CN106904580A - Using the method for the two-dimensional nano piece of hydro-thermal method synthesis 1T phase degree of disorder coordinated regulations - Google Patents

Using the method for the two-dimensional nano piece of hydro-thermal method synthesis 1T phase degree of disorder coordinated regulations Download PDF

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CN106904580A
CN106904580A CN201710137965.9A CN201710137965A CN106904580A CN 106904580 A CN106904580 A CN 106904580A CN 201710137965 A CN201710137965 A CN 201710137965A CN 106904580 A CN106904580 A CN 106904580A
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CN106904580B (en
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宋波
银颖
张宇民
韩杰才
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Harbin Institute of Technology
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
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Abstract

Using the method for the two-dimensional nano piece of hydro-thermal method synthesis 1T phase degree of disorder coordinated regulations, the present invention relates to a kind of preparation method of two-dimensional nano piece, it will solve existing MX2Nanometer sheet is usually the 2H phase structures of semiconductor property, and the problem to the regulation and control of crystallographic disorder degree relatively difficult to achieve.Synthetic method：First, it is in molar ratio 1：2：Be scattered in deionized water for precursor compound containing transition metal, the simple substance of chalcogen or the compound of elemental precursor containing chalcogen and reducing agent by (2~10)；2nd, control heating-up temperature carries out hydro-thermal reaction, and wash products obtain two-dimentional MX2Nano material；3rd, drying and processing.The present invention realizes the two-dimensional nano piece of a step 1T phase degree of disorder coordinated regulations by hydro-thermal method, and the regulation and control to 1T phase contents are realized by the amount for adjusting reducing agent, and the regulation of the nanometer sheet lattice degree of disorder is realized by the temperature for adjusting hydro-thermal reaction.And the two-dimensional nano piece for obtaining has good catalyzing manufacturing of hydrogen efficiency.

Description

Using the method for the two-dimensional nano piece of hydro-thermal method synthesis 1T phases-degree of disorder coordinated regulation
Technical field
The present invention relates to a kind of preparation method of two-dimensional nano piece.
Background technology
Transistion metal compound MX with two-dimensional structure2(M=Mo, W；X=S, Se, Te) nanometer sheet is due to its uniqueness Atom geometry is distributed and electronic structure, in recent years in electro-catalysis hydrogen manufacturing, ultracapacitor, the conversion of lithium sode cell equal energy source and storage Application field is of great interest, and is to be oriented to carry out reasonable and controllable structure to two-dimension nano materials and set with function Meter, becomes the research emphasis of the material system.
As a example by using two-dimension nano materials as the electrocatalyst materials of electro-catalysis hydrogen manufacturing, theoretical and experimental study shows it Catalysis activity depends on the conductive capability and unsaturated bonding atom (crystal is unordered) two factors of structure simultaneously, efficient to realize Electro-catalysis function, coordinated regulation should be carried out to the electron transfer capacity of two-dimensional material and structural disorder degree.However, current pin To MX2The research work of system is concentrated mainly on design and optimization side to its thermodynamics equilibrium transport i.e. hexagonal phase (2H phases) structure Face.However, the MX of 2H phases2It is semiconductor, the poor ability of electronics is conducted, this greatly limits its electro-chemical activity.
Conversely, metastable octahedral structure (1T phases) MX2Electronic structure with metallicity, this is advantageous to catalysis The electric charge transfer of material internal so that the atomic ratio for participating in liberation of hydrogen catalytic reaction is significantly increased, and can be greatly enhanced MX2's Catalytic capability.Therefore, rational structure 1T phase structures turn into realize one of key point of efficient catalytic.Further, effectively adjusting On the basis of control 1T phase structures, introduce lattice disorder to increase avtive spot, to realize MX by multifactor cooperative effect2Urge Change the maximization of activity.
At present, in design and construction technology there is larger difficulty in phase transformation-unordered concerted catalysis material.First, crystal without The introducing of sequence generally follows the route of " from bottom to top ", i.e., in the method such as solvent heat or chemical vapor deposition, by reducing material The synthesis temperature of material, relative amount of feed change etc. control the crystallization degree of material, so as to realize order-disorder structure Regulation；However, the MX of 1T phase structures2Crystal typically but follows the mentality of designing of " from top to bottom ", i.e., molten first with n-BuLi Liquid, electrochemistry insert the lithium ion intercalation method of lithium, liquefied ammonia/lithium solution etc., induction 2H MX2There is 2H-1T phase transformations in crystal, then Further peel off is individual layer or few layer 1T phase nanometer sheets.Therefore, the contradiction of disordered structure and 1T phases on design direction is caused Two-dimentional MX2Coordinated regulation becomes difficult to be realized to the two in material.So far, there is not been reported for the research work of this respect.
The content of the invention
The invention aims to solve existing MX2Nanometer sheet is usually the 2H phase structures of semiconductor property, and relatively difficult to achieve To the problem of crystallographic disorder degree regulation and control, and provide a kind of two-dimensional nano of utilization hydro-thermal method synthesis 1T phases-degree of disorder coordinated regulation The method of piece.
The present invention follow these steps to reality using the method for the two-dimensional nano piece of hydro-thermal method synthesis 1T phases-degree of disorder coordinated regulation It is existing：
First, by the precursor compound containing transition metal M, the simple substance of chalcogen X or elemental precursor containing chalcogen Compound and reducing agent A example M in molar ratio：X：A=1：2：(2~10) mix, at room temperature by mixture be scattered in from In sub- water, mixed solution is obtained after being sufficiently stirred for；
2nd, the mixed solution that step one is obtained is transferred in sealing container, is carried out with steady temperature heating sealing container Hydro-thermal reaction, reaction stops to be cooled to room temperature after terminating, and collection, wash products obtain two-dimentional MX2Nano material；
3rd, drying and processing is finally carried out, dry powdered two-dimentional MX is obtained2Nanometer sheet material；
M wherein described in step one represents Mo or W, and the precursor compound containing transition metal M is positive ammonium molybdate ((NH4)2MoO4), ammonium paramolybdate ((NH4)6Mo7O24), ammonium dimolybdate ((NH4)2Mo2O7), ammonium tetramolybdate ((NH4)2Mo4O13), molybdenum Sour sodium and its hydrate (Na2MoO4·H2O), ammonium tungstate and its hydrate ((NH4)2WO4) or sodium tungstate and its hydrate (Na2WO4·H2O)；Described X represents S, Se or Te；Reducing agent A is lithium borohydride (LiBH4), sodium borohydride (NaBH4), boron hydrogen Change potassium (KBH4) or hydrazine hydrate (N2H4·H2O)。
The present invention realizes the two-dimentional MX of 1T phases-degree of disorder coordinated regulation by one step hydro thermal method2The preparation of nanometer sheet, with Existing synthesis mode is compared, MX prepared by traditional approach2Nanometer sheet is usually the 2H phase structures of semiconductor property, and relatively difficult to achieve Regulation and control to crystallographic disorder degree, and MX prepared by the present invention2Nanometer sheet is metallicity 1T phase structures, is advantageously being received in electric charge Transfer inside rice piece, and can realize, to the Effective Regulation of 1T phase contents, on this basis, leading to by adjusting the ratio of reducing agent The temperature for overregulating hydro-thermal reaction realizes the Effective Regulation of the nanometer sheet lattice degree of disorder.
The two-dimentional MX prepared using the present invention2Nanometer sheet material as electrocatalytic decomposition water catalyst for preparing hydrogen, through reality Test the two-dimentional MX that result shows present invention preparation2Nanometer sheet can simultaneously optimize electron transfer capacity and avtive spot, with excellent Good catalyzing manufacturing of hydrogen efficiency.
Brief description of the drawings
Fig. 1 is the two selenizing molybdenum (MoSe obtained in embodiment one2) nanometer sheet transmission microscopy figure (TEM)；
Fig. 2 is the Raman spectrogram (Raman of the two selenizing molybdenum nanometer sheets that different reducing agent ratios are obtained in embodiment one Shift), wherein represents 1T phases, and zero represents 2H phases；
Fig. 3 is the high-resolution x-ray photoelectron of the two selenizing molybdenum nanometer sheets that different reducing agent ratios are obtained in embodiment one Energy spectrum diagram (XPS)；
Fig. 4 is the SEAD figure of the two selenizing molybdenum nanometer sheets that reaction temperature is obtained at 140 DEG C in embodiment two (SAED)；
Fig. 5 is the SEAD figure of the two selenizing molybdenum nanometer sheets that reaction temperature is obtained at 160 DEG C in embodiment two；
Fig. 6 is the SEAD figure of the two selenizing molybdenum nanometer sheets that reaction temperature is obtained at 180 DEG C in embodiment two；
Fig. 7 is the SEAD figure of the two selenizing molybdenum nanometer sheets that reaction temperature is obtained at 200 DEG C in embodiment two；
Fig. 8 is the Raman shift figure of the two selenizing molybdenum nanometer sheets that differential responses temperature is obtained in embodiment two, wherein generations Table 1T phases, zero represents 2H phases；
Fig. 9 is the high-resolution x-ray photoelectron power spectrum of the two selenizing molybdenum nanometer sheets obtained in embodiment two；
Figure 10 is the two selenizing molybdenum nanometer sheet electro-catalysis hydrogen manufacturing polarization curves that differential responses temperature is obtained in embodiment two, ☆ represents MoSe in figure2- 1-180, represent MoSe2- 4-140, zero represents MoSe2- 4-160, △ represent MoSe2- 4-180, ▽ Represent MoSe2- 4-200,Represent Pt.
Specific embodiment
Specific embodiment one：Present embodiment synthesizes the two-dimensional nano of 1T phases-degree of disorder coordinated regulation using hydro-thermal method The method of piece follow these steps to realize：
First, by the precursor compound containing transition metal M, the simple substance of chalcogen X or elemental precursor containing chalcogen Compound and reducing agent A example M in molar ratio：X：A=1：2：(2~10) mix, at room temperature by mixture be scattered in from In sub- water, mixed solution is obtained after being sufficiently stirred for；
2nd, the mixed solution that step one is obtained is transferred in sealing container, heating sealing container carries out hydro-thermal reaction, instead Room temperature is cooled to after should terminating, collection, wash products obtain two-dimentional MX2Nano material；
3rd, drying and processing is finally carried out, dry powdered two-dimentional MX is obtained2Nanometer sheet material；
M wherein described in step one represents Mo or W, and the precursor compound containing transition metal M is positive ammonium molybdate ((NH4)2MoO4), ammonium paramolybdate ((NH4)6Mo7O24), ammonium dimolybdate ((NH4)2Mo2O7), ammonium tetramolybdate ((NH4)2Mo4O13), molybdenum Sour sodium and its hydrate (Na2MoO4·H2O), ammonium tungstate and its hydrate ((NH4)2WO4) or sodium tungstate and its hydrate (Na2WO4·H2O)；Described X represents S, Se or Te；Reducing agent A is lithium borohydride (LiBH4), sodium borohydride (NaBH4), boron hydrogen Change potassium (KBH4) or hydrazine hydrate (N2H4·H2O)。
The purity of the reaction raw materials in present embodiment step one is not less than 99.99%, and the simple substance of the chalcogen X is Sulphur powder (S), selenium powder (Se) or tellurium powder (Te).
Present embodiment utilizes hydrothermal synthesis method, by one-step method in two-dimentional MX21T phases-structural disorder association is constructed in material Same adjustment and control system.In hydrothermal reaction process, along with MX2Formation, excessive reducing agent potentially acts as electron donor, to MX2 Middle injection electronics, induces it that 2H-1T phase transformations occur.By changing the ratio of reducing agent in synthesis material, to MX2Middle 1T phases contain Effective regulation of amount；Further, by changing Hydrothermal Synthesiss temperature, can realize to two-dimentional MX2Crystallinity (i.e. lattice without Sequence degree) regulation and control, finally realize the MX of 1T phases-degree of disorder collaboration optimization2Catalyst system and catalyzing.
Specific embodiment two：Present embodiment from unlike specific embodiment one described in step one containing chalcogen Elemental precursor compound is vulcanized sodium (Na2S), ATS (Ammonium thiosulphate) ((NH4)2S2O3), sodium thiosulfate (Na2S2O3), half Guang ammonia Acid (C3H7NO2S), thiocarbamide (CH4N2S), sodium selenide (Na2) or telluride sodium (Na Se2Te).Other steps and parameter and specific implementation Mode one is identical.
Specific embodiment three：Present embodiment will contain transition gold from step one unlike specific embodiment one or two Belong to precursor compound, the simple substance of chalcogen X or the compound of elemental precursor containing chalcogen and the reducing agent A massages of element M You are ratio M：X：A=1：2：2 mixing.Other steps and parameter are identical with specific embodiment one or two.
Specific embodiment four：Described in step 2 unlike one of present embodiment and specific embodiment one to three Sealing container is the stainless steel cauldron with polytetrafluoroethyllining lining.Other steps and parameter and specific embodiment one to three it One is identical.
Specific embodiment five：Step 2 unlike one of present embodiment and specific embodiment one to four is placed in drum Wind drying box or Muffle furnace are heated to sealing container.Other steps and parameter are identical with one of specific embodiment one to four.
Specific embodiment six：Step 2 is with 140 unlike one of present embodiment and specific embodiment one to five DEG C~240 DEG C of temperature hydro-thermal reaction 2~48 hours.Other steps and parameter are identical with one of specific embodiment one to five.
Present embodiment realizes the Effective Regulation of the nanometer sheet lattice degree of disorder by adjusting the temperature of hydro-thermal reaction.
Specific embodiment seven：Present embodiment is from step 2 unlike specific embodiment six with 140 DEG C~200 DEG C Temperature hydro-thermal reaction 8~12 hours.Other steps and parameter are identical with specific embodiment six.
Specific embodiment eight：Present embodiment is from step 2 unlike specific embodiment seven with 180 DEG C of temperature Hydro-thermal reaction 12 hours.Other steps and parameter are identical with specific embodiment seven.
Specific embodiment nine：Step 2 reaction knot unlike one of present embodiment and specific embodiment one to eight Room temperature is cooled to after beam, the solid product in sealing container is collected, cleans multiple using deionized water, and by centrifuge Collect product.Other steps and parameter are identical with one of specific embodiment one to eight.
Specific embodiment ten：Present embodiment from unlike specific embodiment nine by centrifuge with 3000~ The speed of 15000r/min is collected by centrifugation product.Other steps and parameter are identical with specific embodiment nine.
Embodiment one：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, by the positive ammonium molybdates of 0.001mol and 0.002mol selenium powders, a series of sodium borohydride respectively with moles mixes, It is scattered at room temperature in 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtains mixed solution；Wherein boron The mole of sodium hydride is respectively 0.001mol, 0.002mol, 0.003mol, 0.004mol；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum In wind drying box hydro-thermal be heated to 180 DEG C react 12 hours, reaction terminate after be cooled to room temperature, by deionized water clean it is many It is secondary, it is collected by centrifugation and obtains two-dimentional two selenizings molybdenum (MoSe2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two-dimentional two selenizings molybdenum nanometer sheet material is obtained.
The two-dimension nano materials that the present embodiment is obtained are the selenizing molybdenum nanometer sheet of partially crystallizable two of different 1T phases contents, boron hydrogen The transmission electron microscope figure of two selenizing molybdenum nanometer sheet materials that the mole for changing sodium is obtained when being 0.004mol as shown in figure 1, Raman spectrum is as shown in Fig. 2 x-ray photoelectron power spectrum is as shown in Figure 3, it is seen that with the raising of the amount of reducing agent, two selenizing molybdenums 1T phase characters peak is more and more obvious in nanometer sheet, and corresponding 1T phases content gradually increases.MoSe in figure2- 1-180 represents hydroboration The embodiment when mole of sodium is 0.001mol, MoSe2When -2-180 represents the mole of sodium borohydride as 0.002mol Embodiment, MoSe2Embodiment when -3-180 represents the mole of sodium borohydride as 0.003mol, MoSe2- 4-180 represents boron hydrogen The embodiment when mole for changing sodium is 0.004mol.
Embodiment two：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, the positive ammonium molybdates of 0.001mol and 0.002mol selenium powders are mixed with 0.004mol sodium borohydrides, is divided at room temperature Dissipate in 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtain mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 140 DEG C are separately heated in wind drying box, 160 DEG C, 180 DEG C, 200 DEG C are reacted 12 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain two-dimentional two selenizings molybdenum (MoSe2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two-dimentional two selenizings molybdenum nanometer sheet material is obtained.
The two-dimension nano materials that the present embodiment is obtained are the selenizing molybdenum nanometer sheet of 1T phases two of different crystallinity (degree of disorder).Its As also shown in e.g. figs. 4-7, Raman spectrum is as shown in figure 8, x-ray photoelectron power spectrum is as shown in figure 9, electrochemistry for SEAD figure Performance liberation of hydrogen polarization curve is as shown in Figure 10.It can be seen that with the rising of reaction temperature, the crystalline quality of two selenizing molybdenum nanometer sheets by Gradually improve, i.e., the degree of disorder is gradually reduced, while embodying obvious 1T phase characters peak, the bar of optimization is cooperateed with the degree of disorder in 1T phases Under part, product embodies optimal catalysis activity.MoSe in figure2- 4-140 represents embodiment at 140 DEG C, MoSe2- 4-160 generations Embodiment during 160 DEG C of table, MoSe2- 4-180 represents embodiment at 180 DEG C, MoSe2- 4-200 represents implementation at 200 DEG C Example.
The electrocatalysis characteristic of sample under different synthesis conditions is summarized in table 1 below, it is seen that in reducing agent NaBH4Mole is 0.004mol, when reaction temperature is 180 DEG C, in sample MoSe21T phases and crystallinity in -4-180 are optimal, so as to realize The optimum value of catalytic performance.Specifically, MoSe2- 4-180 is in current density j=-10mA cm-2The overpotential η at place= 152mV vs RHE, Tafel slope are 52mV dec-1。
Table 1 is the phase content and electrocatalysis characteristic parameter of sample under different synthesis conditions
Embodiment three：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, the positive ammonium molybdates of 0.001mol and 0.002mol thiocarbamides are mixed with 0.002mol sodium borohydrides, is divided at room temperature Dissipate in 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtain mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 140 DEG C are separately heated in wind drying box, 160 DEG C, 180 DEG C, 200 DEG C are reacted 12 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain molybdenum bisuphide (MoS2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered molybdenum bisuphide (MoS is obtained2) nanometer sheet material.
The two-dimension nano materials that the present embodiment is obtained are the 1T phase molybdenum disulfide nano sheets of different crystallinity (degree of disorder).
Example IV：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, 0.001mol sodium tungstates and 0.002mol thiocarbamides are mixed with 0.002mol sodium borohydrides, is disperseed at room temperature In 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtains mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 160 DEG C are separately heated in wind drying box, 180 DEG C, 200 DEG C, 220 DEG C are reacted 24 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain two-dimentional tungsten disulfide (WS2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two-dimentional tungsten disulfide (WS is obtained2) nanometer sheet material.
The two-dimension nano materials that the present embodiment is obtained are the 1T phase tungsten disulfide nano slices of different crystallinity (degree of disorder).
Embodiment five：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, 0.001mol sodium tungstates and 0.002mol selenium powders are mixed with 0.002mol sodium borohydrides, is disperseed at room temperature In 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtains mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 160 DEG C are separately heated in wind drying box, 180 DEG C, 200 DEG C, 220 DEG C are reacted 12 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain two tungsten selenide (WSe2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two tungsten selenides (WSe is obtained2) nanometer sheet material.
The two-dimension nano materials that the present embodiment is obtained are the tungsten selenide nanometer sheet of 1T phases two of different crystallinity (degree of disorder).
Embodiment six：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, 0.001mol sodium molybdates and 0.002mol selenium powders are mixed with 0.002mol hydrazine hydrates, is scattered at room temperature In 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtains mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 140 DEG C are separately heated in wind drying box, 160 DEG C, 180 DEG C, 200 DEG C are reacted 12 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain two selenizing molybdenum (MoSe2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two selenizings molybdenum (MoSe is obtained2) nanometer sheet material.
The two-dimension nano materials that the present embodiment is obtained are the selenizing molybdenum nanometer sheet of 1T phases two of different crystallinity (degree of disorder).
Embodiment seven：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, 0.001mol sodium molybdates and 0.002mol telluriums powder are mixed with 0.002mol hydrazine hydrates, is scattered at room temperature In 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtains mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 140 DEG C are separately heated in wind drying box, 160 DEG C, 180 DEG C, 200 DEG C are reacted 12 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain two telluride molybdenum (MoTe2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two telluride molybdenum (MoTe is obtained2) nanometer sheet material.
The two-dimension nano materials that the present embodiment is obtained are the telluride molybdenum nanometer sheet of 1T phases two of different crystallinity (degree of disorder).
Embodiment eight：The present embodiment synthesizes the method for the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method It follow these steps to realize：
First, 0.001mol sodium tungstates and 0.002mol telluriums powder are mixed with 0.002mol hydrazine hydrates, is scattered at room temperature In 30mL deionized waters, 40min is sufficiently stirred for by magnetic stirring apparatus, obtains mixed solution；
2nd, the mixed solution that step one is obtained is transferred in the stainless steel cauldron of 40mL polytetrafluoroethyllining linings, drum 140 DEG C are separately heated in wind drying box, 160 DEG C, 180 DEG C, 200 DEG C are reacted 12 hours, and reaction is cooled to room temperature after terminating, and are led to Cross deionized water cleaning multiple, be collected by centrifugation and obtain two telluride tungsten (WTe2) nanometer sheet；
3rd, drying and processing is finally carried out, dry powdered two telluride tungsten (WTe is obtained2) nanometer sheet material.
The two-dimension nano materials that the present embodiment is obtained are the telluride tungsten nanometer sheet of 1T phases two of different crystallinity (degree of disorder).
Shown by above example, the present invention can successfully prepare 1T phases-degree of disorder coordinated regulation by hydro-thermal method Two-dimentional MX2Nanometer sheet, and can be realized to the Effective Regulation of 1T phase contents, by adjusting hydro-thermal by adjusting the ratio of reducing agent The environment temperature of reaction realizes effective regulation of the nanometer sheet lattice degree of disorder.The two-dimentional MX2Nanometer sheet optimizes electronics simultaneously Transfer ability and avtive spot, realize the hydrogen production efficiency of high catalytic activity.

Claims (10)

1. the method for synthesizing the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation using hydro-thermal method, it is characterised in that be by following Step is realized：
First, by the precursor compound containing transition metal M, the simple substance of chalcogen X or the chemical combination of elemental precursor containing chalcogen Thing and reducing agent A example M in molar ratio：X：A=1：2：(2~10) mix, mixture is scattered in deionized water at room temperature In, obtain mixed solution after being sufficiently stirred for；
2nd, the mixed solution that step one is obtained is transferred in sealing container, hydro-thermal is carried out with steady temperature heating sealing container Reaction, reaction stops to be cooled to room temperature after terminating, and collection, wash products obtain two-dimentional MX2Nano material；
3rd, drying and processing is finally carried out, dry powdered two-dimentional MX is obtained2Nanometer sheet material；
M wherein described in step one represents Mo or W, and the precursor compound containing transition metal M is positive ammonium molybdate, secondary molybdenum Sour ammonium, ammonium dimolybdate, ammonium tetramolybdate, sodium molybdate and its hydrate, ammonium tungstate and its hydrate or sodium tungstate and its hydrate；Institute The X for stating represents S, Se or Te；Reducing agent A is lithium borohydride, sodium borohydride, potassium borohydride or hydrazine hydrate.
2. the method that utilization hydro-thermal method according to claim 1 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that the compound of elemental precursor containing chalcogen described in step one be vulcanized sodium, ATS (Ammonium thiosulphate), sodium thiosulfate, Cysteine, thiocarbamide, sodium selenide or telluride sodium.
3. the method that utilization hydro-thermal method according to claim 1 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that before step one is by the precursor compound containing transition metal M, the simple substance of chalcogen X or containing chalcogen Drive body compound and reducing agent A example M in molar ratio：X：A=1：2：2 mixing.
4. the method that utilization hydro-thermal method according to claim 1 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that the sealing container described in step 2 is the stainless steel cauldron with polytetrafluoroethyllining lining.
5. the method that utilization hydro-thermal method according to claim 1 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that step 2 is placed in air dry oven or Muffle furnace being heated to sealing container.
6. the method that utilization hydro-thermal method according to claim 1 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that step 2 is with 140 DEG C~240 DEG C of temperature hydro-thermal reaction 2~48 hours.
7. the method that utilization hydro-thermal method according to claim 6 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that step 2 is with 140 DEG C~200 DEG C of temperature hydro-thermal reaction 8~12 hours.
8. the method that utilization hydro-thermal method according to claim 7 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that step 2 is with 180 DEG C of temperature hydro-thermal reaction 12 hours.
9. the method that utilization hydro-thermal method according to claim 1 synthesizes the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation, It is characterized in that step 2 reaction is cooled to room temperature after terminating, the solid product in sealing container is collected, it is clear using deionized water Wash repeatedly, and product is collected by centrifuge.
10. utilization hydro-thermal method according to claim 9 synthesizes the side of the two-dimensional nano piece of 1T phases-degree of disorder coordinated regulation Method, it is characterised in that product is collected by centrifugation with the speed of 3000~15000r/min by centrifuge.
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