CN107117659A - The side NiPS of high-quality ultra-thin six3Nanometer sheet and its large area preparation method - Google Patents
The side NiPS of high-quality ultra-thin six3Nanometer sheet and its large area preparation method Download PDFInfo
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- CN107117659A CN107117659A CN201710427138.3A CN201710427138A CN107117659A CN 107117659 A CN107117659 A CN 107117659A CN 201710427138 A CN201710427138 A CN 201710427138A CN 107117659 A CN107117659 A CN 107117659A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The present invention relates to the side NiPS of high-quality ultra-thin six3Nanometer sheet and its large area preparation method, belong to inorganic semiconductor nanometer material technical field, mainly employ two step chemical gas phase reaction methods.Ni (OH) is grown in different substrate surfaces by the method for Hydrothermal Synthesiss first2Nanometer sheet, the sulphur powder and phosphorus powder for being then heated to 450 470 DEG C and heating sublimation simultaneously chemically reacts, and finally gives six ultra-thin side NiPS3Nanometer sheet, six obtained side NiPS3Nanometer sheet thickness is about 3 5nm, and lateral dimension is about 10 20 μm.The method of the invention preparation technology is simple, simple operation and cost is low, has broad application prospects.
Description
Technical field
The invention belongs to inorganic semiconductor nanometer material technical field, it is related to a kind of six sides NiPS3Nanometer sheet and its preparation
Method, more particularly to a kind of side NiPS of high-quality ultra-thin six3Nanometer sheet and its large area chemical gaseous phase preparation method.
Background technology
Two-dimensional layer semi-conducting material is because its unique physics and chemical property are in the recent period in international community by extensive
Concern, this material can reach the ultra-thin thickness of atom level while keeping high surface area.Compared with body material, these ultra-thin half
Conductor material presents numerous advantages, thus tool in opto-electronic device, logical device, photoelectrocatalysis and clean energy resource field
Have wide practical use.As a kind of novel layered semiconductor material, the sulfur family phosphide (MPTs) of transition metal three causes
The interest of domestic and international scientist, wherein M can be IVB, VB and VIB metallic element, including NiPS3、MnPS3、NiPSe3
And FePS3Deng.Characteristic in terms of often showing more ferroelectricities or magnetics due to the complexity of its Chemical Diversity and structure.
But, the growth of such current material is mainly using the elemental metals of corresponding atomic ratio：Phosphorus powder：The mixture of sulphur powder is by changing
Gas phase transmission (CVT) method (ACS Nano 2015,10,1738；Mater.Res.Bull.1970,5,419) obtain, this
Kind of method is than relatively time-consuming, and general growth time will be up to ten days；Meanwhile, required reaction temperature is also higher (600 DEG C of ＞)；Separately
Outside, the simply bulk material finally given.Therefore, the preparation of such material nano structure is the significant challenge faced at present.
In order to meet extensive application demand, preparing, there is high-quality large-area two-dimensional MPT nano materials to be problem urgently to be resolved hurrily.
The NiPS of stratiform3The interlayer of semi-conducting material is formed with Van der Waals force stacking, six Ni in layer2+Ion is located at one
Double centrum (P2S6)4-Around, P atoms are with S atom with Covalent bonding together.This material has good photo absorption performance, and it is partly led
Body band gap changes with the change of nanometer sheet thickness.So far, ultra-thin NiPS3The growth of nanometer sheet is that one urgently captured is big
Problem.Therefore, a kind of efficiently feasible NiPS is developed3Nanometer sheet growing method has great importance.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of six sides NiPS3Nanometer sheet
And preparation method thereof, it is provided in particular in a kind of side NiPS of high-quality ultra-thin six3Nanometer sheet and its large area chemical gaseous phase preparation side
Method, its can by quick and inexpensive chemical vapor deposition (CVD) method in different base (for example, carbon cloth fiber, ITO
Glass and FTO glass) on the side NiPS of growing large-area six3Nanometer sheet.Resulting NiPS3Nanometer sheet good crystallinity, chemically
Matter is stable, and thickness is about 3-5nm, and size is up to 10-20 μm；In addition, the NiPS3Nanometer sheet easily and can be shifted intactly
To other substrates (for example, SiO2/ Si substrates) surface.This method is easy to operate, required equipment simple, and can expeditiously answer
In terms of using large-scale industrial production.
To reach above-mentioned purpose, the present invention uses following technical scheme：
" the side NiPS of high-quality ultra-thin six of the present invention3In nanometer sheet ", " high-quality " refers to：The six sides NiPS3Nanometer sheet knot
Crystalline substance is good, and chemical property is stable；" ultra-thin " refers to：The six sides NiPS3The thickness of nanometer sheet is 3-5nm.
" the side NiPS of high-quality ultra-thin six of the present invention3In nanometer sheet and its large area preparation method ", " large area " refers to：
A large amount of six sides NiPS can disposably be prepared by the method for the present invention3Nanometer sheet.
In a first aspect, the present invention provides a kind of six sides NiPS3Nanometer sheet, it is a kind of new two-dimensional layer material, especially
It is a kind of side NiPS of high-quality ultra-thin six3Nanometer sheet, the six sides NiPS3The thickness of nanometer sheet be 3-5nm, for example, 3nm,
4nm or 5nm etc..The six sides NiPS3The lateral dimension of nanometer sheet be 10-20 μm, for example, 10 μm, 12 μm, 13 μm, 15 μm,
16 μm, 17 μm, 18 μm, 19 μm or 20 μm etc..
It is used as six sides NiPS of the present invention3The optimal technical scheme of nanometer sheet, the six sides NiPS3Nanometer sheet is distributed in
Substrate surface, is preferably evenly distributed through substrate surface.
Preferably, the substrate includes the tin indium oxide conduction of carbon cloth fiber, indium tin oxide-coated glass ITO or Fluorin doped
In glass FTO any one or at least two combination, preferred carbon cloth fiber.But the above-mentioned substrate enumerated is not limited to, its
He can also be used for the present invention at the substrate that can reach same effect commonly used in the art.
Preferably, the six sides NiPS3In nanometer sheet, the atomic ratio of three kinds of elements is Ni:P:S=1:1:3.
Second aspect, the present invention provides six side NiPS as described in relation to the first aspect3The preparation method of nanometer sheet, especially greatly
Area preparation method, methods described is two-step growth method, is comprised the following steps：
(1) synthesis Ni (OH)2Nanometer sheet；
(2) sulphur and phosphorus atmosphere and Ni (OH) are passed through2The chemical gas phase reaction of nanometer sheet, obtains six side NiPS3Nanometer sheet.
In the present invention, use Ni (OH)2Nanometer tablet raw material, is heated to certain temperature, Ni (OH)2Nanometer sheet is with heating simultaneously
The sulphur powder and phosphorus powder of distillation chemically react, and finally give six ultra-thin side NiPS3Nanometer sheet.
As the optimal technical scheme of the method for the invention, step (2) chemical gas phase reaction is in dual temperature area tubular type
Completed in stove.
Preferably, the detailed process of the step (2) is：By Ni (OH)2Nanometer sheet is placed in the downstream of double temperature-area tubular furnaces,
The mixed-powder of red p and ses is placed in the upstream of double temperature-area tubular furnaces, while to downstream and heated upstream, carrying out chemical gaseous phase anti-
Should.
In the present invention, the red phosphorus that step (2) is used can also replace with the phosphorus of other forms, but be due to that white phosphorus is easy certainly
Combustion and severe toxicity, dangerous big, present invention preferably uses red phosphorus.
Preferably, in step (2), the downstream temperature of described pair of temperature-area tubular furnace is set to 400-500 DEG C, for example, 400
DEG C, 420 DEG C, 425 DEG C, 430 DEG C, 440 DEG C, 445 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C or 500 DEG C etc., preferably
For 450-470 DEG C.
Preferably, in step (2), the upstream temperature of described pair of temperature-area tubular furnace is set to 100-300 DEG C, for example, 100
℃、110℃、130℃、145℃、155℃、160℃、180℃、200℃、220℃、225℃、235℃、250℃、260℃、
270 DEG C, 280 DEG C or 300 DEG C etc., preferably 110-270 DEG C.
As the optimal technical scheme of the method for the invention, the mode of heating in downstream is set to step heating, upstream
Mode of heating is set to the heating of two steps, while to downstream and heated upstream.
Preferably, the mode of heating in downstream is step heating, is warming up to 400-500 DEG C, for example, 400 DEG C, 420 DEG C, 430
DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 480 DEG C, 485 DEG C, 490 DEG C or 500 DEG C etc., preferably 470 DEG C.
Preferably, the mode of heating of upstream is set to the heating of two steps, is specially：100-120 is first warming up in 30min
DEG C, 270-300 DEG C is then warming up in 5min.100 DEG C first for example are warming up in 25min, then 280 are warming up in 4min
℃；Or 120 DEG C first are warming up in 20min, then it is warming up to 300 DEG C in 3min；Or 110 DEG C first are warming up in 10min, with
Afterwards 290 DEG C are warming up in 2min；Or 100 DEG C first are warming up in 5min, then it is warming up to 270 DEG C in 2min.
In this optimal technical scheme, " subsequent " refers to：Without insulation.
As the optimal technical scheme of the method for the invention,
It is described by Ni (OH)2Nanometer sheet is placed in the downstream of double temperature-area tubular furnaces, and the mixed-powder of red p and ses is placed in
The mode of the upstream of double temperature-area tubular furnaces is：
(A) small one and large one quartz ampoule composition quartz socket tube of 2 end closures and diameter is taken, the small quartz ampoule of diameter is inserted in
Inside the big quartz ampoule of diameter, the sealing end of the small quartz ampoule of diameter and the big quartz ampoule of diameter is in not homonymy (i.e. respectively in stone
The two ends of English sleeve pipe)；
(B) length of the big quartz ampoule of diameter and the small quartz ampoule of diameter be heat warm area between distance (0.8~
1.2) again, such purpose is to ensure the abundant progress of chemical gas phase reaction；
Wherein, distance is between the heating warm area：The distance between the heating source in downstream and the heating source of upstream, such as
The distance between the thermocouple in downstream and the thermocouple of upstream；
(C) Ni (OH) is placed2Nanometer sheet, and ensure Ni (OH)2Nanometer sheet is located at the downstream of double temperature-area tubular furnaces；By red phosphorus
The sealing end of the small quartz ampoule of diameter is placed in the mixed-powder of sulphur, and ensures that the mixed-powder of red p and ses is managed positioned at dual temperature area
The upstream of formula stove；
Wherein, as Ni (OH)2Nanometer sheet is the Ni (OH) for being grown in substrate surface2During nanometer sheet, with Ni (OH)2Nanometer
The half of piece substrate is located inside the openend of the small quartz ampoule of diameter, and second half is externally-located；As Ni (OH)2Nanometer sheet is nothing
During the powder of base load, Ni (OH)2Nanometer sheet is located at the sealing end of the big quartz ampoule of diameter.
Preferably, the sealing end of the openend of the small quartz ampoule of the diameter and the big quartz ampoule of diameter is in the same side, and
Spacing is 1~1.5cm, for example, 1cm, 1.2cm, 1.3cm or 1.5cm etc..
Preferably, in step (2), the argon gas that purity is 99.999wt% is connected with described pair of temperature-area tubular furnace (i.e. high-purity
Argon gas), the flow of the argon gas is preferably 15-25sccm, for example, 15sccm, 16sccm, 18sccm, 20sccm, 22sccm,
23sccm or 25sccm etc..
Preferably, in step (2), it is passed through before argon gas, vacuumize process is carried out to tube furnace system, and in chemical gaseous phase
It is 60-100Pa (being in low-pressure state under the conditions of this) that quartzy intraductal pressure is maintained in course of reaction, and the vacuumize process is used
Device be mechanical pump.
Preferably, in step (2), time of the chemical gas phase reaction is 30-90min, for example, 30min, 40min,
45min, 50min, 60min, 65min, 70min, 80min or 90min etc..
It is used as the optimal technical scheme of the method for the invention, step (1) described Ni (OH)2Nanometer sheet is grown in substrate table
On face, the substrate is included in the indium tin oxide-coated glass FTO of carbon cloth fiber, indium tin oxide-coated glass ITO or Fluorin doped
Any one or at least two combination, preferred carbon cloth fiber.But the above-mentioned substrate enumerated is not limited to, other this areas are normal
The substrate that can reach same effect can also be used for the present invention.
Preferably, the step (1) synthesizes Ni (OH) by hydrothermal method2Nanometer sheet.
Preferably, the process of the step (1) is：In the aqueous solution that substrate is immersed to nickel source and hexa, in
80-105 DEG C of progress hydro-thermal reaction, obtains being grown in the Ni (OH) of substrate surface2Nanometer sheet.
In this optimal technical scheme, the temperature of hydro-thermal reaction is 80-105 DEG C, for example, 80 DEG C, 82 DEG C, 85 DEG C, 87 DEG C,
90 DEG C, 92.5 DEG C, 95 DEG C, 100 DEG C, 102 DEG C or 105 DEG C etc., more preferably preferably 80-100 DEG C, 100 DEG C.
Preferably, synthesis Ni (OH)2During nanometer sheet, the nickel source is Nickelous nitrate hexahydrate (Ni (NO3)2·
6H2) or Nickel dichloride hexahydrate (NiCl O2·6H2O the combination of any one or two kinds in).
Preferably, synthesis Ni (OH)2During nanometer sheet, the concentration of the nickel source is 1.25mM, the hexa-methylene
The concentration of tetramine is preferably 2.5mM.
Preferably, synthesis Ni (OH)2During nanometer sheet, the hydro-thermal reaction is carried out in the water heating kettle of closing.
Preferably, synthesis Ni (OH)2During nanometer sheet, time of the hydro-thermal reaction is 8-12h, for example, 8h,
8.5h, 9h, 10h, 11h or 12h etc., preferably 10h.
Preferably, synthesis Ni (OH)2During nanometer sheet, it is additionally included in after hydro-thermal reaction terminates and is washed and dried
The step of.The washing is：Secondary water is repeatedly washed.
Preferably, the drying is completed in air dry oven, and the temperature of the drying is preferably 60-80 DEG C, is, for example,
60 DEG C, 63 DEG C, 65 DEG C, 70 DEG C, 72 DEG C, 75 DEG C or 80 DEG C etc..
As the further preferred scheme of the method for the invention, it the described method comprises the following steps：
(1) substrate is immersed in the aqueous solution of nickel source and hexa, hydro-thermal reaction, reaction is carried out in 80-100 DEG C
Product is washed and dried after end, obtains being grown in the Ni (OH) of substrate surface2Nanometer sheet；
(2) Ni (OH) of substrate surface will be grown in2Nanometer sheet is placed in the openend of the small quartz ampoule of diameter, and (i.e. diameter is big
Quartz ampoule sealing end, the small quartz ampoule of diameter and the homogeneous end closure of the big quartz ampoule of diameter, and the small quartz pipe sleeve of diameter
In the inside of the big quartz ampoule of diameter, the sealing end of the two is in not homonymy), the mixed-powder of red p and ses is placed in the small stone of diameter
The sealing end of English pipe, and ensure to be grown in the Ni (OH) of substrate surface2Nanometer sheet is located at the downstream of double temperature-area tubular furnaces, red phosphorus and
The mixed-powder of sulphur is located at the upstream of double temperature-area tubular furnaces, and vacuumize process is carried out to tube furnace system with mechanical pump, then logical
Enter the argon gas that purity is 99.999wt%, intake is 15-25sccm, keeps the flow to continue to reaction to terminate；
(3) downstream is set to step heating, upstream is set to the heating of two steps, while to downstream and heated upstream, carrying out
30-90min chemical gas phase reactions, then natural cooling, obtains being grown in six side NiPS of substrate surface3Nanometer sheet；
Wherein, the temperature of the step of downstream one heating is：400-500℃；The step of upstream two heats up：First it is warming up in 30min
100-120 DEG C, 270-300 DEG C is then warming up in 5min.
Compared with the prior art, the invention has the advantages that：
(1) present invention utilizes Ni (OH)2Nanometer sheet occurs chemical gas phase reaction with sulphur and phosphorus atmosphere at a certain temperature and obtained
To six side NiPS3Nanometer sheet.Methods described synthesis step is simple, required equipment is simple, cost is low, can efficiently be applied to big rule
In terms of the production of die worker's industry.
(2) method of the invention does not have strict selectivity, and gained NiPS to substrate3Nanometer sheet can be easy and complete
Site preparation is transferred to other substrates (for example, SiO2/ Si substrates) surface.
(3) NiPS obtained by the present invention3Nanometer sheet good crystallinity, chemical stability is high；Resulting six sides NiPS3Nanometer sheet
Thickness be 3-5nm, lateral dimension is about 10-20 μm；Resulting six sides NiPS3Nanometer sheet large area is evenly distributed on different bases
Basal surface, can grow the ultra-thin NiPS of uniform fold in 2cm × 4cm substrate surface3Nanometer sheet；Six prepared side NiPS3Receive
Three kinds of element Ni in rice piece:P:S atom ratio is 1:1:3.
Brief description of the drawings
Accompanying drawing shows some exemplary implementation figures of the present invention.In various figures, similar or identical reference refers to
Show similar or identical element.What accompanying drawing was not necessarily drawn to scale.
Fig. 1 is that embodiment 1 prepares the side NiPS of large area six3Double temperature-area tubular furnace structure drawing of device of nanometer sheet, 1# is stone
Ying Guan, 2# are quartz socket tube；
Fig. 2 is the Ni (OH) for being grown in carbon cloth fiber surface that the hydro-thermal of embodiment 1 is obtained2The large area scanning electricity of nanometer sheet
Sub- microscope (SEM) figure；
Fig. 3 a are that the large area carbon cloth fiber (2cm × 4cm) of embodiment 1 grows NiPS3Photo comparison's result before and after nanometer sheet；
Fig. 3 b are that the large area FTO glass (2cm × 4cm) of embodiment 1 grows NiPS3Photo comparison's result before and after nanometer sheet；
Fig. 4 a are the six side NiPS that embodiment 1 is grown in carbon cloth fiber surface3Nanometer sheet large area scanning electron microscope
(SEM) photo；
Fig. 4 b are the six side NiPS that embodiment 1 is grown in FTO glass surfaces3Nanometer sheet large area scanning electron microscope
(SEM) photo, its illustration is single six sides NiPS3SEM figures after nanometer sheet amplification；
Fig. 4 c are the six side NiPS that embodiment 1 is grown in ito glass surface3Nanometer sheet large area scanning electron microscope
(SEM) photo；
Fig. 5 a are NiPS obtained by embodiment 2 (the gas phase reaction time is 30min) carbon cloth fiber surface3After the amplification of nanometer sheet
SEM (SEM) photo；
Fig. 5 b are single NiPS obtained by embodiment 1 (the gas phase reaction time is 60min) carbon cloth fiber surface3Nanometer sheet is put
SEM (SEM) photo after big；
Fig. 6 a are NiPS obtained by embodiment 3 (when T2 warm area reaction temperatures are set to 400 DEG C)3Nanometer sheet is in carbon cloth fiber table
SEM (SEM) photo in face；
Fig. 6 b are NiPS obtained by embodiment 1 (T2 warm area reaction temperatures are set to 450-470 DEG C)3Nanometer sheet is in carbon cloth fiber
SEM (SEM) photo on surface；
Fig. 6 c are obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C, and >=500 DEG C are denoted as in figure)
NiPS3SEM (SEM) photo of nanometer sheet in carbon cloth fiber surface；
Fig. 7 a are the gained NiPS of embodiment 13Transmission electron microscope (TEM) photo under nanometer sheet low power number；
Fig. 7 b are NiPS shown in Fig. 7 a3The SEAD figure of nanometer sheet；
Fig. 7 c are NiPS shown in Fig. 7 a3High resolution transmission electron microscopy (HRTEM) photo of nanometer sheet；
Fig. 8 a are the single NiPS of the gained of embodiment 13The dark field transmission electron microphotograph of nanometer sheet, and Fig. 8 b, Fig. 8 c
It is respectively NiPS shown in Fig. 8 a with Fig. 8 d3Ni, S and the distribution map of P element in nanometer sheet；
Fig. 9 is the gained NiPS of embodiment 13X-ray energy spectrum (EDX) elementary analysis of nanometer sheet；
Figure 10 a, Figure 10 b, Figure 10 c and Figure 10 d are the gained different-thickness NiPS of embodiment 13The atomic force microscopy of nanometer sheet
Mirror (AFM) figure and Thickness Analysis result；
Figure 11 a and Figure 11 b are NiPS obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C)3Nanometer sheet
AFM (AFM) figure under different amplification；
Figure 11 c are NiPS obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C)3The thickness of nanometer sheet point
Analyse result；
Figure 12 a are that embodiment 1 is grown in carbon cloth fiber surface large area NiPS3The X ray diffracting spectrum (XRD) of nanometer sheet
And the comparing result with standard x RD cards；
Figure 12 b are that embodiment 1 is grown in carbon cloth fiber surface large area NiPS3The Raman spectrum (Raman) of nanometer sheet point
Analyse collection of illustrative plates；
Figure 13 a, Figure 13 b and Figure 13 c are the gained NiPS of embodiment 13The X-ray photoelectricity of Ni, P and S element in nanometer sheet
Sub- power spectrum (XPS) analysis.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
The high-quality side NiPS of large area six3It is prepared by nanometer sheet.
(1) clean carbon cloth fiber, ito glass, FTO glass are immersed into 30mL 1.25mM Ni (NO3)2·6H2O and 2.5mM
In the mixed solution of hexa (HMT), it is subsequently placed in 50mL ptfe autoclave and heats 100 DEG C of reactions
10h.After question response terminates, washing and 60 DEG C of dry for standby after sample are taken out, obtain being grown in (i.e. uniform point of different base surface
Cloth is in carbon cloth fiber, ito glass, FTO glass surfaces) Ni (OH)2Nanometer sheet.
(2) 2 end closures and small one and large one quartz ampoule composition quartz socket tube 2# of diameter, the small quartz pipe sleeve of diameter are taken
Enter inside the big quartz ampoule of diameter, the sealing end of the small quartz ampoule of diameter and the big quartz ampoule of diameter is in not homonymy；
Quartz socket tube #2 is positioned over inside quartz ampoule 1#；
The Ni (OH) on different base surface will be grown in2The openend of the small quartz ampoule of nanometer sheet diameter, makes with Ni
(OH)2The half of nanometer sheet substrate is located inside openend, and second half is externally-located, and ensures to be grown in different base surface
Ni(OH)2Nanometer sheet is located at the downstream (i.e. T2 warm areas in Fig. 1 a) of double temperature-area tubular furnaces；
Red phosphorus/sulphur mixed-powder is placed in the sealing end of the small quartz ampoule of diameter, and ensures to be located at double temperature-area tubular furnaces
Upstream (i.e. T1 warm areas in Fig. 1 a)；
Vacuumize process is carried out to tube furnace system with mechanical pump, high-purity argon gas 15-25sccm is subsequently passed, and keeps being somebody's turn to do
Flow continues to reaction to terminate.The temperature of T2 warm areas is risen to 450-470 DEG C in 30min, meanwhile, T1 warm areas are subjected to two steps
Heating process, is warming up to 110 DEG C in 30min first, is then warming up to 270 DEG C in 5min again, is finally heated up in 60min
To 300 DEG C, gas phase reaction duration 60min is kept, then natural cooling, obtains being grown in the six side NiPS on different base surface3
Nanometer sheet.
The side NiPS of gained six3Nanometer sheet is equably covered in carbon cloth fiber, ito glass, FTO glass surfaces.
Following part briefly illustrates its performance indications：
Fig. 1 is that embodiment 1 is used to prepare the side NiPS of large area six3Double temperature-area tubular furnace structure drawing of device of nanometer sheet, its
Middle 1# is quartz ampoule, and 2# is quartz socket tube.
Fig. 2 is the Ni (OH) for being grown in carbon cloth fiber surface that the hydro-thermal of embodiment 1 is obtained2The large area scanning electricity of nanometer sheet
Sub- microscope (SEM) figure, figure it is seen that prepared Ni (OH)2Nanometer sheet vertical distribution in carbon cloth fiber surface, and
It has ultra-thin thickness.
Fig. 3 a are large area carbon cloth fiber (2cm × 4cm) growth Ni (OH)2Photo comparison's result before and after nanometer sheet, Fig. 3 b
For large area FTO glass (2cm × 4cm) growth Ni (OH)2Photo comparison's result before and after nanometer sheet, passes through both Fig. 3 a and Fig. 3 b
The uniform color change in surface can be seen that superficial growth material.
Fig. 4 a are the six side NiPS for being grown in carbon cloth fiber surface3Nanometer sheet large area scanning electron microscope (SEM) shines
Piece；Fig. 4 b are the six side NiPS for being grown in FTO glass surfaces3Nanometer sheet large area scanning electron microscope (SEM) photo, Fig. 4 b
In illustration be single six sides NiPS3SEM figures after nanometer sheet amplification；Fig. 4 c are the six side NiPS for being grown in ito glass surface3
Nanometer sheet large area scanning electron microscope (SEM) photo.Six side NiPS can be seen that by Fig. 4 a- Fig. 4 c3Nanometer sheet is uniform
Ground vertical distribution can be seen that six resulting side NiPS from Fig. 4 b illustrations on different base surface3The lateral dimension of nanometer sheet
About 5 μm, and be made up of multilayer.Simultaneously it can thus be seen that NiPS3The growth of nanometer sheet is not rely on the selection of substrate.
Fig. 5 a are NiPS obtained by embodiment 2 (the gas phase reaction time is 30min) carbon cloth fiber surface3After the amplification of nanometer sheet
SEM (SEM) photo.
Fig. 5 b are single NiPS obtained by embodiment 1 (the gas phase reaction time is 60min) carbon cloth fiber surface3Nanometer sheet is put
SEM (SEM) photo after big；Six resulting side NiPS are can be seen that by Fig. 5 b3The lateral dimension of nanometer sheet
Up to more than ten microns.
Fig. 6 a are NiPS3 nanometer sheets obtained by embodiment 3 (when T2 warm area reaction temperatures are set to 400 DEG C) in carbon cloth fiber table
SEM (SEM) photo in face.
Fig. 6 b are NiPS obtained by embodiment 1 (T2 warm area reaction temperatures are set to 450-470 DEG C)3Nanometer sheet is in carbon cloth fiber
SEM (SEM) photo on surface, substantial amounts of six sides NiPS is can be seen that from Fig. 6 b3Nanometer sheet vertical distribution is in carbon
Fiber surface.
Fig. 6 c are NiPS3 nanometer sheets obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C) in carbon cloth fiber
SEM (SEM) photo on surface.
Fig. 7 a are the gained NiPS of embodiment 13Transmission electron microscope (TEM) photo under nanometer sheet low power number.
Fig. 7 b are NiPS shown in Fig. 7 a3The SEAD figure of nanometer sheet；Fig. 7 c are NiPS shown in Fig. 7 a3Nanometer sheet
High resolution transmission electron microscopy (HRTEM) photo.It is can be seen that from Fig. 7 b and Fig. 7 c by the NiPS obtained by embodiment 13
Nanometer sheet has high crystal mass.
Fig. 8 a are the single NiPS of the gained of embodiment 13The dark field transmission electron microphotograph of nanometer sheet, and Fig. 8 b, Fig. 8 c
It is respectively the corresponding NiPS of Fig. 8 a with Fig. 8 d3Ni, S and the distribution map of P element in nanometer sheet, Ni, S are can be seen that from Fig. 8 a- Fig. 8 d
It is uniformly distributed with the elements of P tri- on the hexagonal nano-flake, the enrichment of Partial Elements is not occurred.
Fig. 9 is the gained NiPS of embodiment 13X-ray energy spectrum (EDX) elementary analysis of nanometer sheet, each element atomic ratio situation
Referring to table 1, the atomic ratio for obtaining the element of Ni, S and P tri- is 1:0.9:2.8.
Table 1
| Element | Atomic ratio (%) |
| P | 18.6 |
| S | 60.26 |
| Ni | 21.28 |
| Percent of total | 100.00 |
Figure 10 a, Figure 10 b, Figure 10 c and Figure 10 d are the gained different-thickness NiPS of embodiment 13The atomic force microscopy of nanometer sheet
Mirror (AFM) figure and Thickness Analysis result, as a result show：The NiPS of different-thickness can be obtained simultaneously by the method for embodiment 13Receive
Rice piece, wherein 80%NiPS3The thickness of nanometer sheet is 3-5nm, and keeps lateral dimension to be 10-12 μm simultaneously；From Figure 10 c and figure
10d can be seen that six partially complete side NiPS3Nanometer sheet is made up of multilayer, and most thin layer is up to 2.6nm.
Figure 11 a and Figure 11 b are NiPS3 nanometer sheets obtained by embodiment 4 (T2 warm areas temperature setting is 500-550 DEG C) not
With AFM (AFM) figure under multiplication factor.
Figure 11 c are the thickness point of NiPS3 nanometer sheets obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C)
Analyse result.
Figure 12 a are that embodiment 1 is grown in carbon cloth fiber surface large area NiPS3The X ray diffracting spectrum (XRD) of nanometer sheet
And the comparing result with standard x RD cards, it is therefore seen that the NiPS of gained3Nanometer sheet has monoclinic structure.
Figure 12 b are that embodiment 1 is grown in carbon cloth fiber surface large area NiPS3The Raman spectrum (Raman) of nanometer sheet point
Analyse collection of illustrative plates, the NiPS it can be seen from Figure 12 b3Nanometer sheet shows typical one-level Raman vibration peak, including in four faces
Raman vibration peak Eg (~130cm-1,~175cm-1,~281cm-1With~555cm-1) and two interlayer Raman vibration peak A1g (~
381cm-1With~585cm-1), also obvious two grades of Raman vibration peaks in addition.
Figure 13 a, Figure 13 b and Figure 13 c are the gained NiPS of embodiment 13In nanometer sheet Ni, P and S element respectively Ni2p,
X-ray photoelectron power spectrum (XPS) analysis in P2p and S2p regions, the position of their combination energy and the XPS previously reported
Analyze data is consistent.
Embodiment 2
High-quality large area NiPS3It is prepared by nanometer sheet
(1) clean carbon cloth fiber is immersed into 30mL 1.25mM Ni (NO3)2·6H2O and 2.5mM hexas
(HMT) in mixed solution, it is subsequently placed in 50mL ptfe autoclave and heats 100 DEG C of reaction 10h.Question response terminates
Afterwards, washing and 60 DEG C of dry for standby after sample are taken out, the Ni (OH) in carbon cloth fiber surface is evenly distributed2Nanometer sheet.
(2) Ni (OH) for being grown in carbon cloth fiber surface is placed2Nanometer sheet and red phosphorus/sulphur mixed-powder to quartz socket tube
In, modes of emplacement is same as Example 1, carries out vacuumize process to tube furnace system with mechanical pump, is subsequently passed high-purity argon gas
15-25sccm, and keep the flow to continue to reaction to terminate.The temperature of T2 warm areas is risen to 450-470 DEG C in 30min, together
When, T1 warm areas are subjected to two step heating processes, 110 DEG C is warming up in 30min first, is then warming up to 270 in 5min again
DEG C, 300 DEG C are finally warming up in 60min, gas phase reaction duration 30min is kept, then natural cooling, obtains being grown in carbon cloth
The six side NiPS on fibrous substrate surface3Nanometer sheet.
Gained NiPS3Nanometer sheet is equably covered in carbon cloth fiber surface.
Following part briefly illustrates its performance indications
Fig. 5 a are the NiPS obtained by the carbon cloth fiber surface of embodiment 23The SEM (SEM) of nanometer sheet is shone
Piece, the resulting NiPS it can be seen from Fig. 5 a3Nanometer sheet is generally imperfect six sides thin slice, and vertical in carbon cloth fiber surface
Distribution, the lateral dimension of the nanometer sheet is about 6-8 μm.
Embodiment 3
Large area NiPS3It is prepared by nanometer sheet
(1) clean carbon cloth fiber is immersed into 30mL 1.25mM Ni (NO3)2·6H2O and 2.5mM hexas
(HMT) in mixed solution, it is subsequently placed in 50mL ptfe autoclave and heats 100 DEG C of reaction 10h.Question response terminates
Afterwards, washing and 60 DEG C of dry for standby after sample are taken out, the Ni (OH) in carbon cloth fiber surface is evenly distributed2Nanometer sheet.
(2) Ni (OH) for being grown in carbon cloth fiber surface is placed2Nanometer sheet and red phosphorus/sulphur mixed-powder to quartz socket tube
In, modes of emplacement is same as Example 1, carries out vacuumize process to tube furnace system with mechanical pump, is subsequently passed high-purity argon gas
15-25sccm, and keep the flow to continue to reaction to terminate.The temperature of T2 warm areas is risen to 400 DEG C in 30min, meanwhile, will
T1 warm areas carry out two step heating processes, are warming up to 110 DEG C in 30min first, are then warming up to 270 DEG C in 5min again, most
300 DEG C are warming up in 60min eventually, gas phase reaction duration 60min is kept, then natural cooling, obtains being grown in carbon cloth fiber
The six side NiPS on surface3Nanometer sheet.
Gained NiPS3Nanometer sheet is equably covered in carbon cloth fiber surface.
Following part briefly illustrates its performance indications
Fig. 6 a are NiPS obtained by embodiment 3 (T2 warm area reaction temperatures are set to 400 DEG C)3Nanometer sheet is in carbon cloth fiber surface
SEM (SEM) photo, from Fig. 6 a can be seen that reaction temperature than it is relatively low when, NiPS3The growth of nanometer sheet
And do not complete, resulting NiPS3Nanometer sheet in irregular shape and lateral dimension is all smaller, about 0.5~1 μm；Simultaneously
Also there are many presoma residues in carbon cloth fiber surface.
Embodiment 4
Large area flakey NiPS3It is prepared by nanometer sheet
(1) clean carbon cloth fiber is immersed into 30mL 1.25mM Ni (NO3)2·6H2O and 2.5mM hexas
(HMT) in mixed solution, it is subsequently placed in 50mL ptfe autoclave and heats 100 DEG C of reaction 10h.Question response terminates
Afterwards, washing and 60 DEG C of dry for standby after sample are taken out, the Ni (OH) in carbon cloth fiber surface is evenly distributed2Nanometer sheet.
(2) Ni (OH) of carbon cloth fiber surface will be grown in2Nanometer sheet and red phosphorus/sulphur mixed-powder are respectively placed in two quartz
The sealing end of sleeve pipe, and T2 the and T1 heating zones of double temperature-area tubular furnaces are put in, tube furnace system is vacuumized with mechanical pump
Processing, is subsequently passed high-purity argon gas 15-25sccm, and keep the flow to continue to reaction to terminate.The temperature of T2 warm areas is existed
500-550 DEG C is risen in 30min, meanwhile, T1 warm areas are subjected to two step heating processes, 110 DEG C are warming up in 30min first,
270 DEG C are then warming up in 5min again, 300 DEG C are finally warming up in 60min, gas phase reaction duration 60min is kept, then
Natural cooling, obtains being grown in six side NiPS of carbon cloth fiber surface3Nanometer sheet.
Gained NiPS3Nanometer sheet is equably covered in carbon cloth fiber surface.
Following part briefly illustrates its performance indications
Fig. 6 c are NiPS obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C)3Nanometer sheet is in carbon cloth fiber
SEM (SEM) photo on surface, it can be seen from Fig. 6 c after reaction temperature is more than 500 DEG C, six sides'
NiPS3Flakey is presented in the edge of nanometer sheet, because too high reaction temperature can cause NiPS3Nanometer sheet surface is again
Desorption process and make it that its edge is no longer complete, but the NiPS of these flakeys3Nanometer sheet is still evenly distributed in carbon cloth fiber
Surface.
Figure 11 a and Figure 11 b are NiPS obtained by embodiment 4 (T2 warm areas temperature setting is 500-550 DEG C)3Nanometer sheet not
With AFM (AFM) figure under multiplication factor.
Figure 11 c are NiPS obtained by embodiment 4 (T2 warm area reaction temperatures are set to 500-550 DEG C)3The thickness of nanometer sheet point
Analyse result.
By Figure 11 a- Figure 11 c, from single flakey NiPS3AFM figures are it can be seen that its pattern under the low power number of nanometer sheet
As seen in fig. 6 c, NiPS3Corrugated is presented in the edge of nanometer sheet, after its marginal portion is amplified obtained by
AFM it can be seen from the figure thats, the NiPS3Nanometer sheet is made up of multilayer, its Thickness Analysis result as shown in fig. 11c, one layer of NiPS3
The thickness of nanometer sheet is down to 0.73nm, this and individual layer NiPS30.66 nanometer shown of thickness is suitable.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of six sides NiPS3Nanometer sheet, it is characterised in that the six sides NiPS3The thickness of nanometer sheet is 3-5nm, lateral dimension
For 10-20 μm.
2. six sides NiPS according to claim 13Nanometer sheet, it is characterised in that the six sides NiPS3Nanometer sheet is distributed in
Substrate surface, the substrate includes the indium tin oxide-coated glass of carbon cloth fiber, indium tin oxide-coated glass ITO or Fluorin doped
In FTO any one or at least two combination, preferred carbon cloth fiber；
Preferably, the six sides NiPS3In nanometer sheet, the atomic ratio of three kinds of elements is Ni:P:S=1:1:3.
3. six sides NiPS as claimed in claim 1 or 23The preparation method of nanometer sheet, it is characterised in that methods described is two steps
Growth method, comprises the following steps：
(1) synthesis Ni (OH)2Nanometer sheet；
(2) sulphur and phosphorus atmosphere and Ni (OH) are passed through2The chemical gas phase reaction of nanometer sheet, obtains six side NiPS3Nanometer sheet.
4. method according to claim 3, it is characterised in that step (2) chemical gas phase reaction is in dual temperature area tubular type
Completed in stove；
Preferably, the detailed process of the step (2) is：By Ni (OH)2Nanometer sheet is placed in the downstream of double temperature-area tubular furnaces, red phosphorus
The upstream of double temperature-area tubular furnaces is placed in the mixed-powder of sulphur, while to downstream and heated upstream, carrying out chemical gas phase reaction；
Preferably, in step (2), the downstream temperature of described pair of temperature-area tubular furnace is set to 400-500 DEG C, preferably 450-470
℃；
Preferably, in step (2), the upstream temperature of described pair of temperature-area tubular furnace is set to 100-300 DEG C, preferably 110-270
℃。
5. method according to claim 4, it is characterised in that the mode of heating in downstream is set to step heating, upstream
Mode of heating is set to the heating of two steps, while to downstream and heated upstream；
Preferably, the mode of heating in downstream heats up for a step, is warming up to 400-500 DEG C, preferably 470 DEG C；
Preferably, the mode of heating of upstream is set to the heating of two steps, is specially：100-120 DEG C is first warming up in 30min, with
270-300 DEG C is warming up in 5min afterwards.
6. the method according to claim 4 or 5, it is characterised in that described by Ni (OH)2Nanometer sheet is placed in dual temperature area tubular type
The downstream of stove, and the mixed-powder of red p and ses is placed in the mode of the upstream of double temperature-area tubular furnaces is：
(A) small one and large one quartz ampoule composition quartz socket tube of 2 end closures and diameter is taken, the small quartz ampoule of diameter is inserted in diameter
Inside big quartz ampoule, the sealing end of the small quartz ampoule of diameter and the big quartz ampoule of diameter is in not homonymy；
(B) length of the big quartz ampoule of diameter and the small quartz ampoule of diameter is (0.8~1.2) of distance between heating warm area
Times；
Wherein, distance is between the heating warm area：The distance between the heating source in downstream and the heating source of upstream；
(C) Ni (OH) is placed2Nanometer sheet, and ensure Ni (OH)2Nanometer sheet is located at the downstream of double temperature-area tubular furnaces；By red p and ses
Mixed-powder be placed in the sealing end of the small quartz ampoule of diameter, and ensure that the mixed-powder of red p and ses is located at double temperature-area tubular furnaces
Upstream；
Wherein, as Ni (OH)2Nanometer sheet is the Ni (OH) for being grown in substrate surface2During nanometer sheet, growth has Ni (OH)2Nanometer sheet
Substrate half be located inside the openend of the small quartz ampoule of diameter, second half is externally-located；As Ni (OH)2Nanometer sheet is without base
During the powder of bed load, Ni (OH)2Nanometer sheet is located at the sealing end of the big quartz ampoule of diameter；
Preferably, the sealing end of the openend of the small quartz ampoule of the diameter and the big quartz ampoule of diameter is in the same side, and spacing
For 1~1.5cm.
7. the method according to claim any one of 3-6, it is characterised in that in step (2), in described pair of temperature-area tubular furnace
The argon gas that purity is 99.999wt% is connected with, the flow of the argon gas is preferably 15-25sccm；
Preferably, in step (2), it is passed through before argon gas, vacuumize process is carried out to tube furnace system, and in chemical gas phase reaction
During maintain intraductal pressure be 60-100Pa, the device that the vacuumize process is used be mechanical pump；
Preferably, in step (2), the time of the chemical gas phase reaction is 30-90min.
8. the method according to claim any one of 3-7, it is characterised in that step (1) described Ni (OH)2Nanometer sheet grows
In substrate surface, the substrate includes the indium tin oxide-coated glass of carbon cloth fiber, indium tin oxide-coated glass ITO or Fluorin doped
In FTO any one or at least two combination, preferred carbon cloth fiber.
9. the method according to claim any one of 3-8, it is characterised in that the step (1) is synthesized by hydrothermal method
Ni(OH)2Nanometer sheet；
Preferably, the process of the step (1) is：In the aqueous solution that substrate is immersed to nickel source and hexa, in 80-
105 DEG C of progress hydro-thermal reactions, obtain being grown in the Ni (OH) of substrate surface2Nanometer sheet；
Preferably, synthesis Ni (OH)2During nanometer sheet, the nickel source is in Nickelous nitrate hexahydrate or Nickel dichloride hexahydrate
The combination of any one or two kinds；
Preferably, synthesis Ni (OH)2During nanometer sheet, the concentration of the nickel source is 1.25mM, the hexa
Concentration is preferably 2.5mM；
Preferably, synthesis Ni (OH)2During nanometer sheet, the hydro-thermal reaction is carried out in the water heating kettle of closing；
Preferably, synthesis Ni (OH)2During nanometer sheet, the temperature of the hydro-thermal reaction is 80-100 DEG C, preferably 100 DEG C；
Preferably, synthesis Ni (OH)2During nanometer sheet, the time of the hydro-thermal reaction is 8-12h, preferably 10h；
Preferably, synthesis Ni (OH)2During nanometer sheet, the step washed and dried after hydro-thermal reaction terminates is additionally included in
Suddenly, the drying is completed in air dry oven, and the temperature of the drying is preferably 60-80 DEG C.
10. the method according to claim any one of 3-9, it is characterised in that the described method comprises the following steps：
(1) substrate is immersed in the aqueous solution of nickel source and hexa, hydro-thermal reaction is carried out in 80-100 DEG C, reaction terminates
Product is washed and dried afterwards, obtains being grown in the Ni (OH) of substrate surface2Nanometer sheet；
(2) Ni (OH) for being grown in substrate surface is placed2Nanometer sheet, makes with Ni (OH)2The half of nanometer sheet substrate is located at diameter
The inside of the openend of small quartz ampoule, second half is externally-located；The mixed-powder of red p and ses is placed in the small quartz ampoule of diameter
Sealing end, and ensure to be grown in the Ni (OH) of substrate surface2Nanometer sheet is located at the downstream of double temperature-area tubular furnaces, red p and ses
Mixed-powder is located at the upstream of double temperature-area tubular furnaces, carries out vacuumize process to tube furnace system with mechanical pump, is subsequently passed pure
The argon gas for 99.999wt% is spent, intake is 15-25sccm, keeps the flow to continue to reaction to terminate；
Wherein, the small quartz ampoule of diameter and the homogeneous end closure of the big quartz ampoule of diameter, and the small quartz pipe sleeve of diameter is big in diameter
Quartz ampoule inside, the sealing end of the two is in not homonymy；
(3) downstream is set to step heating, upstream is set to the heating of two steps, while to downstream and heated upstream, carrying out 30-
90min chemical gas phase reactions, then natural cooling, obtains being grown in six side NiPS of substrate surface3Nanometer sheet；
Wherein, the temperature of the step of downstream one heating is：400-500℃；The step of upstream two heats up：100- is first warming up in 30min
120 DEG C, 270-300 DEG C is then warming up in 5min.
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| CN108097281A (en) * | 2017-11-14 | 2018-06-01 | 国家纳米科学中心 | A kind of MnPS3Nanometer sheet and its preparation method and application |
| CN109052495A (en) * | 2018-11-06 | 2018-12-21 | 深圳大学 | A kind of NiPS3Nanometer sheet and preparation method thereof |
| CN109772386A (en) * | 2019-03-22 | 2019-05-21 | 哈尔滨工业大学 | The NiPS of self supporting structure3The preparation method and applications of nanometer sheet |
| CN111092224A (en) * | 2018-10-23 | 2020-05-01 | 国家纳米科学中心 | NiPS3Application of nanosheet in sodium-ion battery and sodium-ion battery |
| CN111203255A (en) * | 2020-01-16 | 2020-05-29 | 西安交通大学 | N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst |
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| CN108097281A (en) * | 2017-11-14 | 2018-06-01 | 国家纳米科学中心 | A kind of MnPS3Nanometer sheet and its preparation method and application |
| CN108097281B (en) * | 2017-11-14 | 2021-04-27 | 国家纳米科学中心 | MnPS3Nanosheet and preparation method and application thereof |
| CN111092224A (en) * | 2018-10-23 | 2020-05-01 | 国家纳米科学中心 | NiPS3Application of nanosheet in sodium-ion battery and sodium-ion battery |
| CN109052495A (en) * | 2018-11-06 | 2018-12-21 | 深圳大学 | A kind of NiPS3Nanometer sheet and preparation method thereof |
| CN109052495B (en) * | 2018-11-06 | 2021-01-12 | 深圳大学 | NiPS3Nanosheet and preparation method thereof |
| CN109772386A (en) * | 2019-03-22 | 2019-05-21 | 哈尔滨工业大学 | The NiPS of self supporting structure3The preparation method and applications of nanometer sheet |
| CN111203255A (en) * | 2020-01-16 | 2020-05-29 | 西安交通大学 | N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst |
| CN111203255B (en) * | 2020-01-16 | 2021-05-28 | 西安交通大学 | N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst |
| CN112551599A (en) * | 2020-12-10 | 2021-03-26 | 西安交通大学深圳研究院 | Nickel sulfate phosphate nanosheet/graphene composite material and preparation method thereof |
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