CN102786038B - Hydro-thermal synthesis method of cubic phase InSe nano sheet - Google Patents
Hydro-thermal synthesis method of cubic phase InSe nano sheet Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesis of environment-friendly nano material, relates to a synthesis method of the nano material, and particularly relates to a hydro-thermal synthesis method of cubic phase InSe nano sheet. The hydro-thermal synthesis method of cubic phase InSe nano sheet comprises the followings steps of: using a ternary hybrid solution of diethylenetriamine, hydrazine hydrate and water as solvent, carrying out hydro-thermal synthesis reaction on hydro-thermal synthesis aqueous solution and sodium selenite aqueous solution in a reaction kettle at 180 DEG C, rinsing by absolute ethyl alcohol, centrifugally separating, drying, and roasting, so as to obtain the nano material. Inferred from the growth mechanism, the method is suitable for the preparation of other selenium and tellurium metal compound nano materials. From the scanning electron microscope (SEM), after roasting, the nano sheet has high crystallinity, smooth surface and even size, and is 0.6-1.3microns in length, 0.5-1micron in width and 60nm in thickness, and most nano sheets are square. The preparation method has the following characteristics of simplicity, low cost, high controllability, high crystallinity of product, high yield, green and environmental protection.
Description
Technical field
The invention belongs to environmentally friendly nano material synthesis technical field, relate to the synthetic method of nano material, relate in particular to the hydrothermal synthesis method of a kind of cube of crystalline phase InSe nanometer sheet.
Background technology
In a broad sense, nano material just refers in three-dimensional space, to have the material of one dimension within the scope of nanoscale at least, or as elementary cell, assembles by them the structured material forming.If divided according to dimension, nano material can be divided into four classes substantially: (i) zero dimension, refers at space three-dimensional yardstick all at nanoscale, as the particle of nanoscale, Nano microsphere, elementide etc.; (ii) one dimension, referring to has bidimensional in nanoscale in space, as nano wire, nanometer rod, nanotube, nano belt and nanofiber etc.; (iii) two dimension, refers to have one dimension at nanoscale, as ultrathin membrane, nanometer sheet, superlattice etc. in three-dimensional space.(v) three-dimensional, refer to the material that formed according to certain rule assembling by one dimension or two-dimensional nano material, as nano flower, nanometer sea urchin etc.
And nanometer sheet is as a kind of important two-dimensional nano material, there is significant physico-chemical property in day by day flourish nanostructure, to play the part of important role, can be widely used in various important research and production field.For example: single nanometer sheet can be used as elementary cell and is assembled into nano flower and nanometer ball, be widely used on button cell, solar cell, catalyzer and macromolecular material.Multiple different nanometer sheet can form various semi-conductors, catalyzer, magnet and plasma nano particle and can be applied in many devices such as optomagnetic catalyzer and the hydrogen manufacturing of photoelectrolysis water.Graphene is exactly an example, and the electrical properties of two-dimentional graphene nanometer sheet is better than other nanostructures.The dimension of a large amount of sulfur family inorganic nano materials is determining its application performance, and the inorganic materials that therefore obtains two-dimensional nano sheet is very important.
Indium selenide is as important III-VI main group compound, the laminate structure being formed by Se-In-In-Se key, strong covalent linkage and faint Van der Waals force make its performance such as anisotropy, electricity, optics and magnetics, catalysis and air-sensitive with height between layers, thereby make indium selenide on the devices such as polarized radiation, photovoltaic solar cells, lithium cell, fluorescent apparatus, dielectric medium, field-effect transistor, cause numerous people's attention.Meanwhile, indium selenide for example also can be used as structural unit, for the preparation of the raw material of different ternary systems, CuInSe
2and AgInSe
2, and these materials have good photoelectric property, be widely used on photoelectric material device.In addition, indium selenide is the photoelectric material that a kind of direct band gap is 1.36eV, due to photoelectronic anisotropy, within the scope of visible light wave, has very high uptake factor, can effectively convert solar energy into electrical energy, and be a kind of photovoltaic energy material of excellence., compare with lead selenide with cadmium selenide, indium selenide also has hypotoxicity and environment friendly in low band-gap nano material meanwhile.
Indium selenide has cube crystalline phase and hexagonal crystal phase, and cube crystalline phase is low-temperature phase, and hexagonal crystal is high-temperature-phase mutually.Be subject to the restriction of synthetic method, cube crystalline phase InSe is difficult to synthesize by traditional method, and synthetic InSe major part is all hexagonal crystal phase at present, seldom relevant for a cube relevant report of crystalline phase InSe.The method of the synthetic InSe having developed mainly contains field-effect method, solid phase method, organo-metallic hot steam method etc., but above-mentioned synthetic method needs the instrument of high-end precision, temperature of reaction is at 400 ~ 1000 ℃, energy consumption is large, can produce poisonous gas, human body and environment are caused to certain harm, and the sample that these methods obtain also have the shortcomings such as heterogeneity and low yield.Therefore find simple, cheap, green, a controlled method, it is necessary and challenging synthesizing InSe nanometer structure.
Hydrothermal method has the advantages such as the product purity that equipment is simple, raw material easily obtains, obtain is high, good uniformity, chemical constitution precise control, is subject to many researchers' favor.Hydrothermal method is in special closed reactor (autoclave), the fluids such as water or organic solvent of take are reactive material, by reaction system being heated to critical temperature (or approaching critical temperature), create a High Temperature High Pressure reflection environment, impel reaction to carry out in liquid phase or gas phase, make indissoluble or insoluble substance dissolves recrystallization originally, then through separated and thermal treatment, obtain a kind of effective ways of product.Hydrothermal method has the following advantages: (1) is warm (generally between 120 ~ 200 ℃) liquid phase control in adopting, and energy consumption is relatively low, and suitability is wide, both can be used for the nanoparticle preparation that size is less, also can obtain larger-size monocrystalline; (2) raw material is relatively inexpensive is easy to get, and reaction is carried out in the quick convection current of liquid phase, and productive rate is high, phase is even, purity is high, well-crystallized, and shape size is controlled; (3), in water-heat process, can, by regulating temperature of reaction, pressure, time, pH value, precursor and tensio-active agent etc., reach the object of effective control reaction and growth characteristics; (4) reaction is carried out in the container of sealing, is applicable to the building-up reactions in poisonous system, can reduce environmental pollution.
Summary of the invention
For the defect existing in prior art and deficiency, the invention provides the hydrothermal synthesis method of a kind of cube of crystalline phase InSe nano material.
The hydrothermal synthesis method of a kind of cube of crystalline phase InSe nanometer sheet, that to take diethylenetriamine, hydrazine hydrate and water ternary mixing solutions be solvent, by the aqueous solution of the aqueous solution of indium chloride and Sodium Selenite hydrothermal synthesis reaction in the reactor of 180 ℃, then use absolute ethanol washing, centrifugation makes after being dried and calcining.From growth mechanism, infer, the method can be applicable to the preparation of other selenium, tellurium metal compound nano-material.
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
Steps A, take four hydration indium chlorides respectively, Sodium Selenite is dissolved in separately in deionized water and makes solution, wherein, described indium ion concentration is 0.1mmol/L, concentration of sodium selenite is 0.1mol/L;
Step B, measure above-mentioned solution mix and blend respectively, add diethylenetriamine, hydrazine hydrate and deionized water mix,
Wherein said indium ion: the mol ratio of Sodium Selenite is 2:3,
Described diethylenetriamine, the volume ratio of hydrazine hydrate and deionized water is 5:2:12;
Step C, at 180 ℃, react 72 ~ 96h, be then cooled to room temperature.
The flap that above-mentioned reaction is made, with after absolute ethanol washing, is placed in after 60 ℃ of vacuum drying ovens are dried and makes sheet indium selenide precursor.
In a preferred embodiment of the present invention, described calcining step is under argon shield, 400 ℃ of calcining 4h ~ 8h.
Cube crystalline phase InSe nanometer sheet being prepared from according to the hydrothermal synthesis method of above-mentioned cube of crystalline phase InSe nanometer sheet, from its X-ray diffraction analysis figure (XRD), the InSe of typical cube of crystalline phase.26.8 °, corresponding (110) crystal face, 44.7 °, corresponding is (220) crystal face, and 52.6 °, be (311) crystal face, 64.9 ° is (400) crystal face, 71.6 ° is (314) crystal face; From its scanning electron microscope (SEM) photograph (SEM), after calcining, the crystallinity of nanometer sheet strengthens, and surface is very smooth, and the size of sheet is homogeneous relatively, and length is at 0.6 ~ 1.3 micron, and width is at 0.5 ~ 1 micron, and thickness is 60nm, and major part is cubic sheet.
beneficial effect
Preparation method of the present invention is simple, with low cost, controllability is strong, product good crystallinity, output are high, environmental protection.
Accompanying drawing explanation
Fig. 1 is the sheet indium selenide forerunner's of preparation X-ray diffraction analysis figure (XRD);
Fig. 2 is the sheet indium selenide forerunner's of preparation scanning electron microscope (SEM) photograph (SEM);
Fig. 3 is the sheet indium selenide forerunner's of preparation transmission electron microscope picture (TEM);
Fig. 4 is the calcining X-ray diffraction analysis figure (XRD) of InSe nanometer sheet later;
Fig. 5 is the calcining scanning electron microscope (SEM) photograph (SEM) of InSe nanometer sheet later;
Fig. 6 is the calcining transmission electron microscope picture (TEM) of InSe nanometer sheet afterwards.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0442g indium chloride, the Sodium Selenite of 0.0519g is in the reactor of 25ml;
(2) use respectively 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, 12ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 15ml reactor in (1) in (2), stir 10min, it is mixed;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature three days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 6h, obtain InSe nanometer sheet.
Fig. 1 is the sheet indium selenide forerunner's of preparation XRD figure, and as can be seen from the figure the peak of the inside is many, at 10 °, has in the past the peak that ，Ci peak, a strong peak is typical precursor.
Fig. 2 is the sheet indium selenide forerunner's of preparation SEM figure, as can be seen from the figure, the surperficial smoother of nanometer sheet, long is 0.9-1.5 μ m, and wide is 0.6-1.1 μ m, and thickness is 90nm.
Fig. 3 is the sheet indium selenide forerunner's of preparation TEM figure.As can be seen from the figure, sheet surface smoother, almost approaches transparently, and the plasticity of sheet is fine.
Fig. 4 is the calcining XRD figure of InSe nanometer sheet later.This figure is the InSe of typical cube of crystalline phase, 26.8 °, and corresponding (110) crystal face, 44.7 °, corresponding is (220) crystal face, and 52.6 °, be (311) crystal face, 64.9 ° is (400) crystal face, 71.6 ° is (314) crystal face.
Fig. 5 is the calcining SEM figure of InSe nanometer sheet later.After calcining, the crystallinity of nanometer sheet strengthens, and surface is very smooth, and the size of sheet is homogeneous relatively, and length is at 0.6 ~ 1.3 micron, and width is at 0.5 ~ 1 micron, and thickness is 60nm, and major part is cubic sheet.
Fig. 6 is the calcining TEM figure of indium selenide afterwards.Smooth degree is not calcined before good, and can see what slice was comprised of small-particle from projection.
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0709g indium bromide, 0.0519g Sodium Selenite is in 25ml reactor;
(2) use respectively 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, 12ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 15ml reactor in (1) in (2), stir 10min, make it fully dissolve and mix;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature three days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 6h, obtain InSe nanometer sheet.
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0764g indium nitrate, 0.0519g Sodium Selenite is in 25ml reactor;
(2) use respectively 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, 12ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 15ml reactor in (1) in (2), stir 10min, make it fully dissolve and mix;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature three days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 6h, obtain InSe nanometer sheet.
Embodiment 4
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0884g indium chloride, the Sodium Selenite of 0.1038g is in the reactor of 50ml;
(2) use respectively 10ml transfer pipet, 5ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 10ml, 4ml, 24ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 30ml reactor in (1) in (2), stir 10min, it is mixed;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature three days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 6h, obtain InSe nanometer sheet.
Embodiment 5
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0442g indium chloride, the Sodium Selenite of 0.0519g is in the reactor of 25ml;
(2) use respectively 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, 12ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 15ml reactor in (1) in (2), stir 10min, it is mixed;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature four days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 6h, obtain InSe nanometer sheet.
Embodiment 6
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0442g indium chloride, the Sodium Selenite of 0.0519g is in the reactor of 25ml;
(2) use respectively 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, 12ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 15ml reactor in (1) in (2), stir 10min, it is mixed;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature three days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 4h, obtain InSe nanometer sheet.
Embodiment 7
A hydrothermal synthesis method for cube crystalline phase InSe nanometer sheet, concrete steps are as follows:
(1) with electronic balance, take respectively 0.0442g indium chloride, the Sodium Selenite of 0.0519g is in the reactor of 25ml;
(2) use respectively 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet measures diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, 12ml, in 50ml beaker, stirs 3min with glass stick, and it is mixed;
(3) with transfer pipet, measure mixing solutions 15ml reactor in (1) in (2), stir 10min, it is mixed;
(4) reactor sealing is put into 180 ℃ of baking oven constant temperature three days, then naturally cool to room temperature, use absolute ethanol washing 5 times, the dry nanometer sheet that obtains yellow indium selenide precursor in 60 ℃ of vacuum drying ovens;
(5) the yellow precursor obtaining in (4) is placed in to tube furnace, argon shield, 400 ℃ of calcining 8h, obtain InSe nanometer sheet.
Claims (3)
1. the hydrothermal synthesis method of one kind of cube of crystalline phase InSe nanometer sheet, that to take diethylenetriamine, hydrazine hydrate and water ternary mixing solutions be solvent, by the aqueous solution of the aqueous solution of indium chloride and Sodium Selenite hydrothermal synthesis reaction in the reactor of 180 ℃, then use absolute ethanol washing, centrifugation makes after being dried and calcining, it is characterized in that
Described hydrothermal synthesis reaction comprises the steps:
Steps A, take four hydration indium chlorides respectively, Sodium Selenite is dissolved in separately in deionized water and makes solution, wherein, described indium ion concentration is 0.1mmol/L, concentration of sodium selenite is 0.1mol/L;
Step B, measure above-mentioned solution mix and blend respectively, add diethylenetriamine, hydrazine hydrate and deionized water mix,
Wherein said indium ion: the mol ratio of Sodium Selenite is 2:3,
Described diethylenetriamine, the volume ratio of hydrazine hydrate and deionized water is 5:2:12;
Step C, at 180 ℃, react 72h ~ 96h, be then cooled to room temperature;
Described calcining step is under argon shield, 400 ℃ of calcining 6h.
2. cube crystalline phase InSe nanometer sheet that method is prepared from according to claim 1.
3. according to claim 2 cube of crystalline phase InSe nanometer sheet, is characterized in that the length of nanometer sheet is at 0.6 ~ 1.3 micron, and width is at 0.5 ~ 1 micron, and thickness is 60nm.
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