CN106673063A - Method for preparing component and phase state adjustable transition metal molybdenum disulfide tungsten nanosheet - Google Patents

Method for preparing component and phase state adjustable transition metal molybdenum disulfide tungsten nanosheet Download PDF

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CN106673063A
CN106673063A CN201610888692.7A CN201610888692A CN106673063A CN 106673063 A CN106673063 A CN 106673063A CN 201610888692 A CN201610888692 A CN 201610888692A CN 106673063 A CN106673063 A CN 106673063A
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transition metal
phase
nanometer sheet
metal molybdenum
product
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黄晓
杨凯
黄维
孙方方
戴杰
李彦辰
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Nanjing Tech University
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles

Abstract

The invention discloses a method for preparing a transition metal molybdenum disulfide tungsten nanosheet. Through the adoption of a hydrothermal method, ammonium tungstate, ammonium molybdate and thiourea are taken as raw materials, the transition metal molybdenum disulfide tungsten nanosheet can be synthesized in one step under specific reaction conditions, and the contents of molybdenum element and tungsten element as well as the contents of 1T phase and 2H phase in the product can be changed by adjusting and controlling the reaction conditions such as temperature, reaction time and raw material contents. The reaction product prepared by adopting the technical scheme has good electrochemical and chemical properties, and showa excellent properties in electrochemical hydrogen production. The method is simple and convenient in operation, low in production cost, high in yield and free of byproduct during preparation, and the transition metal molybdenum disulfide tungsten nanosheet can be prepared in large scale commercially.

Description

The method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase
Technical field
The present invention relates to technical field of nano material, and in particular to adjustable using hydro-thermal method one-step synthesis component and phase The preparation method of molybdenum bisuphide tungsten nanometer sheet.
Background technology
Two-dimensional material, such as Graphene and class grapheme material, because its unique property is received with ultra-thin thickness Extensive concern.In numerous class grapheme two-dimension materials, stratiform transition metal dichalcogenide (such as tungsten disulfide, molybdenum bisuphide) Show excellent structure, electricity, optics, chemistry and macroscopic property so that they electronics, catalyst, energy storage and Conversion and sensor field have huge application prospect.
Research finds, the performance of transition metal dichalcogenide be often depending on its crystal structure, pattern, geometry arrangement, Component etc..For example, molybdenum bisuphide and tungsten disulfide produce the catalysis activity on hydrogen and are dependent on phase, octahedral structure in electrochemistry Metallicity 1T compare triangular prism structure semiconductive 2H phases have more preferable electrochemistry produce hydrogen activity, this is due to 1T phases Material has higher electric conductivity and lower hydrogen adsorption energy.
In order to realize the transformation of the phase by 2H phases to 1T phases of molybdenum bisuphide or tungsten disulfide, electronics is generally adopted at present The methods such as doping, lithium ion intercalation, laser emission.
In addition to the method for phase transformation, the alloy material for forming transition metal dichalcogenide by doping can also regulate and control Its property.For example, the MoS for reporting recentlyxSe2-xAnd MoxW1-xS2With adjustable electricity-optics property.However, preparing at present MoxW1-xS2It is the method (such as chemical vapor deposition, ald) by solid state growth.These methods generally need Under hot conditions, and it is usually formed the Mo of 2H phasesxW1-xS2.Although further 1T can be obtained by lithium ion intercalation and stripping The Mo of phasexW1-xS2, but so not only process is loaded down with trivial details and high cost.
The content of the invention
It is an object of the invention to provide a kind of efficient, cheap, the employing one-step synthesis with huge commercial value side Method obtains component and the adjustable transition metal molybdenum bisuphide tungsten alloy nanometer sheet of phase.
Technical scheme：
By hydro-thermal method, with ammonium tungstate, ammonium molybdate and thiocarbamide are raw material, under specific reaction condition, can be closed with a step Into transition metal molybdenum bisuphide tungsten nanometer sheet, its step is as follows：
(1) by ammonium molybdate, either ammonium tungstate is mixed by a certain percentage with thiocarbamide or ammonium molybdate, ammonium tungstate and thiocarbamide with thiocarbamide Close, with water as solvent, in adding the water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) at temperature 200-240 DEG C, 24-60 hours are heated；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice, Obtain transition metal molybdenum bisuphide tungsten nanometer sheet；
(4) constituent content, temperature or the heat time of reactant are adjusted, thus it is possible to vary in product, molybdenum element and tungsten are first The content and 1T phases of element and the content of 2H phases.
Beneficial effect：Using technical scheme, can be with one-step synthesis component and the adjustable transition metal two of phase Sulfuration molybdenum and tungsten alloy nanometer sheet, the raw material that the technical scheme is adopted is cheap and easy to get, and low production cost, yield is high, is adapted to extensive Production, product can be used for the extensive application that electrochemistry produces the fields such as hydrogen as catalyst.
Description of the drawings
Fig. 1 schemes and corresponding crystal structure figure for the SEM of transition metal molybdenum bisuphide tungsten nanometer sheet.
Fig. 2A is the product MoS of embodiment 12The SEM figures of (80%1T, 20%2H).
Fig. 2 B are the product MoS of embodiment 12The EDX figures of (80%1T, 20%2H).
Fig. 2 C are the product MoS of embodiment 12The XRD of (80%1T, 20%2H).
Fig. 2 D are the product MoS of embodiment 12The XPS figures of Mo 3d in (80%1T, 20%2H).
Fig. 2 E are the product figure MoS of embodiment 12The XPS figures of S 2p in (80%1T, 20%2H).
Fig. 3 A are the product MoS of embodiment 22The SEM figures of (10%1T, 90%2H).
Fig. 3 B are the product MoS of embodiment 22The EDX figures of (10%1T, 90%2H).
Fig. 3 C are the product MoS of embodiment 22The XRD of (10%1T, 90%2H).
Fig. 3 D are the product MoS of embodiment 22(10%1T, 90%2H)) in Mo 3d XPS figure.
Fig. 3 E are the product figure MoS of embodiment 22The XPS figures of S 2p in (10%1T, 90%2H).
Fig. 4 A are the product Mo of embodiment 30.96W0.04S2The SEM figures of (80%1T, 20%2H).
Fig. 4 B are the product Mo of embodiment 30.96W0.04S2The EDX figures of (80%1T, 20%2H).
Fig. 4 C are the product Mo of embodiment 30.96W0.04S2The XRD of (80%1T, 20%2H).
Fig. 4 D are the product Mo of embodiment 30.96W0.04S2The XPS figures of Mo 3d in (80%1T, 20%2H).
Fig. 4 E are the product Mo of embodiment 30.96W0.04S2The XPS figures of S 2p in (80%1T, 20%2H).
Fig. 4 F are the product Mo of embodiment 30.96W0.04S2The XPS figures of W 4f in (80%1T, 20%2H).
Fig. 5 A are the product Mo of embodiment 40.92W0.08S2The SEM figures of (60%1T, 40%2H).
Fig. 5 B are the product Mo of embodiment 40.92W0.08S2The EDX figures of (60%1T, 40%2H).
Fig. 5 C are the product Mo of embodiment 40.92W0.08S2The XRD of (60%1T, 40%2H).
Fig. 5 D are the product Mo of embodiment 40.92W0.08S2The XPS figures of Mo 3d in (60%1T, 40%2H).
Fig. 5 E are the product Mo of embodiment 40.92W0.08S2The XPS figures of S 2p in (60%1T, 40%2H).
Fig. 5 F are the product Mo of embodiment 40.92W0.08S2The XPS figures of W 4f in (60%1T, 40%2H).
Fig. 6 A are the product Mo of embodiment 50.87W0.13S2The SEM figures of (30%1T, 70%2H).
Fig. 6 B are the product Mo of embodiment 50.87W0.13S2The EDX figures of (30%1T, 70%2H).
Fig. 6 C are the product Mo of embodiment 50.87W0.13S2The XRD of (30%1T, 70%2H).
Fig. 6 D are the product Mo of embodiment 50.87W0.13S2The XPS figures of Mo 3d in (30%1T, 70%2H).
Fig. 6 E are the product Mo of embodiment 50.87W0.13S2The XPS figures of S 2p in (30%1T, 70%2H).
Fig. 6 F are the product Mo of embodiment 50.87W0.13S2The XPS figures of W 4f in (30%1T, 70%2H).
Fig. 7 A are the product Mo of embodiment 60.87W0.13S2The SEM figures of (10%1T, 90%2H).
Fig. 7 B are the product Mo of embodiment 60.87W0.13S2The EDX figures of (10%1T, 90%2H).
Fig. 7 C are the product Mo of embodiment 60.87W0.13S2The XRD of (10%1T, 90%2H).
Fig. 7 D are the product Mo of embodiment 60.87W0.13S2(10%1T, 90%2H)) in Mo 3d XPS figure.
Fig. 7 E are the product Mo of embodiment 60.87W0.13S2The XPS figures of S 2p in (10%1T, 90%2H).
Fig. 7 F are the product Mo of embodiment 60.87W0.13S2The XPS figures of W 4f in (10%1T, 90%2H).
Fig. 8 A are the product WS of embodiment 72The SEM figures of (80%1T, 20%2H).
Fig. 8 B are the product WS of embodiment 72(80%1T, 20%2H)) EDX figure.
Fig. 8 C are the product WS of embodiment 72The XRD of (80%1T, 20%2H).
Fig. 8 D are the product WS of embodiment 72The XPS figures of Mo 3d in (80%1T, 20%2H).
Fig. 8 E are the product WS of embodiment 62The XPS figures of S 2p in (80%1T, 20%2H).
Specific embodiment
For a better understanding of the present invention, below in conjunction with the accompanying drawings and specific embodiment come further illustrate the present invention skill Art scheme.
As shown in figure 1, the SEM figures and corresponding crystal structure figure of transition metal molybdenum bisuphide tungsten nanometer sheet, and it is corresponding Crystal structure figure, its 1T phase is octahedral structure；2H phases are triangular prism structure.
Embodiment 1：MoS2The synthesis of (80%1T, 20%2H)
(1) take 1mmol, the ammonium molybdate of 1.2483g, the thiocarbamide and 35mL water of 15mmol, 1.1533g, at the same add with 50mL polytetrafluoroethylene (PTFE) is in the water heating kettle of inner bag；
(2) baking oven for being warming up to 200 DEG C in advance is put into after mixing, is heated 24 hours at 200 DEG C；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice.
In the present embodiment, the content of tungsten is 0 in the reactant feed of addition, and the result of above-described embodiment 1 is analyzed, SEM figures as shown in Figure 2 A, the product MoS for finally giving2(80%1T, 20%2H) is nano flower-like.As shown in Figure 2 B, pass through EDX figures can illustrate product MoS2The constituent atoms content accounting of (80%1T, 20%2H) is element sulphur 69.32%, molybdenum element 30.68%, Mo:S≈1:2.As shown in Figure 2 C, MoS2The XRD of (80%1T, 20%2H), 9 ° in figure, 18 °, 33 ° right respectively Answer (002)1T, (004)1T(100) face.
As shown in Figure 2 D, MoS2The XPS figures of Mo 3d in (80%1T, 20%2H), in figure at 228.6eV and 231.7eV Peak correspondence 1T Mo4+, 229.2eV 2H Mos corresponding with the peak at 232.4eV4+, 226.2eV correspondence S 2s tracks.By comparing 1T With the peak area of 2H, can calculate 1T contents are about 80%.
As shown in Figure 2 E, MoS2The XPS figures of S 2p in (80%1T, 20%2H), in figure at 161.2eV and 162.3eV Peak correspondence 1T S2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 80%.
With reference to Fig. 2 C, 2D and 2E, it may be determined that for product MoS2The phase of (80%1T, 20%2H) is octahedral structure Metallicity 1T phase accounting 80%, the semiconductive 2H phases accounting 20% of triangular prism structure.
Embodiment 2：MoS2The synthesis of (10%1T, 90%2H)
(1) 0.5mmol is taken, the ammonium molybdate of 0.6240g, the thiocarbamide of 30mmol, 2.3067g and 35mL water add poly- with 50mL Tetrafluoroethene is in the water heating kettle of inner bag；
(2) baking oven for being warming up to 220 DEG C in advance is put into after mixing, is heated 60 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice.
In the present embodiment, the content of tungsten is 0 in the reactant feed of addition, and the result of above-described embodiment 2 is analyzed, As shown in Figure 3A, MoS2The SEM figures of (10%1T, 90%2H), the MoS that can illustrate to finally give by SEM figures2For nano flower Shape.As shown in Figure 3 B, MoS2The EDX figures of (10%1T, 90%2H), can be illustrated, product transition metal curing by EDX figures The constituent atoms content accounting of molybdenum tungsten nanometer sheet be element sulphur 62.48%, molybdenum element 37.52%, Mo:S≈1:2.
As shown in Figure 3 C, MoS2The XRD of (10%1T, 90%2H), 14 ° in figure, 33 ° correspond to (002) respectively2HWith (100) face.
As shown in Figure 3 D, MoS2The XPS figures of Mo 3d in (10%1T, 90%2H), in figure at 228.6eV and 231.7eV Peak correspondence 1T Mo4+, 229.2eV 2H Mos corresponding with the peak at 232.4eV4+, 226.2eV correspondence S 2s tracks.By comparing 1T With the peak area of 2H, can calculate 1T contents are about 10%.
As shown in FIGURE 3 E, MoS2The XPS figures of S 2p in (10%1T, 90%2H), in figure at 161.2eV and 162.3eV Peak correspondence 1T S2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 10%.
With reference to Fig. 3 C, 3D and 3E, it may be determined that product MoS2The phase of (10%1T, 90%2H) is the gold of octahedral structure Attribute 1T phases accounting 10%, the semiconductive 2H phases accounting 90% of triangular prism structure.
Embodiment 3：Mo0.96W0.04S2The synthesis of (80%1T, 20%2H)
(1) 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g are taken Thiocarbamide and 35mL water add in water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) baking oven for being warming up to 200 DEG C in advance is put into after mixing, is heated 48 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained washes ethanol twice with water and washes twice.
The result of above-described embodiment 3 is analyzed, as shown in Figure 4 A, Mo0.96W0.04S2The SEM of (80%1T, 20%2H) Figure, the Mo that can illustrate to finally give by SEM figures0.96W0.04S2For nano flower-like.
As shown in Figure 4 B, Mo0.96W0.04S2The EDX figures of (80%1T, 20%2H), by EDX figures the group of product can be illustrated Divide atom content accounting for element sulphur 68.23%, molybdenum element 30.17%, wolfram element 1.6%, W:Mo≈1:18.8, correspondence W's Content is about 4%.
As shown in Figure 4 C, Mo0.96W0.04S2The XRD of (80%1T, 20%2H), 9 ° in figure, 18 °, 33 ° correspond to respectively (002)1T,(004)1T(100) face.
As shown in Figure 4 D, Mo0.96W0.04S2In (80%1T, 20%2H) Mo 3d XPS figure, in figure 228.6eV and Peak correspondence 1T Mo at 231.7eV4+, 229.2eV 2H Mos corresponding with the peak at 232.4eV4+, 226.2eV correspondence S 2s rails Road.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 80%.
As shown in Figure 4 E, Mo0.96W0.04S2The XPS figures of S 2p in (80%1T, 20%2H).In figure 161.2eV and Peak correspondence 1T S at 162.3eV2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak face for comparing 1T and 2H Product, can calculate 1T contents are about 80%.
As illustrated in figure 4f, Mo0.96W0.04S2The XPS figures of W 4f, 31.7eV and 33.9eV in figure in (80%1T, 20%2H) The peak correspondence 1T W at place4+, 32.6eV 2H Ws corresponding with the peak at 34.5eV4+, 35.7eV Ws corresponding with the peak at 37.8eV6+, this Outward, the peak at 39.3eV and 36.6eV corresponds to respectively W 5p tracks and Mo 4p tracks.By the peak area for comparing 1T and 2H, can With calculate 1T contents are about 80%.
With reference to Fig. 4 C, 4D, 4E and 4F, product Mo0.96W0.04S2The phase of (80%1T, 20%2H) is octahedral structure Metallicity 1T phase accounting 80%, the semiconductive 2H phases accounting 20% of triangular prism structure.
Embodiment 4：Mo0.92W0.08S2The synthesis of (60%1T, 40%2H)
(1) 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g are taken Thiocarbamide and 35mL water add in water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) baking oven for being warming up to 220 DEG C in advance is put into after mixing, is heated 60 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice.
The result of above-described embodiment 4 is analyzed, as shown in Figure 5A, Mo0.92W0.08S2The SEM of (60%1T, 40%2H) Figure, the Mo that can illustrate to finally give by SEM figures0.92W0.08S2For nano flower-like.
As shown in Figure 5 B, Mo0.92W0.08S2The EDX figures of (60%1T, 40%2H), by EDX figures product component can be illustrated Atom content accounting be element sulphur 64.8%, molybdenum element 32.4%, wolfram element 2.7%, W:Mo≈1:12, the content of correspondence W is about For 8%.
As shown in Figure 5 C, Mo0.92W0.08S2The XRD of (60%1T, 40%2H), 9 ° in figure, 14 °, 33 ° correspond to respectively (002)1T,(002)2H(100) face.
As shown in Figure 5 D, Mo0.92W0.08S2In (60%1T, 40%2H) Mo 3d XPS figure, in figure 228.6eV and Peak correspondence 1T Mo at 231.7eV4+, 229.2eV 2H Mos corresponding with the peak at 232.4eV4+, 226.2eV correspondence S 2s rails Road.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 60%.
As shown in fig. 5e, Mo0.92W0.08S2In (60%1T, 40%2H) S 2p XPS figure, in figure 161.2eV and Peak correspondence 1T S at 162.3eV2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak face for comparing 1T and 2H Product, can calculate 1T contents are about 60%.
As illustrated in figure 5f, Mo0.92W0.08S2The XPS figures of W 4f, 31.7eV and 33.9eV in figure in (60%1T, 40%2H) The peak correspondence 1T W at place4+, 32.6eV 2H Ws corresponding with the peak at 34.5eV4+, 35.7eV Ws corresponding with the peak at 37.8eV6+, this Outward, the peak at 39.3eV and 36.6eV corresponds to respectively W 5p tracks and Mo 4p tracks.By the peak area for comparing 1T and 2H, can With calculate 1T contents are about 60%.
With reference to accompanying drawing 5C, 5D, 5E and 5F, product Mo0.92W0.08S2The phase of (60%1T, 40%2H) is octahedral structure Metallicity 1T phase accounting 60%, the semiconductive 2H phases accounting 40% of triangular prism structure.
Embodiment 5：Mo0.87W0.13S2The synthesis of (30%1T, 70%2H)
(1) 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g are taken Thiocarbamide and 35mL water add in water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) baking oven for being warming up to 240 DEG C in advance is put into after mixing, is heated 48 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice.
The result of above-described embodiment 5 is analyzed, as shown in Figure 6A, Mo0.87W0.13S2The SEM of (30%1T, 70%2H) Figure, the Mo that can illustrate to finally give by SEM figures0.87W0.13S2For nano flower-like.
As shown in Figure 6B, Mo0.87W0.13S2The EDX figures of (30%1T, 70%2H), by EDX figures product transition can be illustrated The constituent atoms content accounting of metal dithionite molybdenum tungsten nanometer sheet be element sulphur 66.7%, molybdenum element 28.32%, wolfram element 4.98%, W:Mo≈1:6, the content of correspondence W is about 13%.
As shown in Figure 6 C, Mo0.87W0.13S2The XRD of (30%1T, 70%2H), 9 ° in figure, 14 °, 33 ° correspond to respectively (002)1T,(002)2H(100) face.
As shown in Figure 6 D, Mo0.87W0.13S2In (30%1T, 70%2H) Mo 3d XPS figure, in figure 228.6eV and Peak correspondence 1T Mo at 231.7eV4+, 229.2eV 2H Mos corresponding with the peak at 232.4eV4+, 233.12eV and 235.91eV The peak correspondence Mo at place6+, 226.2eV correspondence S 2s tracks.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 30%.
As illustrated in fig. 6e, Mo0.87W0.13S2In (30%1T, 70%2H) S 2p XPS figure, in figure 161.2eV and Peak correspondence 1T S at 162.3eV2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak face for comparing 1T and 2H Product, can calculate 1T contents are about 30%.
As fig 6 f illustrates, Mo0.87W0.13S2The XPS figures of W 4f, 31.7eV and 33.9eV in figure in (30%1T, 70%2H) The peak correspondence 1T W at place4+, 32.6eV 2H Ws corresponding with the peak at 34.5eV4+, 35.7eV Ws corresponding with the peak at 37.8eV6+, this Outward, the peak at 39.3eV and 36.6eV corresponds to respectively W 5p tracks and Mo 4p tracks.By the peak area for comparing 1T and 2H, can With calculate 1T contents are about 30%.
With reference to accompanying drawing 6C, 6D, 6E and 6F, product Mo0.87W0.13S2The phase of (30%1T, 70%2H) is octahedral structure Metallicity 1T phase accounting 30%, the semiconductive 2H phases accounting 70% of triangular prism structure.
Embodiment 6：Mo0.87W0.13S2The synthesis of (10%1T, 90%2H)
(1) 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g are taken Thiocarbamide and 35mL water add in water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) it is put into the baking oven for being warming up to 200 DEG C in advance after mixing, heats 24 hours, then heats to 240 DEG C and keep 24 Hour；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice.
The result of above-described embodiment 6 is analyzed, as shown in Figure 7 A, Mo0.87W0.13S2The SEM of (10%1T, 90%2H) Figure, the Mo that can illustrate to finally give by SEM figures0.87W0.13S2For nano flower-like.
As shown in Figure 7 B, Mo0.87W0.13S2The EDX figures of (10%1T, 90%2H), by EDX figures product component can be illustrated Atom content accounting be element sulphur 63.05%, molybdenum element 32.21%, wolfram element 4.73%.W:Mo≈1:6.8, correspondence W's contains Amount about 13%.
As seen in figure 7 c, Mo0.87W0.13S2The XRD of (10%1T, 90%2H), 9 ° in figure, 14 °, 33 ° correspond to respectively (002)1T,(002)2H(100) face.
As illustrated in fig. 7d, Mo0.87W0.13S2In (10%1T, 90%2H) Mo 3d XPS figure, in figure 228.6eV and Peak correspondence 1T Mo at 231.7eV4+, 229.2eV 2H Mos corresponding with the peak at 232.4eV4+, 233.12eV and 235.91eV The peak correspondence Mo at place6+, 226.2eV correspondence S 2s tracks.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 10%.
As seen in figure 7e, Mo0.87W0.13S2In (10%1T, 90%2H) S 2p XPS figure, in figure 161.2eV and Peak correspondence 1T S at 162.3eV2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak face for comparing 1T and 2H Product, can calculate 1T contents are about 10%.
As shown in Figure 7 F, Mo0.87W0.13S2The XPS figures of W 4f, 31.7eV and 33.9eV in figure in (10%1T, 90%2H) The peak correspondence 1T W at place4+, 32.6eV 2H Ws corresponding with the peak at 34.5eV4+, 35.7eV Ws corresponding with the peak at 37.8eV6+, this Outward, the peak at 39.3eV and 36.6eV corresponds to respectively W 5p tracks and Mo 4p tracks.By the peak area for comparing 1T and 2H, can With calculate 1T contents are about 10%.
With reference to accompanying drawing 7C, 7D, 7E and 7F, product Mo0.87W0.13S2The phase of (10%1T, 90%2H) is octahedral structure Metallicity 1T phase accounting 10%, the semiconductive 2H phases accounting 90% of triangular prism structure.
Embodiment 7：WS2The synthesis of (80%1T, 20%2H)
(1) thiocarbamide and 35mL water of 0.5mmol, 1.7485g ammonium tungstate and 30mmol, 2.3067g is added with 50mL poly- four PVF is in the water heating kettle of inner bag；
(2) baking oven for being warming up to 200 DEG C in advance is put into after mixing, is heated 24 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice.
In the present embodiment, the content of molybdenum is 0 in the reactant feed of addition, the result of above-described embodiment 7 is carried out point Analysis, as shown in Figure 8 A, WS2The SEM figures of (80%1T, 20%2H), the WS that can illustrate to finally give by SEM figures2For nanometer sheet Shape.
As shown in Figure 8 B, WS2The EDX figures of (80%1T, 20%2H), can illustrate that the constituent atoms produced contain by EDX figures Amount accounting be element sulphur 66.66%, wolfram element 33.33%, W:S≈1:2.
As shown in Figure 8 C, WS2The XRD of (80%1T, 20%2H), 9 ° in figure, 18 °, 33 ° correspond to (002) respectively1T, (004)1T(100) face.
As in fig. 8d, WS2The XPS figures of W 4f, the peak pair in figure at 31.7eV and 33.9eV in (80%1T, 20%2H) Answer 1T W4+, 32.6eV 2H Ws corresponding with the peak at 34.5eV4+, 35.7eV Ws corresponding with the peak at 37.8eV6+, additionally, 39.3eV The peak correspondence W 5p tracks at place.By the peak area for comparing 1T and 2H, can calculate 1T contents are about 80%.
As illustrated in fig. 8e, WS2The XPS figures of S 2p, the peak in figure at 161.2eV and 162.3eV in (80%1T, 20%2H) Correspondence 1T S2-, 162.1eV 2H Ss corresponding with the peak at 163.3eV2-.By the peak area for comparing 1T and 2H, 1T can be calculated to obtain Content is about 80%.
With reference to accompanying drawing 7C, 7D, 7E and 7F, product WS2The phase of (80%1T, 20%2H) is the metallicity of octahedral structure 1T phases accounting 80%, the semiconductive 2H phases accounting 20% of triangular prism structure.
As shown in table 1, it is transition metal molybdenum bisuphide tungsten nanometer sheet temperature and the relation and temperature of component and the pass of phase System, the temperature of heating is higher, and the 2H phase contents in transition metal molybdenum bisuphide tungsten nanometer sheet are higher；The temperature of heating is higher, mistake The content of the tungsten crossed in metal dithionite molybdenum tungsten nanometer sheet is higher, and the heat time is longer, transition metal molybdenum bisuphide tungsten nanometer sheet In 2H phase contents it is higher.
Temperature (DEG C) The content (%) of W 1T phase contents (%)
200 4 ~80
220 8 ~60
240 13 ~30
Table 1 is transition metal molybdenum bisuphide tungsten nanometer sheet temperature and the relation and temperature of component and the relation of phase.

Claims (10)

1. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase, is characterized in that, by hydro-thermal method One step prepares component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase, and its step is as follows：
(1) by ammonium molybdate, either ammonium tungstate mixes by a certain percentage with thiocarbamide or ammonium molybdate, ammonium tungstate with thiocarbamide with thiocarbamide, with Water is solvent, in adding the water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) at temperature 200-240 DEG C, 24-60 hours are heated；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice, is obtained Transition metal molybdenum bisuphide tungsten nanometer sheet；
(4) by the constituent content of regulation reactant, temperature or heat time, the transition metal of different component and phase is generated Molybdenum bisuphide tungsten nanometer sheet.
2. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, It is characterized in that:
(1) 1mmol, the ammonium molybdate of 1.2483g, the thiocarbamide and 35mL water of 15mmol, 1.1533g are taken, while adding poly- with 50mL Tetrafluoroethene is in the water heating kettle of inner bag；
(2) baking oven for being warming up to 200 DEG C in advance is put into after mixing, is heated 24 hours at 200 DEG C；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal molybdenum disulfide nano sheet for octahedral structure metallicity 1T phase accounting 80%, Rhizoma Sparganii The semiconductive 2H phases accounting 20% of rod structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 69.32%, molybdenum element 30.68%.
3. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, It is characterized in that：
(1) 0.5mmol is taken, the ammonium molybdate of 0.6240g, the thiocarbamide of 30mmol, 2.3067g and 35mL water are added with 50mL polytetrafluoros Ethene is in the water heating kettle of inner bag；
(2) baking oven for being warming up to 220 DEG C in advance is put into after mixing, is heated 60 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal molybdenum disulfide nano sheet for octahedral structure metallicity 1T phase accounting 10%, Rhizoma Sparganii The semiconductive 2H phases accounting 90% of rod structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 62.48%, molybdenum element 37.52%.
4. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, Characterized in that,
(1) sulphur of 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g is taken Urea and 35mL water are added in the water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) baking oven for being warming up to 200 DEG C in advance is put into after mixing, is heated 48 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal molybdenum bisuphide tungsten nanometer sheet for octahedral structure metallicity 1T phase accounting 80%, three The semiconductive 2H phases accounting 20% of prism structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 68.23%, molybdenum element 30.17%, wolfram element 1.6%.
5. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, It is characterized in that：
(1) sulphur of 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g is taken Urea and 35mL water are added in the water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) baking oven for being warming up to 220 DEG C in advance is put into after mixing, is heated 60 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal molybdenum bisuphide tungsten nanometer sheet for octahedral structure metallicity 1T phase accounting 60%, three The semiconductive 2H phases accounting 40% of prism structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 64.8%, molybdenum element 32.4%, wolfram element 2.7%.
6. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, It is characterized in that：
(1) sulphur of 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g is taken Urea and 35mL water are added in the water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) baking oven for being warming up to 240 DEG C in advance is put into after mixing, is heated 48 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal molybdenum bisuphide tungsten nanometer sheet for octahedral structure metallicity 1T phase accounting 30%, three The semiconductive 2H phases accounting 70% of prism structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 66.7%, molybdenum element 28.32%, wolfram element 4.98%.
7. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, It is characterized in that：
(1) sulphur of 0.25mmol, the ammonium molybdate of 0.3120g, 0.25mmol, 0.8743g ammonium tungstate and 30mmol, 2.3067g is taken Urea and 35mL water are added in the water heating kettle with 50mL polytetrafluoroethylene (PTFE) as inner bag；
(2) it is put into the baking oven for being warming up to 200 DEG C in advance after mixing, heats 24 hours, then heats to 240 DEG C and keep 24 little When；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal molybdenum bisuphide tungsten nanometer sheet for octahedral structure metallicity 1T phase accounting 10%, three The semiconductive 2H phases accounting 90% of prism structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 63.05%, molybdenum element 32.21%, wolfram element 4.73%.
8. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, It is characterized in that：
(1) thiocarbamide and 35mL water of 0.5mmol, 1.7485g ammonium tungstate and 30mmol, 2.3067g is added with 50mL polytetrafluoroethyl-nes Alkene is in the water heating kettle of inner bag；
(2) baking oven for being warming up to 200 DEG C in advance is put into after mixing, is heated 24 hours；
(3) reaction terminates rear natural cooling, and the product centrifugation that reaction is obtained is washed with water twice, and ethanol is washed twice；
(4) phase of product transition metal tungsten disulfide nano slices for octahedral structure metallicity 1T phase accounting 80%, Rhizoma Sparganii The semiconductive 2H phases accounting 20% of rod structure；
(5) the constituent atoms content accounting of product transition metal molybdenum bisuphide tungsten nanometer sheet is element sulphur 66.66%, wolfram element 33.33%.
9. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, Characterized in that, the temperature of heating is higher, the 2H phase contents in transition metal molybdenum bisuphide tungsten nanometer sheet are higher；The temperature of heating Higher, the content of the tungsten in transition metal molybdenum bisuphide tungsten nanometer sheet is higher.
10. the method for preparing component and the adjustable transition metal molybdenum bisuphide tungsten nanometer sheet of phase according to claim 1, Characterized in that, the heat time is longer, the 2H phase contents in transition metal molybdenum bisuphide tungsten nanometer sheet are higher.
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CN110697777A (en) * 2019-10-09 2020-01-17 西北工业大学 Preparation method of tin molybdenum disulfide with hollow structure
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