pure tungsten disulfide, and reaches 10mA/cm2When the current density is high, the overpotential is 156mV, the catalytic activity site number per unit area is very high, and no attenuation is generated in the stability test, which indicates that the hydrogen evolution performance is stable and good.
Drawings
FIG. 1a is a schematic representation of the preparation of NbS in example 12/WS2A preparation process schematic diagram of the heterojunction; FIGS. 1b and 1c are Scanning Electron Microscope (SEM) top views of single-layer WS2 and NbS2/WS2 heterojunctions, respectively, prepared in example 1; FIG. 1d shows NbS prepared in example 12/WS2Of heterojunction nanosheetsAtomic Force microscope (Atomic Force Microscopy) diagram;
FIG. 2a shows NbS prepared in example 12/WS2A high resolution Transmission Electron Micrograph (TEM) of the heterojunction nanoplates; FIG. 2b is NbS2/WS2A selected area electron diffraction spot corresponding to the heterojunction area;
FIG. 3a shows WS prepared in example 12And NbS2/WS2Raman analysis patterns (Raman) before and after heterojunction nanoplatelet transfer; FIG. 3b shows WS prepared in example 12And NbS2/WS2Fluorescence Profiles (PL) before and after heterojunction nanotransport;
FIGS. 4a-4c show WS prepared in example 12And NbS2/WS2A HER test performance comparison graph of the heterojunction nanosheets;
FIG. 5 is NbS prepared in example 12/WS2HER stability test analysis plots for the heterojunction nanoplates.
FIG. 6 shows NbS prepared in example 12/WS2SEM photograph of heterojunction nanoplatelets.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise specified, the means used in the examples are all technical means known in the art.
Example 1
NbS2/WS2Preparation of heterojunction nanoplatelets (see figure 1a for a schematic preparation process):
(1) a three-temperature-zone tube furnace is utilized, a low-pressure chemical vapor deposition method is adopted, sulfur powder and tungsten trioxide powder are used as reaction precursors, and sapphire single crystals are used as a growth substrate. And (3) sequentially placing the sulfur powder, the tungsten oxide powder and the sapphire single crystal substrate into a quartz tube from left to right, and cleaning the whole growth system by using a large amount of Ar gas before the reaction is carried out, wherein the flow of the Ar gas is 500sccm, and the gas cleaning time is 25 min.
By means of mechanical pumpsThe whole reaction system is maintained in a low-pressure state, the heating temperature of the sulfur powder is 100 ℃, the heating temperatures of the tungsten oxide and the substrate are 880 ℃ respectively, the temperature rise time is 35 minutes and is maintained for 30 minutes, 5sccm hydrogen and 80sccm argon are introduced in the whole growth reaction process, the temperature is cooled to room temperature after the growth is finished, and the single-layer WS is obtained on the sapphire single crystal substrate2Sheet (product morphology see fig. 1 b).
(2) Mixing sulfur powder (S) and niobium pentachloride powder (NbCl)5) And (1) WS obtained in step (a)2Placing in the upstream, middle-stream and downstream central temperature regions of the three-temperature-region tubular reaction furnace, respectively, cleaning the quartz tube with 500sccm argon (Ar) for 10min, heating the upstream central temperature region to 150 deg.C, and adding NbCl5The temperature is increased to 190 ℃, the furnace temperature of a downstream central temperature zone is increased to 750 ℃, the flow rate of Ar carrier gas is kept to be 100sccm, the hydrogen is kept to be 5sccm, the whole reaction system is in a normal pressure state, the temperature rise time is 25 minutes, the NbS is naturally cooled to room temperature after growing for 10 minutes, and the NbS is obtained2/WS2Heterojunction nanosheets (product morphology see fig. 1c and 1d, fig. 6).
The following sections briefly illustrate their performance indicators:
FIG. 1a is a schematic representation of the preparation of NbS in example 12/WS2A preparation process schematic diagram of the heterojunction; FIG. 1b shows WS prepared in step (1)2Scanning Electron Microscope (SEM) top view of the nanoplates, WS, as can be seen in FIG. 1b2The domain size is larger, about 50 μm, and the shape is similar to triangle piece FIG. 1c is NbS prepared in example 12/WS2Scanning Electron Microscope (SEM) top view of a heterojunction, NbS as can be seen in FIG. 1c2Nanosheet is growing WS2Forming NbS2/WS2An interlayer heterojunction. FIG. 1d shows NbS prepared in example 12/WS2Atomic Force microscope (Atomic Force microscope) diagram of heterojunction nanosheet, from FIG. 1d, it can be seen that the upper NbS layer2The thickness of the sheet was 5nm, thus obtaining a heterojunction with a thickness of about 6 nm.
FIG. 2a shows NbS prepared in example 12/WS2High resolution Transmission Electron Microscopy (TEM) of heterojunction nanoplates, from FIG. 2a one sees the heterogeneityJunction region and pure WS2Distinct boundary, and single-layer WS2The TEM image is subjected to Fourier transform to obtain a set of hexagonal spots; FIG. 2b is NbS2/WS2As can be seen from FIG. 2b, there are two sets of diffraction spots without torsion corresponding to the selected area electron diffraction spots in the heterojunction area, which reflects NbS2/WS2The formation of the heterojunction can also obtain that the two have no torsion and are perfect Van der Waals epitaxial growth;
FIG. 3a shows WS prepared in example 12And NbS2/WS2Raman analysis patterns (Raman) before and after heterojunction nanoplatelet transfer; FIG. 3a shows the WS interaction with the simple WS2The Raman peak comparison of the two groups obtains a new Raman peak appearing in the heterojunction, and the peak belongs to NbS2Thus, NbS is illustrated2/WS2Formation of heterojunctions and by WS2And NbS2/WS2E of (A)2gAnd A1gThe ratio of the peak intensities of (A) can also reflect1gPeaks are enhanced after heterojunction growth, based on A1gReflecting the vibration modes between the layers. FIG. 3b shows WS prepared in example 12And NbS2/WS2Fluorescence Profiles (PL) before and after heterojunction nanotransport; as can be seen from FIG. 3b, with respect to WS2PL peak of (3), NbS2/WS2The fluorescence peak of the heterojunction is significantly red-shifted due to the formation of electrons from the semiconductor WS2Metallic NbS2And (5) transferring.
Example 2
NbS2/WS2Preparing a heterojunction nanosheet:
(1) a three-temperature-zone tube furnace is utilized, a low-pressure chemical vapor deposition method is adopted, sulfur powder and tungsten trioxide powder are used as reaction precursors, and sapphire single crystals are used as a growth substrate. And (3) sequentially placing the sulfur powder, the tungsten oxide powder and the sapphire single crystal substrate into a quartz tube from left to right, and cleaning the whole growth system by using a large amount of Ar gas before the reaction is carried out, wherein the flow of the Ar gas is 500sccm, and the gas cleaning time is 25 min.
The whole reaction system is maintained in a low-pressure state by using a mechanical pump, and sulfur powder is addedThe heating temperature is 100 ℃, the heating temperatures of the tungsten oxide and the substrate are 880 ℃ respectively, the heating time is 35 minutes and is maintained for 35 minutes, 5sccm hydrogen and 80sccm argon are introduced in the whole growth reaction process, the temperature is cooled to room temperature after the growth is finished, and the single-layer WS is obtained on the sapphire single crystal substrate2And (3) slicing.
(2) Mixing sulfur powder (S) and niobium pentachloride powder (NbCl)5) And (1) WS obtained in step (a)2Placing in the upstream, middle-stream and downstream central temperature regions of the three-temperature-region tubular reaction furnace, respectively, cleaning the quartz tube with 500sccm argon (Ar) for 10min, heating the upstream central temperature region to 150 deg.C, and adding NbCl5The temperature is increased to 190 ℃, the furnace temperature of a downstream central temperature zone is increased to 750 ℃, the flow rate of Ar carrier gas is kept at 100sccm, the flow rate of hydrogen is kept at 10sccm, the whole reaction system is in a normal pressure state, the temperature rise time is 25 minutes, the NbS is naturally cooled to room temperature after the NbS grows for 20 minutes, and the NbS is obtained2/WS2A heterojunction nanosheet.
NbS prepared in this example2/WS2In the heterojunction, WS2The domain area is about 30 μm, and the upper NbS layer2The thickness of the sheet-forming continuous film was 5nm, and thus the thickness of the resulting heterojunction was about 6 nm.
Comparative example 1
The comparative example 1 is a method for preparing a tungsten sulfide nanosheet by metal oxide vulcanization, and the specific process brief introduction is as follows: the method comprises the steps of utilizing a three-temperature-zone tube furnace, adopting a low-pressure chemical vapor deposition method, taking sulfur powder and tungsten trioxide powder as reaction precursors, taking a sapphire single crystal as a growth substrate, sequentially placing the sulfur powder, the tungsten oxide powder and the sapphire single crystal substrate into a quartz tube from left to right, utilizing a mechanical pump to enable the whole reaction system to maintain a low-pressure state, heating the sulfur powder at 100 ℃, the tungsten oxide and the substrate at 880 ℃ respectively, keeping the temperature rise time for 35 minutes for 30 minutes, introducing 5sccm hydrogen and 80sccm argon in the whole growth reaction process, cooling to room temperature after the growth is finished, and obtaining single-layer WS on the sapphire single crystal substrate2And (3) slicing.
Through detection, the obtained tungsten sulfide nanosheet is poor in performance, the Tafel slope measured by an electrochemical hydrogen evolution experiment is 110mV/dec, and the Tafel slope reaches 10mV/decmA/cm2The required overpotential is 270 mV.
Electrocatalytic Hydrogen Evolution (HER) experiment
The product of example 1 was used to prepare an electrode with 0.5mol/L of dilute H electrolyte2SO4In the solution, the counter electrode is Pt, and the reference electrode is a calomel electrode. Before the test was performed, pure nitrogen was bubbled through the electrolyte for about 30 minutes in order to eliminate the oxygen from the solution, and then the test could be run.
FIG. 4 compares WS of comparative example 12And NbS of example 12/WS2Hydrogen evolution performance of the heterojunction nanoplatelets. From FIG. 4a, it can be seen that NbS2/WS2The heterojunction greatly improves WS2The hydrogen evolution efficiency of the nano-sheet reaches 10mA/cm2At current of (3), NbS2/WS2Overpotential (165mV) vs WS required for heterojunction nanoplates2The nanosheet (270mV) is much lower, and the Tafel slope also varies from WS2110mV/decade of sample is reduced to NbS2/WS285mV/decade of heterojunction nanosheet.
FIG. 5 reaction NbS2/WS2The hydrogen evolution stability of the heterojunction nanosheet is basically unchanged after 2000 cyclic voltammetry tests, and the stability and the good hydrogen evolution performance of the heterojunction nanosheet are reflected.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. The tungsten disulfide/niobium disulfide heterojunction nanosheet is characterized in that the tungsten disulfide/niobium disulfide heterojunction nanosheet grows on the surface of a substrate, the first layer from the substrate to the top is a single-layer tungsten disulfide layer, at least part of the upper portion of the tungsten disulfide layer is covered with a niobium disulfide layer, and the thickness of the niobium disulfide layer is 4-6 nm;
the niobium disulfide in the niobium disulfide layer is single crystal, and the size of a niobium disulfide domain of the single crystal is 1-10 mu mm; the substrate is one of sapphire, mica and silicon dioxide.
2. A method of making tungsten disulfide/niobium disulfide heterojunction nanosheets as recited in claim 1, comprising the steps of:
(1) synthesizing single-layer WS on substrate by using tungsten oxide powder and sulfur powder as raw materials and utilizing low-pressure chemical vapor deposition method2，
(2) Taking niobium chloride and sulfur powder as raw materials, and obtaining WS in the step (1) by utilizing a normal pressure chemical vapor deposition method2Surface-synthesized thin layer NbS2Thereby obtaining the tungsten disulfide/niobium disulfide heterojunction nanosheet.
3. The preparation method according to claim 2, wherein the step (1) is carried out in a three-temperature-zone tube furnace, the air pressure in the tube furnace is 0.5-10 Pa, and the temperatures of the tungsten oxide powder, the sulfur powder and the substrate are 90-120 ℃, 800-900 ℃ and 800-900 ℃ respectively.
4. The preparation method according to claim 3, wherein in the step (1), argon gas and/or hydrogen gas is introduced into the tube furnace, the flow rate of the argon gas is 10-100 sccm, the flow rate of the hydrogen gas is 1-10 sccm, and the sulfur powder, the tungsten oxide powder and the substrate are respectively arranged at the upstream, the midstream and the downstream in the furnace tube.
5. The method according to any one of claims 2 to 4, wherein the step (2) is carried out in a three-zone tube furnace containing sulfur powder, NbCl5The powder and the substrate with tungsten disulfide are respectively arranged at the upstream, the midstream and the downstream of a furnace tube and are heated for carrying out a vulcanization reaction;
wherein the furnace temperature at the substrate is 650-800 ℃ and NbCl5The furnace temperature is 150-300 ℃, and the furnace temperature is 100-250 ℃ at the sulfur powder.
6. The preparation method according to any one of claims 2 to 4, wherein argon gas and hydrogen gas are introduced into the reaction equipment in the step (2), wherein the flow rate of the argon gas is 70 to 120sccm, and the flow rate of the hydrogen gas is 1 to 10 sccm.
7. The method according to any one of claims 2 to 4, wherein the time for the synthesis reaction in step (2) is 5 to 30 min.
8. The method according to any one of claims 2 to 4, comprising the steps of:
(1) placing sulfur powder, tungsten oxide powder and a substrate in a furnace tube of a three-temperature-zone tube furnace, and cleaning the whole growth system with argon before reaction, wherein the flow of the argon is 400-600 sccm, and the cleaning time is 10-30 min; controlling the temperatures of the tungsten oxide powder, the sulfur powder and the substrate to be 95-110 ℃, 860-containing 900 ℃ and 860-containing 900 ℃, respectively, and maintaining the temperature rise time for 30-40 minutes and 20-40 minutes;
(2) mixing sulfur powder and NbCl5Respectively placing the powder and the substrate with the tungsten disulfide on the upstream, the midstream and the downstream of a furnace tube, cleaning the furnace tube by argon, then heating, controlling the furnace temperature at the substrate to be 700-800 ℃, and NbCl5The furnace temperature is 160-210 ℃, the furnace temperature of the sulfur powder is 120-180 ℃, the heating time is 15-50min, the temperature is maintained for 5-15 min, and then the furnace is naturally cooled.
9. Use of tungsten disulphide/niobium disulphide heteroj unction nanoplatelets according to claim 1 for the catalytic electrochemical hydrogen evolution.
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