A nano tellurium / carbon composite material, a preparation method and application thereof
By embedding tellurium nanorods into reduced graphene oxide through a one-step redox reaction, the problems of complex synthesis process and uneven dispersion of nano-tellurium/carbon composite materials are solved, realizing the efficient preparation of nano-tellurium/carbon composite materials, which are suitable for semiconductor, conductive, thermoelectric and acousto-optic fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGZHOU UNIVERSITY
- Filing Date
- 2023-09-06
- Publication Date
- 2026-06-02
AI Technical Summary
Existing nano-tellurium/carbon composite material synthesis processes are complex, and tellurium nanotubes are prone to agglomeration and uneven dispersion, making large-scale production difficult.
A one-step redox reaction was used to embed tellurium nanorods into reduced graphene oxide, using sodium telluride hydride as the reducing agent and tellurium source, and graphene oxide as the oxidant and loading material, to prepare nano-tellurium/carbon composite materials in a simple one-step process.
The uniform distribution and tight embedding of tellurium nanorods in composite materials were achieved, simplifying the synthesis steps, shortening the reaction time, making them suitable for large-scale production, and improving the crystallinity of the materials.
Smart Images
Figure CN117361515B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of new energy materials, specifically relating to a nano-tellurium / carbon composite material, its preparation method, and its application. Background Technology
[0002] Nanoscale tellurium (Te) / carbon composites possess unique properties in semiconductors, electrical conductivity, thermoelectricity, and acousto-optics, leading to their widespread application in electronics, sensors, optoelectronics, and energy devices. Numerous synthetic methods have been developed to obtain various forms of nanoscale tellurium / carbon materials, such as vapor deposition, hydrothermal methods, and solution methods. While physical methods like vapor deposition can synthesize well-defined nanostructures down to a few nanometers, developing these techniques for mass production requires specialized and expensive equipment. Considering yield, cost, and the potential for large-scale production, chemical methods such as hydrothermal and solution methods may offer a more promising pathway for nanostructure development.
[0003] In the exploration of various nano-tellurium / carbon composite materials, tellurium nanomaterials are typically synthesized via hydrothermal methods and then physically mixed with carbon materials to obtain nano-tellurium / carbon composite materials; alternatively, different functionalized carbon materials are first synthesized, and then tellurium nanoparticles are loaded onto the carbon materials via melt methods to prepare nano-tellurium / carbon composite materials. However, current synthesis schemes for nano-tellurium / carbon composite materials usually involve multi-step processes or energy-intensive and time-consuming tellurium melt dispersion manufacturing processes. Furthermore, the Te nanotubes in currently synthesized nano-tellurium / carbon composite materials also suffer from easy agglomeration and uneven distribution. Therefore, to achieve large-scale preparation and industrial application of nano-tellurium / carbon composite materials, it is urgent to find new and simple synthesis methods to prepare nano-tellurium / carbon composite materials with uniformly dispersed Te nanotubes. Summary of the Invention
[0004] To overcome the problems existing in the prior art, one objective of this invention is to provide a nano-tellurium / carbon composite material. A second objective is to provide a method for preparing this nano-tellurium / carbon composite material. A third objective is to provide applications of the nano-tellurium / carbon composite material. This invention, through a simple one-step redox reaction, can prepare a nano-tellurium / carbon composite material with uniformly dispersed nano-tellurium in a short time.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] The first aspect of the present invention provides a nano-tellurium / carbon composite material, wherein tellurium nanorods are embedded in reduced graphene oxide and the tellurium nanorods are uniformly dispersed in the composite material.
[0007] Preferably, the length of the tellurium nanorod is 50–300 nm; more preferably, it is 80–200 nm.
[0008] Preferably, the diameter of the tellurium nanorods is 10–20 nm; more preferably, it is 12–20 nm.
[0009] Preferably, the raw materials for preparing the composite material include graphene oxide and telluride.
[0010] The second aspect of the present invention provides a method for preparing the nano-tellurium / carbon composite material described in the first aspect, comprising the following steps: mixing a stabilizer, graphene oxide and tellurium hydride in a solvent and reacting them to obtain the nano-tellurium / carbon composite material.
[0011] Preferably, the method specifically includes the following steps: adding a tellurium hydride solution to a mixed solution containing a stabilizer and graphene oxide, and reacting to obtain the nano-tellurium / carbon composite material. More preferably, the sodium telluride solution is an aqueous solution of sodium telluride; even more preferably, the sodium telluride solution is prepared by reacting sodium borohydride with tellurium powder in water, releasing hydrogen gas generated during the reaction, and producing a white sodium tetraborate precipitate after the reaction, with the clear light purple solution on the upper layer being the aqueous solution of sodium telluride; even more preferably, to ensure that the sodium telluride solution is not oxidized before the reaction, the sodium telluride solution needs to be prepared fresh. More preferably, the method for preparing the mixed solution containing a stabilizer and graphene oxide is: dispersing the stabilizer and graphene oxide in water to obtain a mixed solution containing a stabilizer and graphene oxide.
[0012] Preferably, the tellurium hydride is an alkali metal salt tellurium hydride; more preferably, the tellurium hydride is sodium telluride.
[0013] Preferably, the sodium telluride solution is rapidly added to the mixed solution containing the stabilizer and graphene oxide under vigorous stirring.
[0014] Preferably, the stabilizer is a nonionic surfactant; more preferably, the stabilizer is polyvinylpyrrolidone; even more preferably, the mass ratio of graphene oxide to polyvinylpyrrolidone is 1:350-1600.
[0015] Preferably, the solvent is water. More preferably, the ratio of graphene oxide to water is 1 mg: 40-60 mL. Even more preferably, the ratio of polyvinylpyrrolidone to water is 0.1-0.4 mmol: 40-60 mL.
[0016] Preferably, the ratio of graphene oxide to telluride is 1 mg: 0.1 to 0.4 mmol.
[0017] Preferably, the reaction temperature is 40–60°C; more preferably 45–55°C; including but not limited to 46, 48, 50, 52, and 54°C.
[0018] Preferably, the reaction time is 3 to 24 hours; more preferably, it is 3 to 10 hours; including but not limited to 3, 4, 5, 6, 7, 8, 9, and 10 hours.
[0019] Preferably, the reaction is carried out under a protective atmosphere; argon is preferred.
[0020] Preferably, the method further includes the following steps: the reacted solution is centrifuged, washed, and freeze-dried to obtain the tellurium nanorod / reduced graphene oxide composite material.
[0021] The third aspect of the present invention provides the application of the nano-tellurium / carbon composite material described in the first aspect, wherein the nano-tellurium / carbon composite material is used in the fields of semiconductors, electrical conductivity, thermoelectricity, or acousto-optics.
[0022] The beneficial effects of this invention are:
[0023] This invention provides a method for preparing a tellurium nanorod / reduced graphene oxide composite material. The invention utilizes sodium telluride (NaHTe) as a reducing agent and tellurium source, and graphene oxide (GO) as an oxidizing agent and loading material, so that the tellurium nanorods are uniformly distributed and embedded in the reduced graphene oxide (rGO) in the composite material.
[0024] Specifically, compared with the prior art, the present invention has the following advantages:
[0025] 1) This invention provides a tellurium nanorod / reduced graphene oxide composite material, in which tellurium nanorods are tightly embedded in reduced graphene oxide, and the resulting tellurium nanorods are small in size and have good crystallinity.
[0026] 2) The preparation method of this invention requires only a simple one-step process and can be completed in a short time. The synthesis steps are simple and time-saving, with a minimum time of 3 hours, solving the problem of complex synthesis processes for various nano-tellurium / carbon composite materials. This is beneficial for the large-scale production of this composite material. This invention uses PVP as a surfactant, which results in the formation of small tellurium nanorods during the reaction. This invention uses NaHTe as a reducing agent and tellurium source, and GO as an oxidant and loading material, so that the tellurium nanorods are uniformly distributed and embedded in rGO in the composite material, overcoming the problems of easy agglomeration and uneven dispersion of nano-tellurium materials.
[0027] 3) The tellurium nanorod / reduced graphene oxide composite material of the present invention has application potential in the fields of semiconductors, electrical conductivity, thermoelectricity and acousto-optics. Attached Figure Description
[0028] Figure 1 Flowchart of the preparation process for Te NRs / rGO composite materials;
[0029] Figure 2 The image shows the XRD pattern of the Te NRs / rGO composite material from Example 1.
[0030] Figure 3 This is a TEM image of the Te NRs / rGO composite material from Example 1. Detailed Implementation
[0031] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials used in the following embodiments can be obtained from conventional commercial channels or prepared and isolated through simple synthesis; unless otherwise specified, the processes employed are conventional processes in the art.
[0032] The graphene oxide used in the following examples is commercially available. The preparation process of the Te NRs / rGO composite material is as follows: Figure 1 As shown.
[0033] Example 1
[0034] Preparation of NaHTe: 0.34 g of NaBH4 was dissolved in 6 mL of deionized water. 0.51 g of Te powder was quickly added, and the reaction flask was sealed with a rubber stopper. A small pinhole was left in the stopper to allow the release of hydrogen gas produced during the reaction. During the reaction, the flask was cooled in an ice-water bath and magnetically stirred to ensure a uniform and slow reaction. After 8 hours of reaction, the black Te powder disappeared, and a white sodium tetraborate precipitate was formed. The clear, pale purple supernatant was the prepared NaHTe solution (0.67 mol / L).
[0035] Preparation of Te NRs / rGO composite material: 310 mg PVP and 0.4 mL GO aqueous solution (2 g / L) were completely dispersed in 40 mL deionized water. The atmosphere in the three-necked reaction flask was replaced with argon using a water pump, and the flask was sealed with a rubber stopper to prevent oxygen from entering. Then, under vigorous magnetic stirring, 0.3 mL of freshly prepared NaHTe (0.67 mol / L) aqueous solution was rapidly injected into the mixed solvent containing PVP and GO using a syringe. The three-necked flask was placed in a water bath at 50 °C to allow NaHTe and GO to react fully. After reacting for 3 h, the final product, tellurium nanorod / reduced graphene oxide composite material, i.e., Te NRs / rGO composite material, was obtained by centrifugation at 10000 rpm for 5 min and washing three times with deionized water, followed by freeze-drying for 24 h.
[0036] Figure 2The XRD pattern of the Te-NRs / rGO composite material synthesized using 310 mg PVP is shown. The XRD curve of the Te-NRs / rGO composite material is completely consistent with the characteristic peaks of pure Te (JCPDS card number 36-1465). The broad peaks of 15-26° correspond to carbon materials, and the sharp peaks correspond to Te elements, indicating that the Te material in the composite material has good crystallinity.
[0037] Figure 3 TEM images of the Te NRs / rGO composite synthesized using 310 mg PVP show that Te nanorods are uniformly distributed and tightly embedded in rGO. Further statistical analysis revealed that the length and diameter of the Te nanorods (Te NRs) are 99.7 ± 17.8 nm and 14.3 ± 2.4 nm, respectively.
[0038] Example 2
[0039] Unlike Example 1, Example 2 used 620 mg PVP, 0.3 mL NaHTe (preparation method same as Example 1), and a reaction temperature of 50°C. The specific preparation method is as follows:
[0040] 620 mg PVP and 0.4 mL of GO aqueous solution (2 g / L) were completely dispersed in 40 mL of deionized water. The atmosphere in the three-necked reaction flask was replaced with argon using a water pump, and the flask was sealed with a rubber stopper to prevent oxygen from entering. Then, under vigorous magnetic stirring, 0.3 mL of freshly prepared NaHTe (0.67 mol / L) aqueous solution was rapidly injected into the mixed solvent using a syringe. The three-necked flask was placed in a 50 °C water bath to allow NaHTe and GO to react fully. After 3 h of reaction, the final product, tellurium nanorods / reduced graphene oxide composite material (Te NRs / rGO composite material), was obtained by centrifugation at 10000 rpm for 5 min, washing three times with deionized water, and then freeze-drying for 24 h.
[0041] XRD and TEM analyses were performed on the composite material of Example 2. The XRD results showed that the characteristic peaks were completely consistent with those of pure Te. TEM analysis also revealed that the Te nanorods were uniformly distributed and tightly embedded in the rGO in the composite material. Further statistical analysis showed that the length and diameter of the Te nanorods were 166.5 ± 15.7 nm and 14.7 ± 2.5 nm, respectively.
[0042] Example 3
[0043] Unlike Example 1, Example 3 used 1240 mg PVP, 0.3 mL NaHTe (preparation method same as Example 1), and a reaction temperature of 50°C. The specific preparation method is as follows:
[0044] 1240 mg PVP and 0.4 mL of GO aqueous solution (2 g / L) were completely dispersed in 40 mL of deionized water. The atmosphere in the three-necked reaction flask was replaced with argon using a water pump, and the flask was sealed with a rubber stopper to prevent oxygen from entering. Then, under vigorous magnetic stirring, 0.3 mL of freshly prepared NaHTe (0.67 mol / L) aqueous solution was rapidly injected into the mixed solvent using a syringe. The three-necked flask was placed in a 50 °C water bath to allow NaHTe and GO to react fully. After 3 h of reaction, the final product, tellurium nanorod / reduced graphene oxide composite material (Te NRs / rGO composite material), was obtained by centrifugation at 10000 rpm for 5 min, washing three times with deionized water, and then freeze-drying for 24 h.
[0045] XRD and TEM analyses were performed on the composite material of Example 3. The XRD results showed that the characteristic peaks were completely consistent with those of pure Te. TEM analysis also revealed that the Te nanorods were uniformly distributed and tightly embedded in rGO in the composite material. Further statistical analysis showed that the length and diameter of the Te nanorods were 169.4 ± 12.1 nm and 16.0 ± 2.2 nm, respectively.
[0046] Example 4
[0047] Unlike Example 1, Example 4 used 620 mg PVP, 0.4 mL NaHTe (preparation method same as Example 1), and a reaction temperature of 50°C. The specific preparation method is as follows:
[0048] 620 mg PVP and 0.4 mL of GO aqueous solution (2 g / L) were completely dispersed in 40 mL of deionized water. The atmosphere in the three-necked reaction flask was replaced with argon using a water pump, and the flask was sealed with a rubber stopper to prevent oxygen from entering. Then, under vigorous magnetic stirring, 0.4 mL of freshly prepared NaHTe (0.67 mol / L) aqueous solution was rapidly injected into the mixed solvent using a syringe. The three-necked flask was placed in a 50 °C water bath to allow NaHTe and GO to react fully. After 3 h of reaction, the final product, tellurium nanorod / reduced graphene oxide composite material (Te NRs / rGO composite material), was obtained by centrifugation at 10000 rpm for 5 min, washing three times with deionized water, and then freeze-drying for 24 h.
[0049] XRD and TEM analyses were performed on the composite material of Example 4. The XRD results showed that the characteristic peaks were completely consistent with those of pure Te. TEM analysis also revealed that the Te nanorods were uniformly distributed and tightly embedded in the rGO in the composite material. Further statistical analysis showed that the length and diameter of the Te nanorods were 180.5 ± 14.1 nm and 17.2 ± 2.7 nm, respectively.
[0050] Example 5
[0051] Unlike Example 1, Example 5 used 620 mg PVP, 0.3 mL NaHTe (preparation method same as Example 1), and a reaction temperature of 40°C. The specific preparation method is as follows:
[0052] 620 mg PVP and 0.4 mL of GO aqueous solution (2 g / L) were completely dispersed in 40 mL of deionized water. The atmosphere in the three-necked reaction flask was replaced with argon using a water pump, and the flask was sealed with a rubber stopper to prevent oxygen from entering. Then, under vigorous magnetic stirring, 0.3 mL of freshly prepared NaHTe (0.67 mol / L) aqueous solution was rapidly injected into the mixed solvent using a syringe. The three-necked flask was placed in a 40 °C water bath to allow NaHTe and GO to react fully. After 3 h of reaction, the mixture was centrifuged at 10000 rpm for 5 min and washed three times with deionized water, then freeze-dried for 24 h to obtain the tellurium nanorod / reduced graphene oxide composite material, i.e., the TeNRs / rGO composite material.
[0053] XRD and TEM analyses were performed on the composite material of Example 5. The XRD results showed that the characteristic peaks were completely consistent with those of pure Te. TEM analysis also revealed that the Te nanorods were uniformly distributed and tightly embedded in the rGO in the composite material. Further statistical analysis showed that the length and diameter of the Te nanorods were 122.3 ± 13.2 nm and 15.3 ± 2.4 nm, respectively.
[0054] In summary, this invention provides a tellurium nanorod / reduced graphene oxide composite material in which tellurium nanorods are tightly embedded in reduced graphene oxide, resulting in small-sized tellurium nanorods with good crystallinity. The preparation method of this invention requires only a simple one-step process and can be completed in a short time. The synthesis steps are simple and time-efficient, with a minimum time of 3 hours, solving the problem of complex synthesis processes for various current nano-tellurium / carbon composite materials, which is beneficial for the large-scale production of this composite material. This invention uses PVP as a surfactant, which results in the formation of small-sized tellurium nanorods during the reaction. This invention uses NaHTe as a reducing agent and tellurium source, and GO as an oxidant and loading material, ensuring that the tellurium nanorods are uniformly distributed and embedded in rGO in the composite material, overcoming the problems of easy agglomeration and uneven dispersion of nano-tellurium materials. The tellurium nanorod / reduced graphene oxide composite material of this invention has application potential in the fields of semiconductors, electrical conductivity, thermoelectricity, and acousto-optics.
Claims
1. A nano-tellurium / carbon composite material, characterized in that, It includes reduced graphene oxide and tellurium nanorods dispersed in the reduced graphene oxide; the tellurium nanorods are embedded in the reduced graphene oxide; The preparation method of the nano-tellurium / carbon composite material includes the following steps: mixing a stabilizer, graphene oxide and tellurium hydride in a solvent and reacting them to obtain the nano-tellurium / carbon composite material. The telluride is sodium telluride; The ratio of graphene oxide to telluride is 1 mg: 0.1~0.4 mmol; The stabilizer is polyvinylpyrrolidone; The mass ratio of graphene oxide to polyvinylpyrrolidone is 1:350~1600.
2. The nano-tellurium / carbon composite material according to claim 1, characterized in that, The length of the tellurium nanorods is 50~300 nm; And / or, the diameter of the tellurium nanorods is 10~20 nm.
3. The method for preparing the nano-tellurium / carbon composite material according to claim 1 or 2, characterized in that, The process includes the following steps: mixing a stabilizer, graphene oxide, and tellurium hydride in a solvent and reacting them to obtain the nano-tellurium / carbon composite material. The telluride is sodium telluride; The ratio of graphene oxide to telluride is 1 mg: 0.1~0.4 mg.
4. The method for preparing the nano-tellurium / carbon composite material according to claim 3, characterized in that, Specifically, the following steps are included: The tellurium hydride solution was added to a mixed solution containing a stabilizer and graphene oxide to react and obtain the nano-tellurium / carbon composite material.
5. The method for preparing the nano-tellurium / carbon composite material according to claim 3, characterized in that, The solvent is water.
6. The method for preparing the nano-tellurium / carbon composite material according to claim 3, characterized in that, The conditions for the reaction are selected from one or more of the following: A) Reaction temperature 40~60℃; B) Reaction time: 3~24 h; C) Conducted under a protective atmosphere.
7. The application of the nano-tellurium / carbon composite material according to claim 1 or 2 in the fields of semiconductors, electrical conductivity, thermoelectricity, or acousto-optics.