CN111137926A - Non-equilibrium state nanowire and preparation method thereof - Google Patents

Non-equilibrium state nanowire and preparation method thereof Download PDF

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CN111137926A
CN111137926A CN202010004822.2A CN202010004822A CN111137926A CN 111137926 A CN111137926 A CN 111137926A CN 202010004822 A CN202010004822 A CN 202010004822A CN 111137926 A CN111137926 A CN 111137926A
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杨晴
张莉
游苏
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University of Science and Technology of China USTC
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Abstract

The invention provides a preparation method of a non-equilibrium state nanowire, which comprises the following steps: s1) mixing a silver source and a sulfur source or a selenium source in unsaturated amine of C10-C30, and heating for reaction to obtain an intermediate product; s2) mixing the intermediate product, a cobalt source and a sulfur source or a selenium source, and heating for reaction to obtain the non-equilibrium state nanowire. Compared with the prior art, the preparation method has the advantages that the preparation of the non-equilibrium sphalerite phase cobaltous sulfide one-dimensional nanostructure is realized for the first time, the added unsaturated amine is simultaneously used as a solvent and a surfactant, the reaction raw materials are simplified, the reaction temperature is reduced by introducing the silver source, the reaction conditions are mild, the reaction time is shortened, the reaction efficiency is improved, the growth behavior of the nanocrystal is changed, and the appearance and the phase are changed; meanwhile, the length and the particle size of the non-equilibrium nanowire can be regulated and controlled by regulating the reaction temperature, the reaction time, the concentration of a reaction precursor and the type of a catalyst, and the obtained nanowire has uniform particle size distribution and high quality.

Description

Non-equilibrium state nanowire and preparation method thereof
Technical Field
The invention belongs to the technical field of solid nano materials, and particularly relates to a non-equilibrium nanowire and a preparation method thereof.
Background
As can be seen from the cobalt-sulfur binary phase diagram, cobalt sulfide has various chemical compositions, and Co is common9S8、CoS、Co3S4、CoS2Etc. this cobaltous sulfide (CoS) in which the ratio of cobalt to sulfur is 1 to 1 has three phases, a thermodynamically stable hexa-coordinated NiAs structure (Hexagonal, H) Hexagonal phase, a non-equilibrium tetradentate Wurtzite (Wurtzite, WZ) phase and a Zincblende (ZB) phase at normal temperature and pressure.
Early research products are mostly prepared by solid phase element reaction, with the abundance and development of liquid phase synthesis methods, various preparation methods and various shapes of cobaltous sulfide are reported in sequence, but in the report, most research objects are NiAs structure hexagonal CoS. In 2003, the journal of Materials Chemistry and Physics reported that hexagonal phase CoS nanoparticles were prepared from metal salts and thiourea in ethylene glycol solvent by microwave-assisted synthesis (Materials Chemistry and Physics,2003,82, 206-. In 2008, the Power supply Journal reports for the first time that an environment-friendly green chemical synthesis method, namely a biomolecule-assisted hydrothermal method is used for synthesizing hexagonal-phase CoS nanospheres and similar nanowires assembled by the nanospheres, L-cysteine is used as a sulfur source in the reaction, the nanospheres can be obtained by reacting for 6 hours at 190 ℃, and the polarity of the reaction precursor solution is adjusted by adding ethanol, so that the similar nanowires assembled by the nanospheres are prepared (Journal of Power Sources,2008,180,676 and 681.). In 2012, a needle-point hexagonal CoS nanorod array was prepared on a fluorine-doped tin oxide conductive substrate by a two-step method, and Co was used as a Co-dopant3O4The needle-tip-shaped nanorod array is firstly deposited on a fluorine-doped tin oxide conductive substrate and then is converted into a CoS needle-tip-shaped nanorod array through a chemical bath method, and a pure-phase hexagonal-phase NiAs structure CoS array can be obtained after 12h of reaction, and the report is published in journal of American chemical society nanometer (ACS Nano,2012,6,8, 7016-7025.). In 2013, hexagonal-phase CoS spherical nanoparticles of 3.6nm to 12.8nm were prepared by a one-pot method, and the research work is published in journal of Particle and Particle system characterization (Particle)&Particle systems Characterization,2013,30, 501-. In 2014, journal of physical chemistry C reports preparation of two-dimensional CoS nanosheetsThe product was obtained by a typical hydrothermal method using cobalt nitrate and thiourea as reaction precursors and reacting at 180 ℃ for 24h (The Journal of Physical Chemistry C,2014,118, 20238-20245.).
Nonequilibrium CoS has long been obtained in the form of a wurtzite phase film. The first report of the chemical preparation of wurtzite phase CoS was recorded in 1986 in journal of Rapid report of Material science1.035Thin films (Journal of materials Science Letters, 1986,5, 1216-1218). In 2011, the journal of the Material Kuai newspaper reports the chemical bath deposition synthesis of a deep green wurtzite phase CoS film, cobaltous sulfate and thiourea are used as a metal source and a sulfur source respectively in the reaction, ammonia water is used as a solvent, triethylamine is used as a coordination solvent, and a product can be obtained after 24 hours of reaction (Materials Letters,2011,65, 2639-.
Two recent studies indicate that the non-equilibrium CoS nanostructure including wurtzite phase and sphalerite phase can be prepared by cation exchange method, 2016, reports the liquid phase preparation of wurtzite phase CoS nanoplate, reaction via magnesite type Cu2-xS nano-discs were used as templates, and wurtzite phase CoS nano-discs were prepared by cation exchange in a liquid phase environment consisting of trioctylphosphine, oleylamine, toluene, and the like (Journal of the American chemical society,2016,138, 471-474.). In 2017, using the same cation exchange method, researchers of this research group changed the reaction template to make chalcocite phase Cu2-xThe S nanometer disc is used as a reaction template to prepare the sphalerite phase CoS nanometer disc, and the report is published in the journal of German applied chemistry (Angewandte Chemie International Edition,2017,56, 6464-6467), and the non-equilibrium sphalerite phase CoS phase is reported for the first time.
In the above many studies on CoS, reports on one-dimensional nanostructures, especially high-quality nanowires, are few. 2003, journal of chemical communications reports that NiAs structure hexagonal phase CoS nanowires are prepared by a chemical vapor deposition method, and reaction precursor CoCl is heated under the condition that no catalyst exists on a Si substrate2Reacting with sulfur powder at 850 deg.C for 2h to obtain film composed of single crystal nanowire (Chemical Communication),2003,2498-2499). However, up to now, non-equilibrium CoS nanowires, especially zinc blende phase nanowires, have not been reported because of the preparation difficulties that have been pending.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a non-equilibrium nanowire and a method for preparing the same, wherein the method for preparing the non-equilibrium nanowire is simple and mild.
The invention provides a non-equilibrium state nanowire comprising a sphalerite phase CoS or an orthorhombic phase CoSe2The sphalerite phase CoS or orthorhombic phase CoSe2With Ag2S or Ag2Se is formed as a catalyst.
Preferably, the length of the non-equilibrium state nanowire is 30 nm-1 μm; the diameter of the non-equilibrium state nanowire is 5-50 nm.
The invention also provides a preparation method of the non-equilibrium state nanowire, which comprises the following steps:
s1) mixing a silver source and a sulfur source or a selenium source in unsaturated amine of C10-C30, and heating for reaction to obtain an intermediate product;
s2) mixing the intermediate product, a cobalt source and a sulfur source or a selenium source, and heating for reaction to obtain the non-equilibrium state nanowire.
Preferably, the silver source is selected from silver nitrate and/or silver acetate;
the sulfur source is selected from one or more of dibenzyl disulfide, diphenyl disulfide and sulfur powder;
the selenium source is selected from dibenzyl diselenide and/or selenium powder;
the cobalt source is selected from one or more of cobaltous chloride, cobaltous acetate and cobalt (II) acetylacetonate;
the unsaturated amine of C10-C30 is oleylamine.
Preferably, the molar ratio of the silver ions in the silver source to the cobalt ions in the cobalt source is (1-10): 100.
preferably, the step S1) is specifically;
heating unsaturated amine of C10-C30, adding silver source solution and sulfur source or selenium source, and heating for reaction to obtain an intermediate product; the silver source solution is a solution of a silver source and C10-C30 unsaturated amine.
Preferably, the heating temperature in the step S1) is 110-150 ℃; the heating time is 10-60 min; the temperature of the heating reaction is 110-200 ℃; the heating reaction time is 10-60 min.
Preferably, in the step S2), the cobalt source and the sulfur source or the selenium source are dissolved in a small amount of C10-C30 unsaturated amine to form a reaction stock solution, and then the reaction stock solution is mixed with the intermediate product and heated to react, so as to obtain the non-equilibrium state nanowire.
Preferably, the concentration of the cobalt source in the mixed solution after the intermediate, the cobalt source and the sulfur source or the selenium source are mixed in the step S2) is 0.009-0.02 mmol/ml.
Preferably, the heating reaction temperature in the step S2) is 110-220 ℃; the heating reaction time is 2 min-3 h.
The invention provides a preparation method of a non-equilibrium state nanowire, which comprises the following steps: s1) mixing a silver source and a sulfur source or a selenium source in unsaturated amine of C10-C30, and heating for reaction to obtain an intermediate product; s2) mixing the intermediate product, a cobalt source and a sulfur source or a selenium source, and heating for reaction to obtain the non-equilibrium state nanowire. Compared with the prior art, the preparation method has the advantages that the preparation of the non-equilibrium sphalerite phase cobaltous sulfide one-dimensional nanostructure is realized for the first time, the added unsaturated amine is simultaneously used as a solvent and a surfactant, the reaction raw materials are simplified, the reaction temperature is reduced by introducing the silver source, the reaction conditions are mild, the reaction time is shortened, the reaction efficiency is improved, the growth behavior of the nanocrystal is changed, and the appearance and the phase are changed; meanwhile, the length and the particle size of the non-equilibrium nanowire can be regulated and controlled by regulating the reaction temperature, the reaction time, the concentration of a reaction precursor and the type of a catalyst, the preparation procedure is simple and easy to operate, and the obtained non-equilibrium nanowire has uniform particle size distribution and high quality and is suitable for large-scale industrial production.
Experiments show that the preparation method can prepare high-quality uniform sphalerite phase cobaltous sulfide CoS nanowires and Ag at lower temperature and in a wider temperature range (110-200 ℃), and2S-CoS one-dimensional nanostructure, Ag2One-dimensional nanostructure of Se-CoS and orthorhombic CoSe2A nanowire.
Drawings
FIG. 1 is an X-ray diffraction pattern diagram of non-equilibrium sphalerite phase CoS nanowires obtained in example 1 of the present invention;
FIG. 2 is a TEM photograph of non-equilibrium sphalerite phase CoS nanowires obtained in example 1 of the present invention;
FIG. 3 is a TEM image of non-equilibrium sphalerite phase CoS nanowires obtained in example 1 of the present invention;
FIG. 4 is a high resolution TEM (transmission electron microscope) photograph and a selected Fourier transform electron diffraction pattern of a non-equilibrium sphalerite phase CoS nanowire obtained in example 1 of the present invention;
FIG. 5 is a scanning transmission electron microscopy high-angle annular dark field image of a non-equilibrium sphalerite phase CoS nanowire obtained in example 1 of the present invention;
FIG. 6 is a TEM image of non-equilibrium sphalerite phase CoS nanowires obtained in example 2 of the present invention;
FIG. 7 shows the non-equilibrium orthorhombic CoSe obtained in example 3 of the present invention2Scanning electron micrographs of nanowires;
FIG. 8 shows the non-equilibrium orthorhombic CoSe obtained in example 3 of the present invention2Transmission electron microscopy of nanowires;
FIG. 9 shows the non-equilibrium orthorhombic CoSe obtained in example 3 of the present invention2An X-ray diffraction pattern of the nanowires;
FIG. 10 shows the non-equilibrium orthorhombic CoSe obtained in example 4 of the present invention2Transmission electron microscopy of nanowires.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a non-equilibrium state nanowire comprising a sphalerite phase CoS or an orthorhombic phase CoSe2The sphalerite phase CoS or orthorhombic phase CoSe2With Ag2S or Ag2Se is formed as a catalyst.
In the present invention, the sphalerite phase CoS or orthorhombic phase CoSe2Preferably as Ag2S or Ag2Se is a Solid catalyst and is obtained by catalytic growth of a liquid-Solid (SSS) growth mechanism; wherein the molar ratio of Ag to Co is preferably (1-10): 100, more preferably (1.5 to 8): 100, and preferably (1.5-5): 100, most preferably (1.5-3): 100, respectively; the length of the non-equilibrium state nanowire is preferably 30 nm-1 mu m, more preferably 45-900 nm, further preferably 55-800 nm, and most preferably 76-800 nm; the diameter of the non-equilibrium state nanowire is preferably 5-50 nm, more preferably 5-30 nm, still more preferably 6-20 nm, and most preferably 6-16 nm.
The invention also provides a preparation method of the non-equilibrium state nanowire, which comprises the following steps: s1) mixing a silver source and a sulfur source or a selenium source in unsaturated amine of C10-C30, and heating for reaction to obtain an intermediate product; s2) mixing the intermediate product, a cobalt source and a sulfur source or a selenium source, and heating for reaction to obtain the non-equilibrium state nanowire.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The silver source is preferably a silver compound that can form a nanocrystal catalyst with selenium ions or sulfur ions, more preferably silver nitrate and/or silver acetate, and even more preferably silver nitrate.
The sulfur source is preferably one or more of dibenzyl disulfide, diphenyl disulfide and sulfur powder, and more preferably dibenzyl disulfide.
The selenium source is preferably dibenzyl diselenide and/or selenium powder, and is more preferably dibenzyl diselenide.
The cobalt source is preferably a cobaltous salt soluble in unsaturated amines from C10 to C30, more preferably one or more of cobaltous chloride, cobaltous acetate and cobalt (II) acetylacetonate, and still more preferably one or more of cobaltous chloride hexahydrate, cobaltous acetate hexahydrate and cobalt (II) acetylacetonate.
The unsaturated amine of C10-C30 is preferably an unsaturated amine of C12-C25, more preferably an unsaturated amine of C14-C20, and even more preferably oleylamine.
Mixing a silver source and a sulfur source or a selenium source in unsaturated amine of C10-C30; in the invention, the silver source is preferably added in the form of a C10-C30 unsaturated amine solution of the silver source, namely, the silver source is firstly mixed with the C10-C30 unsaturated amine to obtain a silver source solution, and then the silver source solution is mixed with the C10-C30 unsaturated amine and a sulfur source or a selenium source for reaction, and more preferably, the silver source solution is firstly mixed with the sulfur source or the selenium source and then is mixed with the C10-C30 unsaturated amine; the molar ratio of the silver ions in the silver source to the sulfur ions in the sulfur source or the selenium ions in the selenium source is preferably 1: (1 to 4), more preferably 1: (2-4), and more preferably 1; (3-3.5), most preferably 1: (3.3-3.4); the concentration of silver ions in the silver source is preferably 4-10 mmol/L, more preferably 4-8 mmol/L, and still more preferably 6 mmol/L; the molar concentration of the silver ions in the mixed solution after mixing is preferably 0.0001 to 0.0005mmol/ml, more preferably 0.0002 to 0.0005mmol/ml, and still more preferably 0.0003 to 0.0004 mmol/ml.
In the invention, more preferably, C10-C30 unsaturated amine is heated firstly, and then silver source solution is added to be mixed with a sulfur source or a selenium source; the heating temperature is preferably 110-160 ℃, more preferably 130-160 ℃, still more preferably 150-160 ℃, and most preferably heating reflux; the heating time is preferably 10-60 min, and more preferably 20-40 min; low boiling impurities in the C10-C30 unsaturated amines can be removed by heating.
After mixing, heating for reaction to obtain an intermediate product; the temperature of the heating reaction is preferably 110-200 ℃, more preferably 110-180 ℃, and further preferably 150-180 ℃; the heating reaction time is preferably 10-60 min, more preferably 10-50 min, and still more preferably 10-30 min. The silver sulfide or silver selenide nanocrystal catalyst is formed by heating a reactive silver source to react with a sulfur source or a selenium source.
Mixing the intermediate product, a cobalt source and a sulfur source or a selenium source; in the invention, the intermediate product can be directly mixed with the cobalt source and the sulfur source or the selenium source without any treatment, or can be firstly cooled to room temperature and then mixed with the cobalt source and the sulfur source or the selenium source; the molar ratio of the silver ions in the intermediate product to the cobalt ions in the cobalt source is preferably (1-10): 100, more preferably (1.5 to 8): 100, and preferably (1.5-5): 100, most preferably (1.5-3): 100, respectively; the molar ratio of cobalt ions in the cobalt source to sulfur ions in the sulfur source or selenium ions in the selenium source is preferably 1: (2-4), more preferably 1: (2-3), preferably 1: (2-2.85); the concentration of the cobalt source in the mixed solution after mixing is preferably 0.009-0.02 mmol/ml, more preferably 0.0095-0.019 mmol/ml.
In the invention, preferably, a cobalt source and a sulfur source or a selenium source are dissolved in a small amount of unsaturated amine of C10-C30 to form a reaction stock solution, and then the reaction stock solution is mixed with an intermediate product; the volume ratio of the small amount of the C10-C30 unsaturated amine to the intermediate product is preferably 1: (4-5), more preferably 1: (4-4.5), and preferably 1: 4.25.
after mixing, heating for reaction; the temperature of the heating reaction is preferably 110-220 ℃, more preferably 110-200 ℃, and further preferably 150-200 ℃; the heating reaction time is preferably 2min to 3h, more preferably 2min to 120min, still more preferably 5 min to 120min, still more preferably 30min to 120min, and most preferably 60min to 120 min.
After the heating reaction, washing and drying are preferably carried out, so as to obtain the non-equilibrium state nanowire; more preferably, the mixture is cooled to room temperature, and then washed and dried; the solvent used for washing is preferably n-hexane; the drying temperature is preferably 50 ℃ to 80 ℃, and more preferably 60 ℃ to 70 ℃.
The invention realizes the preparation of the one-dimensional cobaltous sulfide nanostructure of the non-equilibrium sphalerite phase for the first time, the added unsaturated amine is simultaneously used as a solvent and a surfactant, the reaction raw materials are simplified, the reaction temperature is reduced by introducing a silver source, the reaction conditions are mild, the reaction time is shortened, the reaction efficiency is improved, the growth behavior of the nanocrystal is changed, and the appearance and the phase are changed; meanwhile, the length and the particle size of the non-equilibrium nanowire can be regulated and controlled by regulating the reaction temperature, the reaction time, the concentration of a reaction precursor and the type of a catalyst, the preparation procedure is simple and easy to operate, and the obtained non-equilibrium nanowire has uniform particle size distribution and high quality and is suitable for large-scale industrial production.
In order to further illustrate the present invention, the following describes a non-equilibrium nanowire and a method for preparing the same in detail with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
Silver sulfide catalytic growth of non-equilibrium cobalt sulfide nanowires:
ultrasonically dissolving 0.0034g of silver nitrate and 3.3mL of oleylamine to form a silver nitrate oleylamine solution with the concentration of 6mmol/L for later use.
Measuring 4mL of oleylamine, placing the oleylamine in a 100mL three-necked flask, heating to 150 ℃, refluxing for 20min, injecting a mixed solution formed by 0.0012g of dibenzyl disulfide and 0.25mL of silver nitrate oleylamine solution, and reacting for 10 min. And (3) injecting reaction stock solution formed by 0.0119g of cobaltous chloride hexahydrate, 0.0123g of dibenzyl disulfide and 1mL of oleylamine, continuing to react for 1h, cooling the reaction to room temperature, washing the product for a plurality of times by using n-hexane, and drying in a vacuum drying oven at 60 ℃ to obtain the non-equilibrium sphalerite phase CoS nanowire.
Irradiation with CuK α radiation (wavelength) using Philips X' pert PRO X-ray powder diffractometer
Figure BDA0002354841490000071
Figure BDA0002354841490000072
) The X-ray diffraction pattern of the nanowire obtained in example 1 was obtained by X-ray diffraction analysis as a diffraction light source, as shown in fig. 1. As can be seen from FIG. 1, the 2 theta in the X-ray diffraction diagram has obvious diffraction peaks at 20-70 degrees, and because the sphalerite phase CoS has no standard card, the journal of German applied chemistry reports the preparation of the sphalerite phase nano disk for the first time, and the diffraction peak position and the relative intensity of the sphalerite phase nano wire prepared by the invention are consistent with those in the literature. 29.3537 °, 49.0310 °, and 58.0401 ° correspond to the (111), (220), and (311) diffraction planes, respectively.
The morphology and size of the non-equilibrium sphalerite phase CoS nanowire obtained in example 1 were observed by a Transmission Electron Microscope (TEM) of Hitach H-7700, japan, and transmission electron micrographs thereof were obtained as shown in fig. 2 and 3, from the morphology photographs at the end point and the main body of the nanowire in fig. 2, the diameter of the nanowire was about 6.7nm, and from the low-magnification electron microscope photograph in fig. 3, the length of the nanowire was about 100 nm.
Further observing the morphology and structure of the non-equilibrium sphalerite phase CoS nanowire obtained in example 1 by using a Japanese Hitach H-7700 type Transmission Electron Microscope (TEM), wherein the obtained high-resolution electron microscope photograph is shown in FIG. 4, the lower right picture is a selected area Fourier transform diffraction pattern, and the high-resolution transmission electron microscope photograph and the Fourier transform diffraction pattern are combined to show that the nanowire has good crystallinity, is a sphalerite phase, and has a lattice spacing of
Figure BDA0002354841490000081
The crystal face of (a) corresponds to the (110) face of the sphalerite phase, and the growth direction of the nanowire is<110>And (4) direction.
Further observation of the scanning transmission electron microscopy high-angle toroidal dark field image (HAADF-STEM) of the nanowires obtained in example 1 was performed using a Transmission Electron Microscope (TEM) of Hitach H-7700, as shown in fig. 5, it was further known from the figure that the particle size distribution of the prepared non-equilibrium zincblende-phase CoS nanowires was uniform, and the presence of semicircular particles at the end points of the nanowires indicated that the nanowires were obtained by catalytic growth of silver sulfide.
Example 2
Silver selenide catalyzes and grows non-equilibrium state cobaltous sulfide nano-wires:
ultrasonically dissolving 0.0034g of silver nitrate and 3.3mL of oleylamine to form a silver nitrate oleylamine solution with the concentration of 6mmol/L for later use.
Weighing 4mL of oleylamine, placing the oleylamine in a 100mL three-necked bottle, heating to 160 ℃, refluxing for 20min, injecting a mixed solution formed by 0.0017g of dibenzyl diselenide and 0.25mL of silver nitrate oleylamine solution, and reacting for 10 min. And injecting a reaction stock solution formed by 0.0238g of cobaltous chloride hexahydrate, 0.0246g of dibenzyl disulfide and 1mL of oleylamine, continuing to react for 1h, cooling the reaction product to room temperature, washing the product for a plurality of times by using n-hexane, and drying the product in a vacuum drying oven at 60 ℃ to obtain the non-equilibrium zinc blende phase CoS nanowire.
The morphology and size of the non-equilibrium CoS nanowires obtained in example 2 were observed by a Transmission Electron Microscope (TEM) of Hitach H-7650, japan, and as shown in fig. 6, the diameter of the prepared nanowires was about 7nm, and the particle size distribution of the nanowires was uniform.
Example 3
Silver selenide catalyzes and grows the cobalt selenide nanowire in the nonequilibrium state:
placing 4mL of oleylamine into a three-necked bottle, carrying out reflux at 150 ℃ for 20min, injecting a reaction stock solution formed by 0.0017g of dibenzyl diselenide and 0.25mL of silver nitrate oleylamine solution, reacting for 30min, cooling to room temperature, transferring the reaction solution to an inner container of a polytetrafluoroethylene reaction kettle, uniformly mixing the reaction stock solution with 0.0257g of cobalt acetylacetonate, 0.0341g of dibenzyl diselenide and 1mL of oleylamine, carrying out reaction for 2h under sealed heating to 160 ℃, cooling to room temperature, washing a product for several times by using n-hexane, and carrying out vacuum drying at 60 ℃ to obtain nonequilibrium orthorhombic phase CoSe2A nanowire.
Observation of the non-equilibrium orthorhombic CoSe obtained in example 3 by means of a JSM-6700F Scanning Electron Microscope (SEM)2The shape of the nanowire, and the scanning electron microscope photograph thereof, were obtained, and the obtained product was linear in shape, as shown in fig. 7.
Observation of the non-equilibrium Quadrature phase CoSe obtained in example 3 with a Transmission Electron Microscope (TEM) of Hitach H-7650 type in Japan2The shape and size of the nanowires are shown in fig. 8, and the diameter of the nanowires is about 10.3nm, and the thickness of the nanowires is uniform.
Irradiation with Cu K α (wavelength) using Philips X' pert PRO X-ray powder diffractometer
Figure BDA0002354841490000091
Figure BDA0002354841490000092
) The X-ray diffraction pattern of the nanowire obtained in example 3 was obtained by X-ray diffraction analysis as a diffraction light source, as shown in fig. 9. Diffraction flowerDiffraction peaks at 24.0157 °, 29.0025 °, 30.7550 °, 34.4926 °, 35.9707 °, 40.2975 °, 44.0225 °, 47.7537 °, 50.3201 °, 51.6947 °, 53.4559 °, 55.4120 °, 56.9317 °, 59.4500 °, 63.2937 ° and 66.2558 ° in the sample respectively correspond to orthogonal-phase CoSe with a card number of (89-2033)2The (110), (011), (020), (111), (120), (200), (210), (121), (211), (002), (130), (031), (221), (131), (310), (122) and (311) crystal planes in the diffraction pattern.
Example 4
The silver nano particles catalyze and grow the nonequilibrium state orthorhombic phase cobalt selenide nano wires:
placing 4mL of oleylamine into a three-necked bottle, refluxing for 20min at 150 ℃, injecting 0.25mL of silver nitrate oleylamine solution (6mmol/L), reacting for 30min, heating to 200 ℃, injecting reaction stock solution formed by 0.0257g of cobalt acetylacetonate, 0.0341g of dibenzyl diselenide and 1mL of oleylamine, continuing to react for 1h, cooling to room temperature, washing the product for a plurality of times by using n-hexane, and drying in vacuum at 60 ℃ to obtain the nonequilibrium state quadrature phase cobalt selenide nanowire.
The non-equilibrium orthorhombic CoSe obtained in example 4 was observed with a Transmission Electron Microscope (TEM) of Hitach H-7650 type in Japan2The morphology and size of the nanowires, a transmission electron micrograph of which is shown in fig. 10. The diameter of the nanowire is about 16nm and the thickness is uniform.
According to the embodiment of the invention, the non-equilibrium sphalerite phase CoS nanowire and the orthorhombic phase CoSe can be treated by using different reaction temperatures, reaction times, reaction precursor concentration, reaction precursor types and catalyst types2Is adjusted for length and particle size. The reaction temperature is 110 ℃, the reaction time is 3 hours, namely, a reaction product CoS one-dimensional nano structure is generated, the diameter of the nano wire is about 15-18 nm, and the length can reach about 250 nm; the reaction temperature is 200 ℃, the reaction time is 2min, and then CoS nanowires are generated, the diameter is 8.4-12.6 nm, and the length is about 120 nm; when the concentration of the reaction precursor source is doubled as compared with the typical reaction, the length of the generated product nanowire is increased and can reach 800nm, and the diameter is about 6 nm; in addition, when the sulfur source of one of the reaction precursor sources is replaced by sulfur powder, the product is still the sulfur powder after the reaction is carried out for 1 hour at the temperature of 150 DEG CA one-dimensional nanostructure having a diameter of about 12.7 nm; when the sulfur source is replaced by diphenyl disulfide, CoS one-dimensional nanostructures are generated after reaction at 190 ℃ for 20min, the length is about 76nm, and the diameter is about 16 nm.

Claims (10)

1. A non-equilibrium state nanowire comprising a sphalerite phase CoS or an orthorhombic phase CoSe2The sphalerite phase CoS or orthorhombic phase CoSe2With Ag2S or Ag2Se is formed as a catalyst.
2. The non-equilibrium nanowire of claim 1, wherein the length of the non-equilibrium nanowire is 30nm to 1 μm; the diameter of the non-equilibrium state nanowire is 5-50 nm.
3. A method for preparing a non-equilibrium nanowire is characterized by comprising the following steps:
s1) mixing a silver source and a sulfur source or a selenium source in unsaturated amine of C10-C30, and heating for reaction to obtain an intermediate product;
s2) mixing the intermediate product, a cobalt source and a sulfur source or a selenium source, and heating for reaction to obtain the non-equilibrium state nanowire.
4. The method according to claim 3, wherein the silver source is selected from silver nitrate and/or silver acetate;
the sulfur source is selected from one or more of dibenzyl disulfide, diphenyl disulfide and sulfur powder;
the selenium source is selected from dibenzyl diselenide and/or selenium powder;
the cobalt source is selected from one or more of cobaltous chloride, cobaltous acetate and cobalt (II) acetylacetonate;
the unsaturated amine of C10-C30 is oleylamine.
5. The preparation method according to claim 3, wherein the molar ratio of the silver ions in the silver source to the cobalt ions in the cobalt source is (1-10): 100.
6. the method according to claim 3, wherein the step S1) is specifically;
heating unsaturated amine of C10-C30, adding silver source solution and sulfur source or selenium source, and heating for reaction to obtain an intermediate product; the silver source solution is a solution of a silver source and C10-C30 unsaturated amine.
7. The method according to claim 6, wherein the heating temperature in the step S1) is 110 ℃ to 150 ℃; the heating time is 10-60 min; the temperature of the heating reaction is 110-200 ℃; the heating reaction time is 10-60 min.
8. The preparation method according to claim 3, wherein in the step S2), the cobalt source and the sulfur source or the selenium source are dissolved in a small amount of C10-C30 unsaturated amine to form a reaction stock solution, and then the reaction stock solution is mixed with the intermediate product and heated to react to obtain the non-equilibrium state nanowire.
9. The method according to claim 3, wherein the concentration of the cobalt source in the mixture of the intermediate, the cobalt source, and the sulfur source or the selenium source in step S2) is 0.009-0.02 mmol/ml.
10. The preparation method according to claim 3, wherein the heating reaction temperature in the step S2) is 110 to 220 ℃; the heating reaction time is 2 min-3 h.
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