CN112678826B - Synthesis method of two-dimensional transition metal chalcogenide - Google Patents
Synthesis method of two-dimensional transition metal chalcogenide Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a two-dimensional transition metal chalcogenide, which comprises the following steps: a heating step: heating a transition metal compound raw material to a reaction temperature in an inert gas environment; topology conversion reaction step: introducing gas containing chalcogen or mixed gas of the gas containing chalcogen and the gas containing phosphorus, and keeping the reaction temperature for a set time to enable the chalcogen or the chalcogen and the phosphorus to perform topological transformation reaction with the transition metal compound raw material to generate the two-dimensional transition metal chalcogenide. The synthesis method has the advantages of high reaction degree, high yield, low energy consumption and high efficiency, and the obtained two-dimensional transition metal chalcogenide has high single-layer rate and narrow layer distribution, can realize macro preparation, and has excellent industrial application prospect.
Description
Technical Field
The invention belongs to the field of energy technology, physics and electronics, relates to a preparation method of metal chalcogenide, and more particularly relates to a synthetic method capable of massively obtaining two-dimensional transition metal chalcogenide.
Background
Once reported, graphene attracts the attention of researchers due to excellent electrical, optical and mechanical properties. Meanwhile, the zero band gap of graphene limits the application of graphene in the field of electronics. A transition metal chalcogenide compound comprising: moS 2 、MoSe 2 、MoTe 2 、TiS 2 、TiSe 2 、WS 2 、WSe 2 、WTe 2 And the like, are a type of interlaminar phase formed by van der Waals interactionsThe force-combined graphite-like structural material presents two crystalline states of a naturally-occurring triangular prism phase (generally represented by 2H) and a non-naturally-occurring tetrahedral phase (generally represented by 1T), and the band gap of the material is adjustable along with the change of the thickness of the material, so that the material has application prospects in the aspects of electronic devices, photoelectric devices, energy storage or catalysis and the like.
The preparation method of single-layer or few-layer two-dimensional transition metal chalcogenide mainly comprises a chemical vapor deposition method, a physical vapor deposition method, a mechanical stripping method, a liquid phase stripping method and an electrochemical stripping method at present. The vapor deposition method is an effective method for preparing two-dimensional transition metal chalcogenide compounds with uniform thickness, large size and more variety, but the method requires severe reaction conditions (such as pressure, temperature, substrate, precursor, cooling rate) and high cost, which limits further popularization and application of the method. With the lift-off method, the thickness of the obtained two-dimensional transition metal chalcogenide generally has a wide distribution (from a single layer to several tens of layers), and the method has a low yield, such as: in 2011, jonathan n, coleman and the like of san sanchi academy of dublin report the work of preparing two-dimensional materials by liquid phase stripping for the first time and are published in journal of science, molybdenum disulfide and tungsten disulfide blocks are subjected to liquid phase ultrasonic treatment in isopropanol and N-methylpyrrolidone and are subjected to centrifugal separation to obtain corresponding molybdenum disulfide and tungsten disulfide nanosheets, wherein the yield of the obtained monolayer two-dimensional nanosheets is less than 1%. HaoLi Zhang et al reported in the journal of german applied chemistry the work of stripping molybdenum disulfide and tungsten disulfide blocks using a mixed solvent of ethanol and water, wherein the stripping yield was maximized when a 35% ethanol aqueous solution was used, wherein the stripping yield of a monolayer of molybdenum disulfide and tungsten disulfide was also less than 1%.
Therefore, how to efficiently and massively prepare the two-dimensional transition metal chalcogenide with a single layer or a few layers is a technical problem which is not solved at present.
Disclosure of Invention
Aiming at the technical problem that single-layer and few-layer two-dimensional transition metal chalcogenide is difficult to prepare massively, the invention provides a synthesis method of the two-dimensional transition metal chalcogenide, which comprises the following steps:
a heating step: heating the transition metal compound to a reaction temperature in an inert gas environment;
topology conversion reaction step: and introducing gas containing chalcogen or mixed gas of the gas containing chalcogen and the gas containing phosphorus, and keeping the reaction temperature for a set time to enable the chalcogen or the chalcogen and the phosphorus to undergo topological transformation reaction with the transition metal compound to generate the two-dimensional transition metal chalcogenide.
In some embodiments, the transition metal compound comprises MAX or MX, wherein M represents one or more of the transition metal elements scandium, titanium, vanadium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, or tungsten, a represents one or more of the elements aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium, or lead, and X represents one of the elements carbon, silicon, boron.
In some embodiments, the reaction temperature is between 300 ℃ and 1100 ℃, and the set time period is less than or equal to 360min.
In some embodiments, the reaction temperature is between 800 ℃ and 1100 ℃, and the set time period is less than or equal to 30min.
In some embodiments, the chalcogen-containing gas comprises one or more of highly reactive gaseous sulfur, selenium, tellurium, hydrogen sulfide, hydrogen selenide, or hydrogen telluride; and/or the gas containing the phosphorus group element comprises one or more of high-activity gaseous phosphorus, arsenic, phosphine or ammonium phosphide.
In some embodiments, prior to the heating step, further comprising the step of preparing the MX as follows:
an etching step: adding the MAX powder into an acid solution, and etching the element A in the MAX by an acid component in the acid solution to obtain a suspension containing MX;
and (3) cleaning and drying: and carrying out suction filtration on the suspension, repeatedly washing the suspension by using deionized water, removing the acidic component, and drying to obtain the MX.
In some embodiments, the MAX comprises Mo 2 Ga 2 C、Mo 2 GeC、Ti 3 SiC 2 、Ti 2 SnC、Ti 2 AlC、Nb 2 AlC、Ta 2 AlC、TiNbAlC、Mo 2 TiAlC 2 Or (W) 2/3 Y 1/3 ) 2 One or more of AlC, MX comprises Mo 2 C、Mo 1.33 C、V 2 C、Nb 2 C、Ti 3 C 2 、Ti 4 C 3 、Mo 2 Ti 2 C 3 、Mo 2 TiC 2 、Ta 2 C、Ta 4 C 3 TiNbC, moB or MoSi 2 One or more of them.
The invention also provides a preparation method of the two-dimensional transition metal chalcogenide dispersion liquid, the two-dimensional transition metal chalcogenide obtained by the synthesis method is placed in a solvent for ultrasonic treatment and centrifugal treatment, and the upper layer liquid is taken to obtain the two-dimensional transition metal chalcogenide dispersion liquid.
In some embodiments, the solvent comprises one or more of water, N-methylpyrrolidone, N-dimethylformamide, ethanol, isopropanol, butanone, or toluene.
In some embodiments, the sonication has a sonication power of 300W to 1000W and a sonication time of 0.5h to 6h.
In some embodiments, the exfoliation yield of the two-dimensional transition metal chalcogenide is less than or equal to 37 wt.%.
Still another aspect of the present invention also includes an aggregate of a two-dimensional transition metal chalcogenide, the aggregate including a powder, a dispersion, or a compacted solid, the two-dimensional transition metal chalcogenide obtained by the above synthesis method being contained in the aggregate, and the monolayer rate of the two-dimensional transition metal chalcogenide being greater than 30%.
In some embodiments, the number of layers of the two-dimensional transition metal chalcogenide contained in the aggregate is between 1 layer and 5 layers.
In some embodiments, the thickness of the two-dimensional transition metal chalcogenide contained in the aggregate is between 0.5nm and 8 nm.
Still another aspect of the present invention also includes the use of the aggregate of two-dimensional transition metal chalcogenides in transistors, logic circuits, sensors, flexible devices, lithium secondary batteries and hydrogen evolution reactions.
The invention has the beneficial technical effects that:
(1) The two-dimensional transition metal chalcogenide is obtained by taking the transition metal compound as a raw material and performing topological transformation reaction with the chalcogenide through a simple heating step, and the topological transformation reaction can be highly reacted and has the characteristic of high yield;
(2) The two-dimensional transition metal chalcogenide obtained by the synthesis method has the outstanding advantages of high single-layer rate and narrow layer number distribution, because the raw material transition metal compound layers are combined by Van der Waals force, when topological transformation reaction occurs, the chalcogenide elements are substituted in situ between the raw material transition metal compound layers to generate the transition metal chalcogenide, and meanwhile, the Van der Waals force between the layers can be destroyed, so that the product transition metal chalcogenide single layer and the single layer can be separated to form an expanded two-dimensional lamellar structure;
(3) The synthesis method has the advantages of simple topological transformation reaction conditions, wide reaction condition range, realization of reaction in relatively short time (hours or minutes), and industrial macro synthesis prospect;
(4) The two-dimensional transition metal chalcogenide obtained by the synthesis method has an expanded two-dimensional lamellar structure, so that a solvent is easier to intercalate into interlayers when the two-dimensional transition metal chalcogenide is used for preparing a dispersion liquid by stripping, and the two-dimensional transition metal chalcogenide also has the advantage of high stripping yield.
Drawings
FIG. 1 shows Mo in the example of the present invention 2 MoS synthesized by taking C nanosheet as raw material 2 An XRD pattern of (a);
FIG. 2 shows Mo as an example of the present invention 2 MoS synthesized by taking C nanosheet as raw material 2 SEM (a) and TEM photograph (b);
FIG. 3 shows an embodiment of the present inventionWith Mo 2 MoS synthesized by taking C nanosheet as raw material 2 Cross-sectional HRTEM photograph (a) and layer number analysis (b);
FIG. 4 shows Mo as an example of the present invention 2 MoSe synthesized by taking C nanosheet as raw material 2 Cross-sectional HRTEM (a) and slice number analysis (b);
FIG. 5 shows Ti in an example of the present invention 2 TiSe synthesized by taking C nanosheet as raw material 2 Cross-sectional HRTEM photograph (a) and layer number analysis (b);
FIG. 6 is a summary of topological transformation reactions of various transition metal compounds MX with gaseous components;
FIG. 7 shows Mo in the example of the present invention 2 MoS synthesized by GeC as raw material 2 SEM photograph of (a);
FIG. 8 shows Mo as an example of the present invention 2 MoS synthesized by GeC as raw material 2 Cross-sectional HRTEM photograph (a) and slice number analysis (b);
FIG. 9 shows Mo as an example of the present invention 2 MoSe synthesized by GeC serving as raw material 2 XRD spectrum (a) and SEM photograph (b) of (a);
FIG. 10 shows Ti in an example of the present invention 3 SiC 2 TiSe synthesized by raw materials 2 XRD spectrum (a) and SEM photograph (b) of (a);
FIG. 11 shows a graph of (W) in an embodiment of the present invention 2/3 Y 1/3 ) 2 Y-WS synthesized by taking AlC as raw material 2 XRD spectrum (a) and SEM photograph (b) of (a);
FIG. 12 shows the Y-WS synthesized in the examples of the present invention 2 (a) With commercially available WS 2 XRD contrast pattern of powder (b);
FIG. 13 is a summary of the topological transformation reactions of different transition metal compounds with gaseous components;
FIG. 14 is a representation of the MoS synthesized in accordance with the present invention 2 Photographs (a, c) of dispersion in IPA and NMP and graphs (b, d) of ultrasonic time versus peel yield;
FIG. 15 shows MoS prepared according to the present invention 2 SEM (a) and TEM (of dispersion liquid: (A))b) Taking a photo;
FIG. 16 is a representation of MoS prepared in accordance with the present invention 2 AFM thickness test profile of the dispersion;
FIG. 17 shows the synthesis of Y-WS according to the present invention 2 Photographs (a, c) of dispersion in IPA and NMP and graphs (b, d) of the relationship between sonication time and stripping yield;
FIG. 18 is a schematic representation of the steps of the synthetic method of the present invention;
FIG. 19 shows the synthetic Y, P-WS sequences of the present invention 2 A raman spectrum of (a).
Symbolic illustration in the drawings:
TMD transition metal disulfide.
Detailed Description
The technical solution of the present invention will be described below by way of specific examples. It is to be understood that one or more of the steps mentioned in the present invention does not exclude the presence of other methods or steps before or after the combined steps, or that other methods or steps may be inserted between the explicitly mentioned steps. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method well known to those skilled in the art.
It is to be understood that one or more of the steps mentioned in the present application do not exclude the presence of other methods or steps before or after the combined steps, or that other methods or steps may be inserted between the explicitly mentioned steps.
Example 1
This example provides a method for preparing a transition metal compound MX, comprising:
1) Etching: placing the powder of the transition metal compound MAX into an acid solution for etching, and etching the element A by an acid component in the acid solution to obtain a suspension containing the transition metal compound MX;
2) A cleaning and drying step: carrying out suction filtration on the suspension obtained in the step 1), repeatedly washing the suspension by using deionized water, removing acid components, and drying to obtain powder of a transition metal compound MX;
in the transition metal compound MAX, M represents one or more transition metal elements such as a transition metal element scandium, titanium, vanadium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, etc., a represents one element such as aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium, lead, etc., and X represents one element such as carbon, silicon, boron, etc. MAX is a layered material, and MX obtained by etching the A element layer by an acidic component is of a single-layer or few-layer nanosheet structure.
Wherein the means for heating in the heating step comprises one of a tube furnace, a box furnace, a rapid annealing furnace, a chemical vapor deposition system, a microwave oven, or a plasma system.
Example 2
In this example, mo is used 2 The C nanosheet is taken as an example to illustrate the preparation method of MX in the invention, and comprises the following steps:
1) Etching: mo is taken as a raw material 2 Ga 2 The powder of C is put into hydrofluoric acid aqueous solution for etching, and the HF etches the Ga element to obtain the product containing Mo 2 C, suspension of nanosheets;
2) A cleaning and drying step: filtering the suspension obtained in the step 1), repeatedly cleaning the suspension with deionized water, removing HF (hydrogen fluoride), and performing freeze drying treatment to obtain Mo 2 C nano-sheet powder.
The preparation method of MX nanosheets described in embodiments 1 and 2, wherein the preferred starting material, MAX, comprises Mo 2 Ga 2 C、Mo 2 GeC、Ti 3 SiC 2 、Ti 2 SnC、Ti 2 AlC、Nb 2 AlC、Ta 2 AlC、TiNbAlC、Mo 2 TiAlC 2 Or (W) 2/3 Y 1/3 ) 2 One or more of AlC. By these preferred starting materialsThe MX nanosheets prepared by MAX and used in the synthesis method of the present invention comprise: mo 2 C、Ti 3 C 2 、Ti 2 C、Nb 2 C、Ta 2 C、TiNbC、Mo 2 TiC 2 Or (W) 2/3 Y 1/3 ) 2 C.
Example 3
This embodiment provides a method for synthesizing a two-dimensional transition metal chalcogenide, as shown in fig. 18, including the steps of:
1) A heating step: heating a raw material transition metal compound MX to a reaction temperature in an inert gas environment;
2) Topology transformation reaction step: introducing gas containing chalcogen or mixed gas of the gas containing chalcogen and the gas containing phosphorus, and keeping the reaction temperature for a set time to enable the chalcogen or the chalcogen and the phosphorus to have topological transformation reaction with the transition metal compound MX to generate the two-dimensional transition metal chalcogenide.
Wherein, the gas containing the chalcogen is one or more of high-activity gaseous sulfur, selenium, tellurium, hydrogen sulfide, hydrogen selenide or hydrogen telluride; the gas containing phosphorus group elements comprises one or more of high-activity gaseous phosphorus, arsenic, phosphine or ammonium phosphide. The phosphorus group element can play a role in adjusting the phase structure of the product two-dimensional transition metal chalcogenide in the topological transformation reaction. The inert gas refers to non-oxygen gas, and comprises one or more of argon, helium, nitrogen and the like.
Example 4
This example describes the synthesis of molybdenum disulfide (MoS) 2 ) For example, the synthesis method of the present invention is illustrated, wherein the starting transition metal compound MX is Mo prepared in example 2 2 A C nanoplate comprising the steps of:
1) A heating step: mixing 100 mg of Mo 2 Placing the powder of the C nano-sheet into a corundum magnet boat, placing the corundum magnet boat in the middle area of a tube furnace, and raising the temperature in the tube to 600 ℃ at the speed of 10 ℃/min under the condition that protective gas (argon with the purity of more than 99.999%) is introduced into the tube。
2) Topology transformation reaction step: switching the atmosphere to H 2 H with the mass fraction of S of 10% 2 And S and argon gas are mixed, the reaction temperature of the middle area of the tube furnace is kept at 600 ℃, after the reaction time is 1h, the atmosphere is switched to protective gas, and the temperature in the tube is reduced to room temperature.
Collecting the product obtained in step 2), and performing XRD test to obtain a result shown in figure 1, wherein the characteristic diffraction peak conforms to MoS 2 (JCPDS card number. 37-1492) and no Mo 2 The characteristic diffraction peak of C appears, which proves that S element replaces Mo under the reaction condition 2 C element in the C nanosheet, and the obtained reaction product is MoS 2 The reaction yield was 100%.
To prove that the reaction product was MoS 2 Structure, scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) characterization, moS is given in FIGS. 2a and 2b, respectively 2 SEM and TEM photographs of (1), moS can be seen 2 The microscopic morphology of the film is an ultrathin two-dimensional lamellar structure, and the size of the lamellar diameter is 2-10 mu m. Demonstration of the reaction product MoS 2 Is MoS 2 Two-dimensional sheet illustrating H in the step of topological transformation reaction 2 S and Mo 2 C performs topology transformation reaction to obtain MoS 2 Mo is still remained 2 And C, the shape and structure of the nanosheet.
To verify the MoS 2 Number of layers in two-dimensional sheet, moS 2 The two-dimensional sheet was embedded in a sprur resin, and then cured in the sprur resin at 70 ℃ for 24 hours to obtain a solid block, and then an ultrathin section obtained by cutting the solid block with a diamond knife at room temperature with a microtome (Leica EM UC 7) was dispersed on a bare carbon grid for cross-sectional HRTEM measurement, and a cross-sectional HRTEM photograph is given in fig. 3a, from which fig. 3a single-layer MoS can be seen 2 Two-dimensional slice, moS in HRTEM test 2 The number of layers of the two-dimensional sheet layer was statistically analyzed, and as shown in FIG. 3b, it can be seen that the MoS obtained by the synthesis method of the present invention 2 The number of the two-dimensional sheet layers is single layer and 2 layers, and the single layer rate is 95%, which shows that the single-layer and few-layer two-dimensional transition metal chalcogenide compound obtained by the synthesis method of the invention,and the obtained two-dimensional transition metal chalcogenide has the remarkable characteristics of narrow layer distribution, high yield and high single-layer rate.
Example 5
This example uses molybdenum diselenide (MoSe) 2 ) For example, the synthesis of the invention is illustrated, wherein MX, the starting material, is Mo prepared as described in example 2 2 A C nanoplate comprising the steps of:
1) A heating step: 100 mg of Mo 2 The powder of the C nano-sheet is put into a corundum magnet boat and placed in the middle area of a tube furnace, the corundum magnet boat filled with a proper amount (1 g) of selenium powder is placed at the upstream of the tube furnace capable of independently controlling the temperature, and the temperature in the tube is increased to 600 ℃ at the speed of 10 ℃/min under the condition that protective gas (argon with the purity of more than 99.999%) is introduced into the tube.
2) Topology transformation reaction step: and (3) starting a switch of a heating device filled with the selenium powder part, heating to 160 ℃, enabling the selenium powder to be heated to generate gaseous selenium to enter the middle area of the tubular furnace, starting reaction timing when the temperature in the upstream tube reaches the set temperature of 160 ℃, keeping the reaction temperature of 600 ℃ in the middle area of the tubular furnace, and stopping the reaction after the reaction time is 1h, and naturally cooling.
Collecting the product obtained in the step 2) as MoSe 2 A two-dimensional sheet. FIGS. 4a and 4b show MoSe respectively 2 HRTEM image and analysis of the cross section of the two-dimensional slice, it can be seen that MoSe 2 The number of the two-dimensional sheet layers is distributed into a single layer, 2 layers and 3 layers, wherein the single layer rate is 70%.
Example 6
The raw material in example 5 was replaced with Ti 2 Powder of C nano sheet to obtain TiSe product 2 Two-dimensional sheet layer, FIGS. 5a and 5b show TiSe respectively 2 The cross section HRTEM picture and analysis of the two-dimensional slice layer can show that the TiSe is 2 The number of the two-dimensional sheet layers is distributed into a single layer, 2 layers and 3 layers, wherein the single layer rate is 80%.
Wherein, ti 2 The preparation method of the powder of the C nano sheet comprises the following steps:
1) Etching: mixing Ti 2 The AlC is placed in 5mol/L HCl solution for etching, and the HCl is used for etching Al element to obtain the Al-based catalystContaining Ti 2 C, suspension of nanosheets;
2) A cleaning and drying step: filtering the suspension obtained in the step 1), repeatedly washing the suspension with deionized water, removing HCl component, and freeze-drying to obtain Ti 2 C nano-sheet powder.
By adopting the synthesis methods described in examples 3 to 5, a series of two-dimensional transition metal chalcogenide products can be obtained by reacting different transition metal compounds MX with gaseous components, and a summary table of topology transformation reactions of different transition metal compounds MX with gaseous components is specifically illustrated in a table in fig. 6. Wherein P represents gaseous phosphorus, which has the effect of regulating the phase state of the product (2H or 1T phase). In specific implementation, the reaction temperature for the topology transformation reaction is in the range of 300 ℃ to 1100 ℃, the higher the reaction temperature is, the less the reaction time is required, when the reaction temperature is 300 ℃, the reaction time is kept for 4h, when the reaction temperature is 800 ℃, the reaction time is less than 30min, when the reaction temperature is 1100 ℃, the reaction time is less than 10min.
Example 6
This example provides another synthesis method of a two-dimensional transition metal chalcogenide, which, like the synthesis method described in example 3, includes the steps of:
1) A heating step: heating a raw material transition metal compound MAX to a reaction temperature in an inert gas environment;
2) Topology transformation reaction step: introducing gas containing chalcogen or mixed gas of the gas containing chalcogen and the gas containing phosphorus, and keeping the reaction temperature for a set time to enable the chalcogen or the chalcogen and the phosphorus to perform topological transformation reaction with a transition metal compound MAX to generate the two-dimensional transition metal chalcogen compound.
The present example is different from the synthesis method in example 3 in that the raw material in the present example is a transition metal compound MAX or MX (wherein X represents one of elements C, si, and B).
Example 7
This example also synthesizesMoS 2 For example, the synthesis method of the present invention will be described, wherein Mo is selected as the transition metal compound MAX 2 GeC, comprising the steps of:
1) A heating step: mixing 100 mg of Mo 2 GeC powder is put into a corundum magnetic boat and placed in the middle area of a tubular furnace, and the temperature in the tube is increased to 800 ℃ at the speed of 10 ℃/min under the condition that protective gas (argon with the purity of more than 99.999%) is introduced into the tube.
2) Topology transformation reaction step: switching the atmosphere to H 2 H with the mass fraction of S of 10 percent 2 And S and argon gas are mixed, the reaction temperature of the middle area of the tube furnace is kept at 800 ℃, and after the reaction time is 1h, the atmosphere is switched to protective gas until the temperature in the tube is reduced to room temperature.
Collecting the product MoS obtained in the step 2) 2 For the product MoS 2 And Mo as a raw material 2 XRD testing was carried out on GeC, and the result was similar to the XRD curve shown in FIG. 1, and the obtained product MoS 2 Visible characteristic diffraction peaks in XRD pattern, and MoS 2 (JCPDS card number 37-1492) and the MoS product 2 Does not contain any raw material Mo in XRD pattern 2 Characteristic peaks of GeC, indicating H in the synthesis 2 S element in S replaces Mo 2 Ge and C elements in GeC, and obtaining MoS through synthetic reaction 2 The yield of (a) was 100%. FIG. 7 shows the product MoS 2 SEM photograph of (1), it can be seen that the product MoS is obtained 2 Is a two-dimensional sheet material in an expanded state. FIG. 8 shows the product MoS 2 The cross-sectional HRTEM image and the layer number analysis of (1) show that MoS is observed 2 The number of the two-dimensional sheet layers is 1 to 5, and the two-dimensional sheet layers are intensively distributed in 1 to 3 layers, wherein the single layer rate is 31%.
Example 8
This example to synthesize MoSe 2 For example, the synthesis method of the present invention will be described, wherein Mo is selected as the transition metal compound MAX 2 GeC, comprising the steps of:
1) A heating step: mixing 100 mg of Mo 2 GeC powder is placed in a corundum magnetic boat and placed in the middle area of a tube furnace, and the corundum magnetic boat filled with a proper amount (1 g) of selenium powder is placed at the upstream of the tube furnace capable of independently controlling the temperatureThe temperature in the tube was raised at a rate of 10 ℃/min to a reaction temperature of 800 ℃ under the conditions of introduction of a protective gas (argon, purity > 99.999%) into the tube.
2) Topology conversion reaction step: and starting a switch of a heating device filled with the selenium powder part, heating to 160 ℃, enabling the selenium powder to be heated to generate gaseous selenium to enter the middle area of the tubular furnace, starting reaction timing when the temperature in the upstream tube reaches the set temperature of 160 ℃, keeping the reaction temperature of the middle area of the tubular furnace at 800 ℃, and stopping the reaction and naturally cooling after the reaction time is 1 h.
Collecting the product MoSe obtained in the step 2) 2 For the product MoSe 2 And Mo as a raw material 2 XRD test of GeC shows that MoSe is the product of GeC shown in FIG. 9a 2 A series of diffraction peaks in XRD pattern and hexagonal crystal form MoSe 2 (JCPDS card number 29-0914) and corresponding to the characteristics of the product MoSe 2 Does not contain any raw material Mo in XRD pattern 2 Characteristic peak of GeC, showing that Se replaces Mo in synthesis 2 Ge and C elements in GeC, and obtaining MoSe through synthetic reaction 2 The yield of (a) was 100%. FIG. 9b is the product MoSe 2 SEM photograph of (5) shows that the obtained product MoSe 2 Is a two-dimensional sheet material in an expanded state.
Example 9
This example used the same synthetic method as in example 8, except that the starting material in the heating step was replaced with Ti 3 SiC 2 The reaction temperature is 900 ℃, the reaction time is 30min, and the obtained product is TiSe 2 . The XRD spectrum and SEM of the product are given in FIGS. 10a and 10b, respectively, and the product TiSe is seen in FIG. 11a 2 A series of diffraction peaks in XRD pattern of (1), and TiSe 2 (JCPDS card numbers 30-1383) and corresponding to the characteristics of the product TiSe 2 Does not contain any raw material Ti in XRD pattern 3 SiC 2 The characteristic peak of (A) indicates that Se replaces Ti in the synthesis 3 SiC 2 Si and C element in the silicon carbide, tiSe obtained by synthesis reaction 2 The yield was 100%. FIG. 10b is the product TiSe 2 SEM photograph of (1), it can be seen that the product TiSe is obtained 2 Is a two-dimensional sheet material in an expanded state.
Example 10
This example used the same synthetic method as example 7, but with the difference that the starting material was replaced by (W) in the heating step 2/3 Y 1/3 ) 2 AlC, the reaction temperature is 1000 ℃, the reaction time is 30min, and WS doped with Y element serving as a product is obtained 2 （Y-WS 2 ). The XRD spectrum and SEM of the product are given in FIGS. 11a and 11b, respectively, from FIG. 11a it is seen that the product Y-WS is 2 A series of diffraction peaks in XRD pattern and hexagonal form WS 2 (JCPDS card number 08-0237) and corresponding to the product Y-WS 2 Does not contain any raw material in XRD pattern (W) 2/3 Y 1/3 ) 2 Characteristic peak of AlC, indicating that Se is substituted during synthesis (W) 2/3 Y 1/3 ) 2 Al and C elements in AlC, and Y-WS obtained by synthetic reaction 2 The yield was 100%. FIG. 11b shows the product Y-WS 2 SEM photograph of (5) shows that the obtained product Y-WS is 2 Is a two-dimensional sheet material in an expanded state.
In FIG. 12, a and b are Y-WS obtained in this example, respectively 2 Two-dimensional sheet and commercially available WS 2 XRD spectrum of (A) in FIG. 12, it can be seen from comparison of a and b that Y-WS is obtained in this example 2 Two-dimensional slice and commercially available WS 2 Corresponds to the (002), (004), (006) and (110) crystal planes of WS2 (JCPDS card number 08-0237) at diffraction angles of 14.3 DEG, 28.9 DEG, 43.9 DEG and 58.4 DEG, respectively, but the Y-WS in the present embodiment 2 Peak type of characteristic diffraction peak of two-dimensional lamella is more commercially available WS 2 Dispersion, this being in comparison with the Y-WS obtained by the synthetic method of the invention 2 The two-dimensional sheet has a two-dimensional sheet structure in an expanded state.
By using the synthesis methods described in examples 6 to 10, a series of two-dimensional transition metal chalcogenide products can be obtained when different transition metal compounds MAX or MX are reacted with gaseous components, and the two-dimensional transition metal chalcogenide products formed by reacting different transition metal compounds MAX or MX with different gaseous components are specifically illustrated in the table in fig. 13. In specific implementation, the reaction temperature for the topological transformation reaction is in the range of 600 ℃ to 1100 ℃, the higher the reaction temperature is, the less the reaction time is required, when the reaction temperature is 600 ℃, the reaction time is kept for 4h, when the reaction temperature is 900 ℃, the reaction time is less than 30min, and when the reaction temperature is 1100 ℃, the reaction time is less than 10min.
As can be seen from examples 4 to 6, the synthesis method using the transition metal compound MX treated with the acidic solution as the raw material can obtain the two-dimensional transition metal chalcogenide having a single layer ratio of more than 70% and has a narrow layer number distribution (1 layer to 3 layers), and therefore the synthesis method using the transition metal compound MAX as the raw material of the present invention has the outstanding technical effects of a high single layer ratio and a narrow layer number distribution. In contrast to the synthesis method in example 7, it can be seen that the synthesis method using the transition metal compound MAX as the raw material has a relatively low monolayer rate (31%) of the two-dimensional transition metal chalcogenide, and a wider layer number distribution (1 to 5 layers), but the synthesis method using the transition metal compound MAX as the raw material according to the present invention has the positive technical advantages of a simple synthesis method and easy industrial amplification since the steps of etching with an acidic solution and cleaning and drying are not required. In addition, the number of layers of the two-dimensional transition metal chalcogenide obtained by the lift-off method reported in the prior literature is distributed in 1 to 10 layers, and the single layer rate is less than 1%. Therefore, the synthesis method using the transition metal compound MAX or MX as the raw material has higher single-layer rate and narrower layer number distribution compared with the two-dimensional transition metal chalcogenide obtained by the stripping method reported in the prior literature. And the synthesis method has the advantages of simple medium topology conversion reaction conditions, wide reaction condition range, realization of reaction in relatively short time (hours or minutes), industrial macro synthesis prospect, and low energy consumption, high efficiency and high yield compared with a gas phase synthesis method.
Example 11
This example to synthesize WS 2 For example, the synthesis method of the present invention will be described, wherein (W) is selected as the transition metal compound MAX 2/3 Y 1/3 ) 2 AlC, comprising the following steps:
1) A heating step: mixing 100 mg (W) 2/3 Y 1/3 ) 2 The powder of AlC is put into a corundum magnetic boat and placed in the middle area of a tubular furnace, the corundum magnetic boat filled with a proper amount (1 g) of phosphorus powder is placed at the upstream of the tubular furnace capable of independently controlling the temperature, and the temperature in the tube is increased to 1000 ℃ at the speed of 10 ℃/min under the condition that protective gas (argon with the purity of more than 99.999%) is introduced into the tube.
2) Topology transformation reaction step: starting a switch of a heating device filled with a phosphorus powder part, heating to 200 ℃, enabling the phosphorus powder to be heated to generate gaseous phosphorus to enter the middle area of the tubular furnace, starting reaction timing when the temperature in the upstream tube reaches 200 ℃, and switching the atmosphere to be H 2 H with the mass fraction of S of 10 percent 2 And S and argon gas are mixed, the reaction temperature of the middle area of the tubular furnace is kept at 1000 ℃, after the reaction time is 10min, the atmosphere is switched to protective gas, and the temperature in the tube is reduced to room temperature.
Collecting the product obtained in the step 2) as Y and P co-doped WS 2 （Y、P-WS 2 ) The Raman spectrum test was carried out, and the result is shown in FIG. 19, in which the characteristic peak J is shown 1 、J 2 、J 3 Corresponding to 1T phase characteristics, E 1 2g And A 1g Corresponding to the characteristics of the 2H phase. Y-WS obtained in comparative example 10 2 The two-dimensional transition chalcogenide compound is a 2H phase when no phosphorus group element exists in the topological transformation reaction, and the two-dimensional transition chalcogenide compound contains a 1T phase and a 2H phase when the phosphorus group element is added in the topological transformation reaction.
Example 12
This example to prepare MoS 2 The method for preparing a dispersion of a two-dimensional transition metal chalcogenide compound of the present invention is described as an example of the dispersion, and includes the steps of:
the product MoS obtained in example 7 was taken 2 The product MoS 2 Dispersed in isopropyl alcohol (IPA) to prepare 2 mg mL -1 Then ultrasonic treatment is carried out, the ultrasonic power is 300W, the ultrasonic time is 0.5h to 4h, the state pictures of the dispersion under different ultrasonic time are shown in figure 14a, then the dispersion is centrifugally treated, and the dispersion is centrifugally treated at the rotating speed of 1500 r/m for 45min to obtain the dispersion containing MoS 2 The supernatant of the two-dimensional sheet layer is MoS 2 A two-dimensional lamellar dispersion. The obtained MoS 2 Testing the two-dimensional lamellar dispersion liquid through UV-vis-IR spectrum to obtain MoS in the dispersion liquid 2 Concentration of two-dimensional sheet and used to calculate product MoS 2 The stripping yield of (1), i.e. MoS in the dispersion 2 Two-dimensional lamella and addition product MoS 2 The results are shown in FIG. 14b, and it can be seen that MoS peeled off from the dispersion with the increase of the ultrasonic time 2 The two-dimensional lamella is increased, and when the ultrasonic time is 4h, the MoS product is obtained 2 The peel yield of (a) was 37 wt.%.
FIGS. 15a and 15b show the MoS obtained for 4h of sonication as described above 2 SEM and TEM photographs of the dispersion samples. MoS can be clearly seen from the photograph 2 The product MoS is in a two-dimensional sheet layer shape after being peeled off, and the product MoS is obtained after ultrasonic treatment and centrifugal treatment 2 Successful exfoliation from a stacked structure of two-dimensional sheets in an expanded state to MoS 2 Two-dimensional sheet layer, and exfoliation of the resulting MoS 2 The two-dimensional sheet layer can be uniformly and stably dispersed in the dispersion liquid.
To learn MoS 2 MoS in dispersion 2 Thickness of two-dimensional sheet layer, moS obtained by the above ultrasonic 4h 2 Atomic Force Microscopy (AFM) was performed on the dispersion samples and the thickness results were counted as shown in FIG. 16, and it can be seen that the MoS was obtained 2 MoS in dispersion 2 The thickness distribution of the two-dimensional sheet layer is between 0.5nm and 8nm, and the thickness distribution is mainly in the range of 1nm to 5nm, and further proves that the two-dimensional transition metal chalcogenide with single layer and few layers can be obtained by the synthetic method.
The solvent isopropanol was replaced by N-methylpyrrolidone (NMP) under the same conditions, and the results obtained are shown in FIGS. 14c and 14d, as the sonication time increased, the MoS stripped from the dispersion 2 The two-dimensional lamella is increased, and when the ultrasonic time is 4h, the product MoS 2 The peel yield of (a) was 26 wt.%.
MoS in this example 2 MoS in dispersion 2 The concentration of the two-dimensional sheet layer is far higher than that of the commercially available MoS reported in the prior literature 2 By stripping as raw materialMoS obtained by the method 2 The peel yield of the two-dimensional sheet (0.6 wt.% to 4 wt.%).
Example 13
This example takes the product Y-WS obtained in example 10 2 The results of the ultrasonic treatment and the centrifugal treatment in IPA and NMP solvents, respectively, in the same manner as in example 11 are shown in FIG. 17. As can be seen from FIG. 17, the MoS in the dispersion increases with the sonication time 2 The content of two-dimensional lamella is increased, and when the ultrasonic time is 4h, the solvents are Y-WS containing IPA and NMP 2 The peel yields in the two-dimensional lamellar dispersion reached 25 wt.% and 15 wt.%, respectively (FIGS. 17b and 17 d), which is much higher than the commercially available WS reported in the prior art 2 WS obtained by exfoliation method as starting material 2 The peel yield of the two-dimensional sheet (1 wt.% to 2 wt.%).
The preparation method can obtain the high-quality-concentration two-dimensional transition metal chalcogenide dispersion liquid, and the transition metal chalcogenide with the single-layer or few-layer two-dimensional lamellar structure is obtained by the synthesis method, the gaps of the two-dimensional lamellar with the expansion state are easier for solvent molecules to intercalate, and the single-layer or few-layer two-dimensional lamellar stripping process is easier to carry out.
In example 12, selecting IPA as a solvent, 300W of ultrasonic power, and 4h of ultrasonic time gives one example of the maximum peeling yield of the preparation method of the present invention that can adjust the peeling yield of the two-dimensional transition metal chalcogenide by adjusting the ultrasonic power and the ultrasonic time, and selecting different solvents, wherein preferably, the ultrasonic power of ultrasonic peeling is 300W to 1000W, and the ultrasonic time is 0.5h to 6h. The solvent optionally comprises one or more of water, N-methylpyrrolidone, N-dimethylformamide, ethanol, isopropanol, butanone, or toluene.
The above embodiments are only some embodiments of the present invention, and it is obvious to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept of the present invention, and these are all within the protection scope of the present invention.
Claims (15)
1. A method for synthesizing a two-dimensional transition metal chalcogenide, comprising the steps of:
a heating step: heating the transition metal compound to a reaction temperature in an inert gas environment;
topology conversion reaction step: introducing gas containing chalcogen, and keeping the reaction temperature for a set time to enable the chalcogen and the transition metal compound to generate topology conversion reaction to generate two-dimensional transition metal chalcogen;
the transition metal compound comprises MAX or MX, wherein M represents one or more transition metal elements of scandium, titanium, vanadium, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten, A represents one or more elements of aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium or lead, and X in MAX represents carbon element; x in MX represents one of carbon, silicon and boron elements;
the gas containing chalcogen comprises one or more of gaseous sulfur, selenium, tellurium, hydrogen sulfide, hydrogen selenide or hydrogen telluride.
2. The method for synthesizing a two-dimensional transition metal chalcogenide according to claim 1, wherein an atmosphere of the topological transformation reaction step further comprises a gas containing a phosphorus group element, and the chalcogen element and the phosphorus group element undergo a topological transformation reaction with the transition metal compound.
3. The method for synthesizing a two-dimensional transition metal chalcogenide as claimed in claim 1 or 2, wherein the reaction temperature is between 300 ℃ and 1100 ℃ and the set time period is 360min or less.
4. The method for synthesizing a two-dimensional transition metal chalcogenide as claimed in claim 1 or 2, wherein the reaction temperature is between 800 ℃ and 1100 ℃ and the set time period is 30min or less.
5. The method of synthesizing a two-dimensional transition metal chalcogenide as claimed in claim 2 wherein said gas containing a phosphorus group element comprises one or more of gaseous phosphorus, arsenic, phosphine or ammonium phosphide.
6. The method for synthesizing a two-dimensional transition metal chalcogenide as claimed in claim 1 or 2 further comprising the step of preparing said MX before said heating step by:
etching: adding the MAX powder into an acid solution, and etching the element A in the MAX by an acid component in the acid solution to obtain a suspension containing MX;
a cleaning and drying step: and carrying out suction filtration on the suspension, repeatedly washing the suspension by using deionized water, removing the acidic component, and drying to obtain the MX.
7. The method for synthesizing a two-dimensional transition metal chalcogenide as claimed in claim 1 or 2 wherein said MAX comprises Mo 2 Ga 2 C、Mo 2 GeC、Ti 3 SiC 2 、Ti 2 SnC、Ti 2 AlC、Nb 2 AlC、Ta 2 AlC、TiNbAlC、Mo 2 TiAlC 2 Or (W) 2/ 3 Y 1/3 ) 2 One or more of AlC, MX comprises Mo 2 C、Mo 1.33 C、V 2 C、Nb 2 C、Ti 3 C 2 、Ti 4 C 3 、Mo 2 Ti 2 C 3 、Mo 2 TiC 2 、Ta 2 C、Ta 4 C 3 TiNbC, moB or MoSi 2 One or more of them.
8. A method for producing a two-dimensional transition metal chalcogenide dispersion liquid, characterized in that the two-dimensional transition metal chalcogenide obtained by the method for synthesizing a two-dimensional transition metal chalcogenide according to any one of claims 1 to 7 is subjected to ultrasonication and centrifugation in a solvent, and a two-dimensional transition metal chalcogenide dispersion liquid is obtained by taking an upper layer liquid.
9. The method of preparing a two-dimensional transition metal chalcogenide dispersion liquid according to claim 8, wherein the solvent comprises one or more of water, N-methylpyrrolidone, N-dimethylformamide, ethanol, isopropanol, butanone, or toluene.
10. The method for preparing a two-dimensional transition metal chalcogenide dispersion liquid according to claim 8, wherein the ultrasonic treatment is performed at an ultrasonic power of 300W to 1000W for an ultrasonic time of 0.5h to 6h.
11. The method for producing a two-dimensional transition metal chalcogenide dispersion liquid according to any one of claims 8 to 10, wherein the peeling yield of the two-dimensional transition metal chalcogenide is 37 wt.% or less.
12. An aggregate of a two-dimensional transition metal chalcogenide, wherein the aggregate is in the form of a powder, a dispersion liquid, or a compacted solid, and the aggregate contains the two-dimensional transition metal chalcogenide obtained by the synthesis method according to any one of claims 1 to 7, and the monolayer rate of the two-dimensional transition metal chalcogenide is greater than 30%.
13. The aggregate of two-dimensional transition metal chalcogenides according to claim 12, comprising between 1 and 5 layers of the two-dimensional transition metal chalcogenide.
14. The aggregate of two-dimensional transition metal chalcogenides according to claim 12, wherein the thickness of the two-dimensional transition metal chalcogenides contained in the aggregate is between 0.5nm and 8 nm.
15. Use of an aggregate of a two-dimensional transition metal chalcogenide according to anyone of claims 12 to 14 in transistors, logic circuits, sensors, lithium secondary batteries and hydrogen evolution reactions.
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