A method for preparing Te nanowires based on hydrolysis of LiBH4 intercalated layered metal tellurides

Abstract

The application relates to the field of frontier new material preparation technology, and discloses a method for preparing Te nanowires based on LiBH4 intercalation layered metal telluride hydrolysis, which takes layered metal telluride as raw material, takes LiBH4 as intercalation agent, carries out intercalation reaction under inert atmosphere, then contacts the lithium intercalation product with deionized water, generates Te nanowires through second-level hydrolysis reaction, and through separation, washing, methanol dispersion, drying treatment, high-crystallinity Te nanowire products are obtained. Compared with the prior art, the application realizes efficient and rapid preparation of pure-phase and Se atom-doped Te nanowires by using the rapid hydrolysis effect induced by LiBH4 intercalation, the preparation process is mild, the operation is simple, the cost is low, the obtained Te nanowires have high crystallinity and good dispersity, and can be widely applied in the fields of photoelectric detection, energy storage devices, catalysis and the like.

Description

Technical Field

[0001] This invention relates to the field of cutting-edge new material preparation technology, and in particular to a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. Background Technology

[0002] Te nanowires are one-dimensional van der Waals semiconductor structures with significant structural anisotropy. They enable efficient axial transport of charge carriers and possess excellent optoelectronic and thermoelectric properties, making them promising for applications in micro-nano devices such as field-effect transistors and photodetectors.

[0003] Existing processes for preparing Te nanowires mainly include hydrothermal methods, chemical vapor deposition (CVD), and molecular beam epitaxy. Hydrothermal methods often use tellurate as a precursor, combined with a reducing agent and surfactant to prepare an aqueous solution, which is then placed in an autoclave and reacted under high pressure at 120-220℃, typically taking 3-24 hours. The reactants undergo a reduction reaction to generate Te nanowires, which are collected after centrifugation and washing. This process has low cost and can be mass-produced, but the crystal quality is usually not high due to the influence of surfactants. Chemical vapor deposition (CVD) typically uses TeO2 or elemental tellurium as a gas source in a tube furnace, where it is reduced with hydrogen to generate Te vapor, which is then transported by a carrier gas to the surface of a low-temperature substrate for nucleation and growth. The resulting nanowires are surfactant-free and have good crystallinity, but usually require high temperatures of 300-700℃, and the yield is low, with reaction times typically exceeding 30 minutes. Molecular beam epitaxy (MBE) uses high-purity tellurium molecular beams for directional deposition in an ultra-high vacuum chamber, achieving atomic-level epitaxial growth at high substrate temperatures. This allows for precise control of nanowire size and orientation, but the equipment is expensive and the production scale is limited.

[0004] Therefore, it is urgent and necessary to explore a method for preparing Te nanowires that has high crystal quality, short preparation time, low equipment cost, can be mass-produced, is compatible with solution processing, and has excellent comprehensive performance. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the existing technology by providing a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal tellurides. The Te nanowires produced by this invention do not require the addition of surfactants and exhibit advantages such as uniform size, high crystallinity, short growth cycle, mass production capability, and ease of processing and storage. The reagents and raw materials used in this invention have low toxicity to humans and are environmentally friendly.

[0006] The objective of this invention can be achieved through the following technical solutions: The technical concept of this application includes: Compared to MoS2 and MoSe2, MoTe2 has longer Mo-Te bond lengths and lower bond energies, allowing for crystal layering under mild LiBH4 intercalation conditions to obtain MoTe2 nanosheets. Simultaneously, the lower Mo-Te bond breaking energy barrier means that slightly increasing the reaction temperature or extending the reaction time not only further promotes complete MoTe2 layering but also directly breaks the Mo-Te covalent bonds. Since Te-Te covalent bonds naturally exist within the MoTe2 crystal, no additional surfactant is needed during Te nanowire growth. The layered structure significantly accelerates the Mo-Te bond dissociation rate, thereby significantly accelerating Te nanowire growth. MoTe2 can also be replaced with WTe2 and TaTe2, which have similar bond lengths. This method is also applicable to telluride precursors WTe2 and TaTe2, which have similar bond lengths and energies to MoTe2. For MoTe... 1.5 Se 0.5 or WTe 1.5 Se 0.5 When the crystal is the precursor, a Se-Te bond structure is naturally formed inside the crystal. In addition, since the size of Se atoms is smaller than that of Te, in-situ doping can be achieved by embedding them into the lattice during the crystallization process of Te, resulting in Se atom-doped Te nanowires.

[0007] This invention provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, the method comprising the following steps: (1) After mixing layered metal telluride and LiBH4 (lithium borohydride), an intercalation reaction was carried out under inert gas conditions, and the lithium intercalation product was obtained after cooling. (2) At room temperature, the lithium intercalation product is brought into contact with water to undergo a second-level hydrolysis reaction to generate Te nanowires, resulting in a mixed system in which Te nanowires (tellurium nanowires) are dispersed.

[0008] Further, in step (1), the layered metal telluride is selected from MoTe2, WTe2, TaTe2, MoTe... 1.5 Se 0.5 ,WTe 1.5 Se 0.5 One or more of them.

[0009] Further, in step (1), the molar ratio of the layered metal telluride to LiBH4 is 0.8-1.2.

[0010] Further, in step (1), the conditions for the intercalation reaction include: heating to the intercalation reaction temperature and holding at the intercalation reaction temperature for 15-30 minutes, wherein the intercalation reaction temperature is 360-390 ℃.

[0011] Furthermore, in step (2), the actual time for the generation of Te nanowires is <1 second (the generation of Te nanowires begins immediately after the lithium intercalation product comes into contact with water), while the actual time for the generation of Te nanowires (i.e., the time of the second-level hydrolysis reaction) is <10 seconds.

[0012] Preferably, the time for the second-level hydrolysis reaction is 1 to 9 seconds.

[0013] Further, after step (2), the following step (3) is performed: The mixed system containing Te nanowires obtained in step (2) was separated, washed, and dispersed in methanol to obtain a Te nanowire dispersion in methanol.

[0014] Further, the separation includes the following process: the mixed system with Te nanowires dispersed in step (2) is subjected to ultrasonic treatment, followed by centrifugation at low speed to discard the lower unreacted solid precipitate and obtain the upper dispersion.

[0015] Further, the washing process includes the following steps: adding methanol to the obtained upper dispersion and washing, centrifuging at high speed to cause the Te nanowires to settle and obtain a solid precipitate, adding methanol to the obtained solid precipitate again and washing, centrifuging at high speed to cause the Te nanowires to settle and obtain a solid precipitate again, repeating the process of adding methanol to the obtained solid precipitate and washing, repeating the operation 3 to 5 times to complete the washing and obtain the washed precipitate.

[0016] Further, in step (3), the methanol dispersion includes the following process: adding methanol to the washed precipitate for dispersion, centrifuging at low speed to obtain the upper dispersion, which is the Te nanowire dispersion dispersed in methanol.

[0017] Furthermore, in step (3), the power of the ultrasonic treatment is 28~60 kHz; More preferably, in step (3), the power of the ultrasonic treatment is 40 kHz.

[0018] Furthermore, in step (3), the ultrasonic treatment time is 5-15 minutes.

[0019] Furthermore, in step (3), the speed of the low-speed centrifugation is 1800-3000 rpm.

[0020] Furthermore, in step (3), the low-speed centrifugation time is 5-10 minutes.

[0021] Furthermore, in step (3), the rotation speed of the high-speed centrifuge is 6000-8000 rpm.

[0022] Furthermore, in step (3), the high-speed centrifugation time is 5-10 minutes.

[0023] Furthermore, in step (3), the mass concentration of methanol is 80 wt.%-99.9 wt.%, and the remaining volume is water.

[0024] Further, after step (3), the following step (4) is performed: The Te nanowire dispersions obtained in steps (4) and (3) in methanol were dried to obtain Te nanowires.

[0025] Furthermore, in step (4), the drying is vacuum drying.

[0026] Furthermore, in step (4), the vacuum drying conditions are room temperature drying for 10 minutes.

[0027] Furthermore, in step (1), the inert gas is selected from nitrogen or argon.

[0028] Furthermore, the water is deionized water.

[0029] Furthermore, in step (1), the heating rate is 5-20 ℃ / minute.

[0030] Furthermore, step (1) specifically includes the following process: LiBH4 and layered metal telluride were mixed in a quartz tube, which was then moved into a tube furnace. Inert gas was introduced to purge the air from the tube furnace and the quartz tube. The temperature was then raised to the intercalation reaction temperature and held at the intercalation reaction temperature. After cooling, the lithiation intercalation product was obtained.

[0031] Further, in step (1), the process of introducing inert gas to purge the air from the tube furnace and quartz tube includes the following steps: the inert gas is purged at a flow rate of 50-120 standard cubic centimeters per minute (sccm) for 1-2 hours to purge the air from the tube furnace and quartz tube.

[0032] Optionally, when the layered metal telluride is selected from one or more of MoTe2 (molybdenum telluride), WTe2 (tungsten telluride), and TaTe2 (tantalum distelluride), the generated Te nanowires are pure-phase Te nanowires. Optionally, when the layered metal telluride is selected from MoTe2 (molybdenum telluride), 211 Te nanowires are counted, with an average thickness of 21 nm ± 5 nm and an average length of 824 nm ± 28 nm.

[0033] Optionally, when the layered metal telluride is selected from MoTe 1.5 Se 0.5 ,WTe 1.5 Se0.5 When one or more of the following are used, the generated Te nanowires are Se-doped Te nanowires (TEM-EDS quantitative analysis shows that the Se atom content is ~5 at.%). In the Se-doped Te nanowires, the Se element originates from the layered metal telluride MoTe. 1.5 Se 0.5 or WTe 1.5 Se 0.5 .

[0034] This invention relates to a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. The method uses layered metal telluride as a raw material, wherein the layered metal telluride is selected from one or more of MoTe2, WTe2, and TaTe2, or MoTe2 may also be used. 1.5 Se 0.5 ,WTe 1.5 Se 0.5 One or more of the following are used: a mixture of LiBH4 and a LiBH4-based intercalation agent is used, and an intercalation reaction is carried out under an inert atmosphere. The lithium-ionized intercalation product is then contacted with deionized water, resulting in a second-level hydrolysis reaction to generate Te nanowires. MoTe is selected as the intercalation agent. 1.5 Se 0.5 ,WTe 1.5 Se 0.5 When used as raw materials, tellurium and selenium in the lithium-ion intercalation product rapidly precipitate and self-assemble to form Se-doped Te nanowires (~5 at.%). When MoTe2, WTe2, or TaTe2 are used as raw materials, tellurium rapidly precipitates and self-assembles to form pure-phase Te nanowires. Finally, after separation, washing, and methanol dispersion, highly crystalline Te nanowire products (pure-phase or Se-doped phase) are obtained. This invention solves the technical problems of long reaction cycles, complex operations, and low crystallinity in existing Te nanowire preparation methods. By utilizing the rapid hydrolysis effect induced by LiBH4 intercalation, it achieves efficient and rapid preparation of pure-phase and Se-doped Te nanowires. The preparation process is mild, simple to operate, and low in cost. The obtained Te nanowires have high crystallinity and good dispersibility, and can be widely used in photoelectric detection, energy storage devices, catalysis, and other fields.

[0035] Compared with the prior art, the present invention has the following beneficial effects: 1) This invention provides a novel method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. This method achieves hydrolysis growth at room temperature with a growth time of <10 seconds, significantly reducing reaction energy consumption compared to the traditional hydrothermal method (which typically requires 120-220℃ and a reaction time of 3-24 hours). Traditional hydrothermal nanowire preparation methods often require the introduction of surfactants, while this method does not require additional surfactants. The product can be directly obtained as a dispersion of Te nanowires through washing, facilitating subsequent solution processing. The resulting nanowires are surfactant-free and exhibit high crystallinity.

[0036] 2) This invention provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. The prepared Te nanowires have uniform thickness (average thickness 21 nm ± 5 nm when the layered metal telluride is selected from MoTe2) and length (average length 824 nm ± 28 nm when the layered metal telluride is selected from MoTe2).

[0037] 3) This invention provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, which can be achieved by simply replacing the raw materials (the layered metal telluride is selected from MoTe). 1.5 Se 0.5 ,WTe 1.5 Se 0.5 Te nanowires with ~5 at.% Se atoms can be prepared by means of one or more of the above methods. Attached Figure Description

[0038] Figure 1 This is a schematic diagram illustrating the synthesis of Te nanowires according to the present invention. In obtaining Te nanowires, MoTe2 can be replaced with WTe2 or TaTe2; furthermore, MoTe2 can be replaced with MoTe... 1.5 Se 0.5 ,WTe 1.5 Se 0.5 Se-doped Te nanowires can be prepared.

[0039] Figure 2 Photograph of the Te nanowire dispersion in methanol prepared according to the present invention.

[0040] Figure 3 The figures show the morphological characterization data of the nanowires prepared in Example 1. Wherein a is a scanning electron microscope (SEM) image of the Te nanowires prepared according to the present invention; b is a transmission electron microscope (TEM) image of the Te nanowires prepared according to the present invention.

[0041] Figure 4The data above represent the structural characterization data of the Te nanowires prepared in Example 1. Wherein a is the Raman spectrum of the Te nanowires prepared in this invention; b is the polycrystalline powder diffraction pattern of the Te nanowires prepared in this invention.

[0042] Figure 5 The statistical distribution of the Te nanowires prepared in Example 1 is shown. Wherein a is the statistical distribution of the thickness of the Te nanowires prepared in this invention; b is the statistical distribution of the length of the Te nanowires prepared in this invention; and c is the statistical distribution of the aspect ratio of the Te nanowires prepared in this invention.

[0043] Figure 6 Characterization data for Se-doped Te nanowires prepared in Example 5 are shown. In the image, a is a transmission electron microscope (TEM) image of the Se-doped Te nanowires; b is a surface scan and elemental mapping distribution of the Se-doped Te nanowires, where HAADF represents high-angle annular dark-field imaging.

[0044] Figure 7 The image shown is a scanning electron microscope (SEM) image of the product obtained in Comparative Example 1.

[0045] Figure 8 This is a scanning electron microscope image of the oxidized Te nanowires prepared in Comparative Example 2.

[0046] Figure 9 The mixture (MoTe2 nanosheets, Te nanowires and MoO2) prepared for Comparative Example 3 x Scanning electron microscope image of ).

[0047] Figure 10 This is a scanning electron microscope image of MoTe2 prepared by the method in Comparative Example 4. Detailed Implementation

[0048] The present invention will now be described in detail with reference to specific embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Component models, material names, connection structures, control methods, and other features not explicitly stated in this technical solution are considered to be common technical features disclosed in the prior art.

[0049] Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0050] It should be noted that the technical terms used in this invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of this invention. Unless otherwise specified, all raw materials, reagents, instruments and equipment used in the following embodiments of this invention can be purchased from the market or prepared by existing methods.

[0051] This invention provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, comprising the following steps performed sequentially: (1) LiBH4 and layered metal telluride are mixed in a quartz tube, wherein the molar ratio of LiBH4 to layered metal telluride is 0.8-1.2; the quartz tube is moved into a tube furnace through which inert gas can be introduced, and inert gas is introduced to exhaust the air in the tube furnace and the quartz tube; then the temperature is raised to 360-390 °C and held at this temperature for 15-30 minutes, and after cooling, a lithiation intercalation product is obtained; deionized water is added to the quartz tube, and the lithiation intercalation product comes into contact with water and undergoes a second-level hydrolysis reaction to generate Te nanowires, thereby obtaining a mixed system in which Te nanowires are dispersed; (2) The mixed system with Te nanowires obtained in step (1) is subjected to ultrasonic treatment, and then centrifuged at low speed to remove the unreacted solid precipitate in the lower layer and obtain the upper dispersion. Methanol (as a replacement solvent) is added to the upper dispersion and washed. The Te nanowires are precipitated by centrifugation at high speed. The upper waste liquid containing impurities is poured off to obtain a solid precipitate. Methanol is added to the solid precipitate again and washed. The Te nanowires are precipitated by centrifugation at high speed and obtain a solid precipitate again. The solid precipitate is added to methanol and washed repeatedly. The operation is repeated 3 to 5 times. After washing, the washed precipitate is obtained. Methanol is added to the washed precipitate to disperse it fully. The small amount of residual coarse impurities is removed by centrifugation at low speed again. The small amount of precipitate in the bottom layer is discarded. The upper liquid is the Te nanowire dispersion in methanol.

[0052] In some embodiments of the present invention, in step (1), the time of the second-level hydrolysis reaction, i.e. the time to generate Te nanowires, is <10 seconds.

[0053] In some embodiments of the present invention, in step (1), the inert gas is selected from nitrogen or argon.

[0054] In some embodiments of the present invention, in step (1), the heating rate is 5-20°C / minute.

[0055] In some embodiments of the present invention, when the layered metal telluride is selected from one or more of MoTe2 (molybdenum telluride), WTe2 (tungsten telluride), and TaTe2 (tantalum telluride), the generated Te nanowires are pure-phase Te nanowires.

[0056] In some embodiments of the present invention, when the layered metal telluride is selected from MoTe 1.5 Se 0.5 ,WTe 1.5 Se 0.5When one or more of the following are used, the generated Te nanowires are Se-doped Te nanowires (~5 at.%), wherein the Se-doped Te nanowires contain Se elements derived from the layered metal telluride MoTe. 1.5 Se 0.5 or WTe 1.5 Se 0.5 .

[0057] In some embodiments of the present invention, the ultrasonic treatment time in step (2) is 5-15 minutes.

[0058] In some embodiments of the present invention, in step (2), the power of the ultrasonic treatment is 28~60 kHz; in some embodiments of the present invention, in step (2), the speed of the low-speed centrifugation is 1800-3000 rpm.

[0059] In some embodiments of the present invention, in step (2), the low-speed centrifugation time is 5-10 minutes.

[0060] In some embodiments of the present invention, in step (2), the rotational speed of the high-speed centrifuge is 6000-8000 rpm.

[0061] In some embodiments of the present invention, in step (2), the high-speed centrifugation time is 5-10 minutes.

[0062] In some embodiments of the present invention, in step (2), the mass concentration of methanol is 80 wt.%-99.9 wt.%, and the balance is water.

[0063] In some embodiments of the present invention, after step (2), the following steps are performed: the Te nanowire dispersion obtained in step (2) is dried to obtain Te nanowires.

[0064] In some embodiments of the present invention, the vacuum drying conditions are drying at room temperature for 10 minutes.

[0065] In the examples below, unless otherwise specified, the reagents used are commercially available products and the methods employed are those known in the art.

[0066] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the respective manufacturers.

[0067] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0068] The preparation methods for all the following layered metal tellurides are as follows: Bulk powder (layered metal telluride) MTe2 (M=Mo, W, Ta) was prepared by chemical vapor deposition. 0.03 mol of metal M and 0.06 mol of Te powder were ground in an agate mortar for 5 minutes. The mixture was sealed in a vacuum-sealed quartz tube (1.5 cm in diameter and 20 cm in length) and placed in a muffle furnace. It was directly heated to 900 °C at a heating rate of 5 °C / min and held at this temperature for 24 hours, after which the furnace was allowed to cool to room temperature. 1.5 Se 0.5 or WTe 1.5 Se 0.5 Prepared according to the above method, except that the 0.06 mol Te powder is replaced with 0.045 mol and 0.015 mol Se powder.

[0069] Among them, Mo (molybdenum, 99.9%), W (tungsten, 99.9%), Ta (tantalum, 99.8%), Se (selenium, 99.9%) and Te (tellurium, 99.9%) all came from Tianjin Special Powder Research Institute.

[0070] Example 1: This embodiment provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, comprising the following steps: (1) LiBH4 and layered metal telluride MoTe2 were mixed in a quartz tube (single-opening round bottom, outer diameter 15 mm, inner diameter 12 mm, length 15 cm), the molar ratio of LiBH4 to layered metal telluride MoTe2 was 0.8, and the mass of MoTe2 was 0.35114 g; the quartz tube was moved into a tube furnace that could be filled with inert gas, and argon gas was introduced at a flow rate of 80 sccm for 2 hours to purge the air from the tube furnace and the quartz tube; then the temperature was increased from 30 ℃ to 365 ℃ at a rate of 5 ℃ / min, and held at this temperature for 15 minutes; after the holding period, the quartz tube was moved to the edge of the tube furnace (still in an argon inert atmosphere) and rapidly cooled for 10 minutes. After cooling, the lithiation intercalation product (Li) was obtained. x MoTe2), at room temperature, 50 mL of deionized water (H2O) was added to a quartz tube to carry out a second-level hydrolysis reaction, and the time to generate Te nanowires was less than 10 seconds, which was 9 seconds in this example, resulting in a mixed system with dispersed Te nanowires. The procedure is as follows: Figure 1 As shown.

[0071] (2) The mixed system containing Te nanowires obtained in step (1) was subjected to ultrasonic treatment at 40 kHz for 5 minutes, followed by centrifugation at 1800 rpm for 5 minutes. The lower unreacted solid precipitate was discarded to obtain the upper dispersion. Three volumes of 99.9 wt.% methanol were added to the supernatant to replace the solvent and wash the mixture. The mixture was then centrifuged at 7000 rpm for 5 minutes. The upper waste liquid containing impurities was discarded. This methanol washing-high-speed centrifugation operation was repeated 3 times. After washing, 45 mL of methanol was added to 5 mL of precipitate for thorough dispersion. The mixture was then centrifuged again at 3000 rpm for 5 minutes to remove trace amounts of residual coarse impurities. The small amount of precipitate at the bottom was discarded. The upper liquid was the Te nanowire dispersion in methanol. Figure 2 As shown, its scanning electron microscope (SEM) image and transmission electron microscope (TEM) image are as follows: Figure 3 a and Figure 3 As shown in Figure b, it exhibits a distinct one-dimensional morphology. Its Raman spectrum and polycrystalline powder diffraction pattern are shown below. Figure 4 a and Figure 4 As shown in Figure b, its Raman spectrum exhibits three characteristic peaks of Te nanowires. E 1, A 1 and E 2. Its polycrystalline powder diffraction pattern agrees well with the standard PDF card. Data on the thickness, length, and aspect ratio of a certain quantity of nanowires are statistically analyzed as follows: Figure 5 a, Figure 5 b and Figure 5As shown in Figure c, Gaussian statistics show 211 nanowires with an average thickness of 21 nm ± 5 nm, an average length of 824 nm ± 28 nm, and an average aspect ratio of 36 ± 0.84. The polycrystalline powder diffraction pattern is obtained from the Te nanowire product after vacuum drying at room temperature for 10 minutes. Scanning electron microscopy (SEM) images, Raman spectroscopy patterns, and statistical data were obtained by vacuum drying a Te nanowire dispersion (dispersed in methanol) on a 1 cm × 1 cm P-type 100-phase silica substrate. Transmission electron microscopy (TEM) images were obtained by vacuum drying a Te nanowire dispersion (dispersed in methanol) on a 400-mesh copper mesh ordinary carbon film.

[0072] Example 2: This embodiment provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, including the following steps: (1) LiBH4 and layered metal telluride MoTe2 were mixed in a quartz tube (single-opening round bottom, outer diameter 15 mm, inner diameter 12 mm, length 15 cm), the molar ratio of LiBH4 to layered metal telluride MoTe2 was 0.8, and the mass of MoTe2 was 0.35114 g; the quartz tube was moved into a tube furnace that could be filled with inert gas, and argon gas was introduced at a flow rate of 50 sccm for 2 hours to purge the air from the tube furnace and the quartz tube; then the temperature was increased from 30 ℃ to 380 ℃ at a rate of 20 ℃ / min, and held at this temperature for 10 minutes; after the holding period, the quartz tube was moved to the edge of the tube furnace (still in an argon inert atmosphere) and rapidly cooled for 10 minutes to obtain the lithiation intercalation product (Li). x MoTe2), at room temperature, 50 mL of deionized water (H2O) was added to a quartz tube to carry out a second-level hydrolysis reaction, and the time to generate Te nanowires was <10 seconds, which was 9 seconds in this example, resulting in a mixed system with dispersed Te nanowires; (2) The mixed system with Te nanowires obtained in step (1) was subjected to ultrasonic treatment at 28 kHz for 10 minutes, and then centrifuged at 1500 rpm for 5 minutes. The lower unreacted solid precipitate was discarded to obtain the upper dispersion. Three times the volume of 80 wt.% methanol was added to the remaining supernatant for washing. The mixture was centrifuged at 8000 rpm for 5 minutes. The upper waste liquid containing impurities was discarded. The methanol washing-centrifugation operation was repeated 3 times. After washing, 45 mL of methanol was added to 5 mL of precipitate for thorough dispersion. The mixture was centrifuged again at 2000 rpm for 5 minutes to remove trace amounts of residual coarse impurities. The small amount of precipitate at the bottom was discarded. The upper liquid was the Te nanowire dispersion in methanol.

[0073] Example 3: This embodiment provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, including the following steps: (1) LiBH4 and layered metal telluride MoTe2 were mixed in a single-opening round-bottom quartz tube (outer diameter 15 mm, inner diameter 12 mm, length 15 cm), wherein the molar ratio of LiBH4 to layered metal telluride MoTe2 was 1, and the mass of MoTe2 was 0.35114 g; the quartz tube was moved into a tube furnace that could be filled with inert gas, and nitrogen gas was introduced at a flow rate of 100 sccm for 1 hour to purge the air from the tube furnace and the quartz tube; then the temperature was increased from 20 °C to 380 °C at a rate of 20 °C / min, and held at this temperature for 10 minutes; after the holding period, the single-opening round-bottom quartz tube was moved to the edge of the tube furnace (still in an argon inert atmosphere) and rapidly cooled for 10 minutes. After cooling, the lithiation intercalation product (Li) was obtained. x MoTe2), at room temperature, 50 mL of deionized water (H2O) was added to a quartz tube to carry out a second-level hydrolysis reaction, and the time to generate Te nanowires was <10 seconds, which was 9 seconds in this example, resulting in a mixed system with dispersed Te nanowires; (2) The mixed system with Te nanowires obtained in step (1) was subjected to ultrasonic treatment at 60 kHz for 10 minutes, followed by centrifugation at 1500 rpm for 10 minutes. The unreacted solid precipitate at the bottom layer was discarded to obtain the upper dispersion. Three times the volume of 90 wt.% methanol was added to the remaining supernatant for washing. The mixture was centrifuged at 8000 rpm for 10 minutes. The waste liquid containing impurities at the top layer was discarded. The methanol washing-centrifugation operation was repeated 3 times. After washing, 45 mL of methanol was added to 5 mL of precipitate for thorough dispersion. The mixture was centrifuged again at 2000 rpm for 10 minutes to remove trace amounts of residual coarse impurities. The small amount of precipitate at the bottom layer was discarded. The upper liquid was the Te nanowire dispersion in methanol.

[0074] Example 4: This embodiment provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, including the following steps: (1) LiBH4 and layered metal telluride WTe2 were mixed in a quartz tube (single-opening round bottom, outer diameter 15 mm, inner diameter 12 mm, length 15 cm), wherein the molar ratio of LiBH4 to layered metal telluride WTe2 was 1, and the mass of WTe2 was 0.043904 g; the quartz tube was moved into a tube furnace that could be filled with inert gas, and argon gas was introduced at a flow rate of 100 sccm for 1 hour to purge the air from the tube furnace and the quartz tube; then the temperature was increased from 30 ℃ to 370 ℃ at a rate of 10 ℃ / min, and held at this temperature for 20 minutes; after the holding period, the quartz tube was moved to the edge of the tube furnace (still in an inert argon atmosphere) and rapidly cooled for 10 minutes. After cooling, the lithiation intercalation product (Li) was obtained. x MoTe2), at room temperature, 30 mL of deionized water (H2O) was added to a quartz tube to carry out a second-level hydrolysis reaction, and the time to generate Te nanowires was <10 seconds, which was 9 seconds in this example, resulting in a mixed system with dispersed Te nanowires; (2) The mixed system with Te nanowires obtained in step (1) was subjected to ultrasonic treatment at 40 kHz for 7 minutes, followed by centrifugation at 1800 rpm for 10 minutes. The unreacted solid precipitate at the bottom layer was discarded to obtain the upper dispersion. Three times the volume of 90 wt.% methanol was added to the remaining supernatant for washing. The mixture was centrifuged at 8000 rpm for 10 minutes. The waste liquid containing impurities at the top layer was discarded. The methanol washing-centrifugation operation was repeated 3 times. After washing, 45 mL of methanol was added to 5 mL of precipitate for thorough dispersion. The mixture was centrifuged again at 1800 rpm for 10 minutes to remove trace amounts of residual coarse impurities. The small amount of precipitate at the bottom layer was discarded. The upper liquid was the Te nanowire dispersion in methanol.

[0075] Example 5: This embodiment provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, including the following steps: (1) Mixing LiBH4 with layered metal telluride WTe 1.5 Se 0.5 The LiBH4 and the layered metal telluride WTe were mixed in a quartz tube (single-opening round bottom, outer diameter 15 mm, inner diameter 12 mm, length 15 cm). 1.5 Se 0.5 The molar ratio is 1.2, where WTe 1.5 Se 0.5The mass was 0.41472 g. The quartz tube was placed in a tube furnace with an inert gas atmosphere, and argon gas was introduced at a flow rate of 60 sccm for 2 hours to purge the air from the tube furnace and the quartz tube. Then, the temperature was increased from room temperature to 370°C at a rate of 10 °C / min and held at that temperature for 30 minutes. After the holding period, the quartz tube was moved to the edge of the tube furnace (still in an inert argon atmosphere) and rapidly cooled for 10 minutes. After cooling, the lithiation intercalation product (Li) was obtained. x MoTe2), at room temperature, 50 mL of deionized water (H2O) was added to a quartz tube to carry out a second-level hydrolysis reaction, and the time to generate Te nanowires was <10 seconds, which was 9 seconds in this example, resulting in a mixed system with dispersed Te nanowires; (2) The mixed system with Te nanowires dispersed in step (1) was subjected to ultrasonic treatment at 40 kHz for 5 minutes, followed by centrifugation at 1800 rpm for 10 minutes. The lower unreacted solid precipitate was discarded to obtain the upper dispersion. Three volumes of 99.9 wt.% methanol were added to the remaining upper dispersion for washing. The mixture was centrifuged at 8000 rpm for 8 minutes, and the upper waste liquid containing impurities was discarded. This methanol washing-centrifugation operation was repeated 3 times. After washing, 45 mL of methanol was added to 5 mL of precipitate for thorough dispersion. The mixture was centrifuged again at 1800 rpm for 8 minutes to remove trace amounts of residual coarse impurities. The small amount of precipitate at the bottom was discarded. The upper liquid was the Se atom-doped Te nanowire dispersion dispersed in methanol. Its transmission electron microscopy image is shown below. Figure 6 As shown in Figure a, Se-doped Te nanowires exhibit a distinct one-dimensional morphology and aspect ratio. Figure 6 Image b shows its surface scan and elemental mapping distribution, clearly revealing Se atoms doped into the Te nanowires. Figure 6 a and Figure 6 Both b were tested by vacuum drying a Se-doped Te nanowire dispersion dispersed in methanol on a 400-mesh copper mesh ordinary carbon film.

[0076] Comparative Example 1 This comparative example provides a method based on the hydrolysis of LiBH4 and non-metallic telluride. Compared with Example 1, this comparative example uses the non-metallic telluride TeO2 instead of MoTe2 in Example 1, while keeping other conditions the same. This comparative example cannot generate Te nanowires. Figure 7 As shown.

[0077] Comparative Example 2 This comparative example provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. Compared with Example 1, the tube furnace in this comparative example uses air and no inert gas is introduced. The Te nanowires prepared in this comparative example are as follows: Figure 8 As shown, the surface oxidation degree is significant.

[0078] Comparative Example 3 This comparative example provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. Compared with Example 1, the molar ratio of LiBH4 to layered metal telluride MoTe2 in this comparative example is 0.5, and other conditions are the same. The Te nanowires prepared in this comparative example are as follows: Figure 9 As shown, the resulting Te nanowires are doped with a large number of impurities and MoTe2 nanosheets.

[0079] Comparative Example 4 This comparative example provides a method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride. Compared with Example 1, the intercalation reaction temperature in this comparative example is 340℃, and other conditions are the same. This comparative example cannot generate Te nanowires. Figure 10 As shown.

[0080] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Anyone skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the invention should still be covered by the claims of the invention. The above description of the embodiments is to facilitate understanding and use of the invention by those skilled in the art. Those skilled in the art can obviously easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative effort. Therefore, the invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the invention without departing from the scope of the invention should be within the protection scope of the invention.

Claims

1. A method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride, characterized in that, Includes the following steps: (1) After mixing layered metal telluride and LiBH4, an intercalation reaction was carried out under inert gas conditions, and the lithium intercalation product was obtained after cooling. (2) The lithium intercalation product is brought into contact with water to undergo a second-level hydrolysis reaction to generate Te nanowires, thus obtaining a mixed system in which Te nanowires are dispersed. In step (1), the layered metal telluride is selected from MoTe2, WTe2, TaTe2, and MoTe. 1.5 Se 0.5 ,WTe 1.5 Se 0.5 One or more of the following; In step (1), the molar ratio of the layered metal telluride to LiBH4 is 0.8-1.2; In step (1), the conditions for the intercalation reaction include: heating to the intercalation reaction temperature and holding at the intercalation reaction temperature for 15-30 minutes, wherein the intercalation reaction temperature is 360-390 °C; In step (2), the time for the second-level hydrolysis reaction is <10 seconds.

2. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 1, characterized in that, After step (2), perform the following step (3): The mixed system containing Te nanowires obtained in step (2) was separated, washed, and dispersed in methanol to obtain a Te nanowire dispersion in methanol.

3. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 2, characterized in that, The separation process includes the following steps: the mixed system containing Te nanowires obtained in step (2) is subjected to ultrasonic treatment, followed by centrifugation at low speed to discard the lower unreacted solid precipitate and obtain the upper dispersion. The washing process includes the following steps: adding methanol to the obtained upper dispersion and washing, centrifuging at high speed to allow the Te nanowires to settle and obtain a solid precipitate, adding methanol to the obtained solid precipitate again and washing, centrifuging at high speed to allow the Te nanowires to settle and obtain a solid precipitate again, repeating the process of adding methanol to the obtained solid precipitate and washing, centrifuging at high speed to allow the Te nanowires to settle and obtain a solid precipitate again for 3 to 5 times to complete the washing process and obtain the washed precipitate; The methanol dispersion includes the following process: methanol is added to the washed precipitate for dispersion, and the mixture is centrifuged at low speed to obtain the upper liquid, which is the Te nanowire dispersion in methanol.

4. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 3, characterized in that, The ultrasonic treatment time is 5-15 minutes; The power of the ultrasonic treatment is 28~60 kHz; The speed of the low-speed centrifuge is 1800-3000 rpm; The low-speed centrifugation time is 5-10 minutes; The high-speed centrifuge operates at a speed of 6000-8000 rpm; The high-speed centrifugation time is 5-10 minutes; The methanol has a mass fraction of 80 wt.%-99.9 wt.%, with the balance being water.

5. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 2, characterized in that, After step (3), perform the following step (4): The Te nanowire dispersion obtained in step (3) in methanol was dried to obtain Te nanowires.

6. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 5, characterized in that, The drying process is vacuum drying.

7. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 1, characterized in that, The inert gas is selected from nitrogen or argon; The water is deionized water.

8. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 1, characterized in that, In step (1), the heating rate is 5-20℃ / minute.

9. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 1, characterized in that, Step (1) specifically includes the following process: LiBH4 and layered metal telluride were mixed in a quartz tube, which was then moved into a tube furnace. Inert gas was introduced to purge the air from the tube furnace and the quartz tube. The temperature was then raised to the intercalation reaction temperature and held at the intercalation reaction temperature. After cooling, the lithiation intercalation product was obtained.

10. The method for preparing Te nanowires based on the hydrolysis of LiBH4 intercalated layered metal telluride according to claim 1, characterized in that, When the layered metal telluride is selected from one or more of MoTe2, WTe2, and TaTe2, the generated Te nanowires are pure-phase Te nanowires; When the layered metal telluride is selected from MoTe 1.5 Se 0.5 ,WTe 1.5 Se 0.5 When one or more of these are used, the resulting Te nanowires are Se-doped Te nanowires.

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