Metal oxide embedded carbon nanotube nano flexoelectric material as well as preparation method and application thereof
By embedding metal oxides into carbon nanotubes, nano-flexoelectric materials with built-in stress gradients were prepared, solving the problem of preparing flexoelectric effects at the nanoscale and realizing efficient organic degradation and energy harvesting.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUZHOU INST OF NANO TECH & NANO BIONICS CHINESE ACEDEMY OF SCI
- Filing Date
- 2026-02-06
- Publication Date
- 2026-05-01
AI Technical Summary
Existing technologies struggle to effectively utilize the flexoelectric effect at the nanoscale, and the fabrication methods are complex and costly, making it difficult to drive conventional electronic devices.
By embedding metal oxides into carbon nanotubes and using hydrolytic salt and annealing treatment, nano-flexoelectric materials with built-in stress gradients are prepared, achieving nanoscale flexoelectric effects.
It significantly improves the geometric dislocation density of flexural electricity, enhances the efficiency of organic matter degradation and energy harvesting, and reduces the preparation cost.
Smart Images
Figure CN121948438A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials preparation technology, specifically relating to a metal oxide embedded carbon nanotube nanoflexible material, its preparation method and application. Background Technology
[0002] Flexoelectricity is a mechanoelectric coupling phenomenon present in all dielectric materials, where polarization occurs when a material undergoes bending or non-uniform deformation (existing strain gradient). Compared to piezoelectric materials, its core advantage lies in its broad applicability (not limited by crystal symmetry) and significant effects at the micro- and nano-scale (the strain gradient increases sharply with decreasing size), making it a key functional material in many cutting-edge fields. Examples include high-sensitivity micro- and nano-sensors (such as detecting microcracks in structures and physiological signals), environmental micro-energy harvesters (collecting low-frequency mechanical energy to power IoT micro-devices), and next-generation smart electronic devices (using strain gradient modulation of semiconductor bands or ferroelectric domains for novel memories, transistors, and neuromorphic computing). Flexoelectricity can directly and efficiently convert microscopic mechanical deformation into controllable electrical signals or chemical activity, providing a unique path for developing adaptive, low-power micro- and nano-systems and smart materials.
[0003] However, in practical applications, problems exist such as weak macroscopic output performance and difficulty in controllable fabrication at the nanoscale. The most fundamental bottleneck stems from the fact that the giant flexural electrical effect at the nanoscale results in weak output signals in macroscopic devices, making it difficult to directly drive conventional electronic devices. To overcome this limitation, materials must be fabricated at the nanoscale or special microstructures must be designed, such as through physical vapor deposition (Nat. Commun., 2022, 13, 5116, CN202510833330, CN202510586672), wet chemical methods (CN202511198740, CN202411947041), or biomimetic structures (PNAS, 2023, 120, e2311755120). However, controllable fabrication processes with atomic-level precision (such as magnetron sputtering, molecular beam epitaxy, atomic layer deposition, etc.) are complex and costly; wet chemical methods are prone to defects and agglomeration; and biomimetic structures are complex and difficult to control precisely. Summary of the Invention
[0004] The purpose of this invention is to provide a metal oxide embedded carbon nanotube nanoflexoelectric material, its preparation method and application. It realizes the preparation of nanoscale built-in stress gradient flexoelectric material, which exhibits a huge flexoelectric effect and shows great potential in the fields of organic pollutant degradation and energy harvesting.
[0005] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:
[0006] A method for preparing a metal oxide-embedded carbon nanotube flexible nanomaterial, the method comprising the following steps:
[0007] Open the carbon nanotubes to obtain open carbon nanotubes;
[0008] Open carbon nanotubes, hydrolyzed salt, and water are mixed to obtain a hydrolyzed salt carbon nanotube solution.
[0009] The hydrolyzed salt carbon nanotube solution was vacuum filtered and dried to obtain a hydrolyzed salt embedded carbon nanotube material.
[0010] Annealing of hydrolyzed salt-embedded carbon nanotube materials yields metal oxide-embedded carbon nanotube nanoflexible materials.
[0011] In one or more embodiments of the present invention, the hydrolyzed salt is at least one selected from zirconium chloride, ferrous chloride, and vanadium chloride; and / or,
[0012] The carbon nanotubes are at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, and few-walled carbon nanotubes.
[0013] In one or more embodiments of the present invention, the mass ratio of the hydrolyzed salt to the open carbon nanotubes is 1:1 to 50:1.
[0014] In one or more embodiments of the present invention, the carbon nanotubes are subjected to air oxidation annealing to open them, wherein the air oxidation annealing temperature is 400℃-700℃ and the time is 0.5h-3h.
[0015] In one or more embodiments of the present invention, the open carbon nanotubes are mixed with water to make the concentration of open carbon nanotubes 0.5 mg / ml-3 mg / ml; then hydrolyzed salt is added and stirred at 100 rpm-500 rpm for 5 h-96 h to obtain a hydrolyzed salt carbon nanotube solution.
[0016] In one or more embodiments of the present invention, the hydrolyzed salt carbon nanotube solution is vacuum filtered, washed with deionized water, and dried to obtain hydrolyzed salt embedded carbon nanotube material.
[0017] The drying operation uses any of the following:
[0018] Air dry naturally for 24-96 hours;
[0019] Dry at 50℃-80℃ for 8h-24h;
[0020] Freeze-dry at -40℃ to -60℃ for 24-72 hours.
[0021] In one or more embodiments of the present invention, the hydrolyzed salt embedded carbon nanotube material is annealed under an inert atmosphere at a temperature of 400℃-800℃ for 0.5h-8h and a gas flow rate of 50sccm-200sccm.
[0022] Another specific embodiment of the present invention provides the following technical solution:
[0023] A metal oxide embedded carbon nanotube nanoflexible material is prepared by the above-described preparation method.
[0024] In one or more embodiments of the present invention, the metal oxide is in the form of nanoribbons in carbon nanotubes, with a width of 1 nm-1.8 nm; and / or,
[0025] The mass percentage of metal oxide in the metal oxide-embedded carbon nanotube nanoflexible material is 3wt.%-6wt.%.
[0026] Another specific embodiment of the present invention provides the following technical solution:
[0027] Application of a metal oxide embedded carbon nanotube nanoflexible material in the fields of organic matter degradation and / or energy harvesting.
[0028] Compared with the prior art, the present invention has the following beneficial effects:
[0029] 1. The preparation method provided by the present invention utilizes the confined space of carbon nanotubes to realize the preparation of flexoelectric materials with built-in stress gradient metal oxide nanoribbons. The width of the nanoribbons is 1nm-1.8nm. By applying a very small stress, the geometrically necessary dislocation density will be significantly increased compared with bulk materials, resulting in a huge flexoelectric effect.
[0030] 2. The present invention provides a method for preparing nano-flexible materials by hydrolyzing salts in carbon nanotubes. This method requires no heating, uses water as a solvent, is simple, has low equipment requirements, and is highly economical. At the same time, after annealing, the metal oxide nanoribbons generated in the confined space of the hydrolyzed salt have their own strain gradient. The material can exhibit flexural electricity regardless of the external stress applied (not limited to bending, compressive stress, tensile stress, etc.). It shows great potential in the fields of organic pollutant degradation and energy harvesting. Attached Figure Description
[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0032] Figure 1 This is a flowchart of a method for preparing a metal oxide-embedded carbon nanotube nanoflexible material according to an embodiment of the present invention;
[0033] Figures 2-4 The images shown are transmission electron microscope (TEM) images and EDS spectra of the metal oxide-embedded carbon nanotube nanoflexible material in Example 1 of this invention.
[0034] Figure 5 This is a statistical diagram of the interplanar spacing of the metal oxide-embedded carbon nanotube nanoflexible material in Example 2 of the present invention;
[0035] Figures 6-7 This is a scanning electron microscope image of the product obtained in Comparative Example 1 of the present invention;
[0036] Figures 8-9 The graph shows the results of catalytic degradation of organic matter using the products obtained in Example 1, Comparative Example 2, and Comparative Example 3.
[0037] Figures 10-11 The working principle diagram of the products obtained in Comparative Examples 2, 3, 4, and 5 under magnetic stirring and the comparison diagram of energy harvesting with pure carbon nanotubes. Detailed Implementation
[0038] To enable those skilled in the art to better understand the technical solutions in this disclosure, the technical solutions in the embodiments of this disclosure are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments in this disclosure, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this disclosure.
[0039] To address the shortcomings of existing technologies, the inventors, through long-term research and extensive practice, have proposed the technical solution of this invention. The main focus is on providing a novel method for preparing metal oxide-embedded carbon nanotube flexoelectric materials, thereby broadening the preparation pathways for nano-flexoelectric materials and improving their performance in practical applications. Specifically, by utilizing the confined space of carbon nanotubes, nanoscale flexoelectric materials with embedded stress gradients are prepared. The size effect is used to increase the geometrically necessary dislocation density, amplifying the flexoelectric effect and improving its performance in organic catalytic degradation and energy harvesting.
[0040] This invention utilizes flexible carbon nanotubes as templates and combines wet chemical methods to prepare controllable nanoflexielectric materials with large strain gradients using a simple and low-cost approach. There are currently no reports on this type of material.
[0041] A specific embodiment of the present invention provides a method for preparing a metal oxide-embedded carbon nanotube nanoflexible material, such as... Figure 1 As shown, the specific steps include the following:
[0042] Step 1: Open the carbon nanotubes to obtain open carbon nanotubes.
[0043] Specifically, carbon nanotubes are placed in a tube furnace for air oxidation annealing to open them up. The specific operating conditions for air oxidation annealing are: temperature 400℃-700℃, time 0.5h-3h. The carbon nanotubes are at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, and few-walled carbon nanotubes.
[0044] Step 2: Mix open carbon nanotubes, hydrolyzed salt, and water to obtain a hydrolyzed salt carbon nanotube solution.
[0045] Specifically, the hydrolysate is at least one of zirconium chloride, ferrous chloride, and vanadium chloride, and the mass ratio of the hydrolysate to open carbon nanotubes is 1:1-50:1. The open carbon nanotubes are mixed with water to disperse them in the water, with a concentration of 0.5 mg / ml-3 mg / ml; then the hydrolysate is added, and the mixture is mechanically stirred at 100 rpm-500 rpm for 5 h-96 h to obtain a hydrolysate carbon nanotube solution.
[0046] Step 3: Vacuum filter and dry the hydrolyzed salt carbon nanotube solution to obtain hydrolyzed salt embedded carbon nanotube material.
[0047] Specifically, the hydrolyzed salt carbon nanotube solution is vacuum filtered and washed repeatedly with deionized water 3-5 times to remove the hydrolyzed salts adsorbed on the surface of the carbon nanotubes. After washing, the sample is dried using methods such as natural drying, oven drying, or freeze drying to remove moisture. Specifically, natural drying involves drying in a fume hood for 24-96 hours; oven drying is performed at a temperature of 50℃-80℃ for 8-24 hours; freeze drying requires freezing the sample before freezing, followed by freeze drying at a temperature range of -40℃ to -60℃ for 24-72 hours.
[0048] Step 4: Anneal the hydrolyzed salt embedded carbon nanotube material to obtain a metal oxide embedded carbon nanotube nanoflexible material.
[0049] Specifically, the hydrolyzed salt-embedded carbon nanotube material is annealed in an inert atmosphere such as argon at a temperature of 400℃-800℃ for 0.5h-8h and a gas flow rate of 50sccm-200sccm. Using hydrolyzed salt as a precursor, the hydrolyzed salt product is embedded in carbon nanotubes through hydrolysis. After annealing, the product interacts with the carbon nanotubes to generate a strain gradient, thereby exhibiting a flexural electrical effect.
[0050] Another specific embodiment of the present invention provides a metal oxide embedded carbon nanotube nanoflexible material, which is obtained by the above preparation method.
[0051] Specifically, the metal oxides in the carbon nanotubes are in the form of nanoribbons with a width of 1 nm to 1.8 nm. The mass ratio of the metal oxides in the metal oxide-embedded carbon nanotube flexoelectric nanomaterial can be adjusted according to the mass ratio of hydrolyzed salts and open carbon nanotubes, such as controlling the mass percentage of metal oxides to be 3 wt.% to 6 wt.%.
[0052] The metal oxide embedded carbon nanotube flexoelectric material obtained by this invention has a size at the nanometer level. The confined space of the carbon nanotubes generates an internal stress gradient. By applying a very small stress, the geometrically necessary dislocation density will be significantly increased compared to the bulk material, thereby generating a huge flexoelectric effect.
[0053] Another specific embodiment of the present invention provides an application of a metal oxide embedded carbon nanotube nanoflexible material in the fields of organic matter degradation and / or energy harvesting.
[0054] Specifically, by utilizing the aforementioned metal oxide-embedded carbon nanotube flexoelectric material, the strain gradient is increased through nano-sizing, amplifying the flexoelectric effect. By incorporating the strain gradient, the initiation potential for the catalytic degradation of organic matter is reduced. In the degradation test of Rhodamine B, under low loading and low power ultrasonic action (0.1 g / L, 40 kHz - 110 W), 84% degradation of Rhodamine B was achieved in 60 minutes, which is 27% higher than that of pure carbon nanotubes.
[0055] Furthermore, in some embodiments, electrodes prepared using the aforementioned metal oxide-embedded carbon nanotube nanoflexible materials can achieve an output current of 1.15µA by applying a certain frequency of fluctuation to a 1mol / L KCl solution through magnetic stirring, which is 7.7 times that of pure carbon nanotubes.
[0056] The present invention will be further described in detail below with reference to specific embodiments.
[0057] All raw materials used in this invention are not particularly restricted in their source; they can be purchased from the market or prepared using conventional methods well-known to those skilled in the art. All processes and equipment used in this invention are given conventional names within the art, and each name is clear and unambiguous within its relevant application. Those skilled in the art can understand the conventional process steps and corresponding equipment used based on the names.
[0058] Example 1
[0059] The preparation method of the metal oxide embedded carbon nanotube flexible nanomaterial in this embodiment is as follows:
[0060] Single-walled carbon nanotube powder (purchased from Ocsial, Russia) was placed in a tube furnace and annealed in air at 500°C for 1 hour. Open-ended single-walled carbon nanotubes were added to deionized water to obtain a 3 mg / ml aqueous solution. Then, zirconium chloride hydrolysate was added to the single-walled carbon nanotube aqueous solution, and the mixture was stirred at 300 rpm for 48 hours. The mass ratio of zirconium chloride to single-walled carbon nanotubes was 5:1.
[0061] The sample was filtered by vacuum filtration, washed three times with deionized water, and then placed in an 80°C drying oven for 12 hours to prepare zirconium chloride-embedded carbon nanotube material.
[0062] Zirconia-embedded carbon nanotube nanomaterials were prepared by annealing zirconium chloride embedded carbon nanotubes at 500℃ and 100 sccm argon for 1 hour.
[0063] Example 2
[0064] The preparation method of the metal oxide embedded carbon nanotube flexible nanomaterial in this embodiment is as follows:
[0065] Few-walled carbon nanotube powder (purchased from Jiangsu Tiannai Technology Co., Ltd.) was placed in a tube furnace and annealed in air at 700 °C for 2 hours. Open-ended few-walled carbon nanotubes were added to deionized water to obtain a few-walled carbon nanotube aqueous solution with a concentration of 1 mg / ml. Then, zirconium chloride hydrolysate was added to the few-walled carbon nanotube aqueous solution, and the mixture was stirred at 500 rpm for 96 hours. The mass ratio of zirconium chloride to few-walled carbon nanotubes was 10:1.
[0066] Zirconium chloride-embedded carbon nanotube material was prepared by filtration under vacuum, washing three times with deionized water, and then drying the sample in a fume hood for 15 hours.
[0067] Zirconia-embedded carbon nanotube nanomaterials were prepared by annealing zirconium chloride material at 600℃ and 150 sccm argon for 2 hours.
[0068] Example 3
[0069] The preparation method of the metal oxide embedded carbon nanotube flexible nanomaterial in this embodiment is as follows:
[0070] Single-walled carbon nanotube powder (purchased from Ocsial, Russia) was placed in a tube furnace and annealed in air at 550°C for 0.8 hours. Open-ended single-walled carbon nanotubes were added to deionized water to obtain a 2 mg / ml aqueous solution of single-walled carbon nanotubes. Then, ferrous chloride hydrolysate was added to the single-walled carbon nanotube aqueous solution, and the mixture was stirred at 350 rpm for 30 hours. The mass ratio of ferrous chloride to single-walled carbon nanotubes was 1:1.
[0071] The sample was filtered by vacuum filtration, washed three times with deionized water, and then freeze-dried at -40°C for 24 hours to prepare ferrous chloride-embedded carbon nanotube material.
[0072] The ferrous chloride-embedded carbon nanotube material was annealed at 650℃ in 200 sccm argon for 5 hours to prepare a strip-shaped iron oxide-embedded carbon nanotube nanoflexible material.
[0073] Example 4
[0074] The preparation method of the metal oxide embedded carbon nanotube flexible nanomaterial in this embodiment is as follows:
[0075] Multi-walled carbon nanotube powder (purchased from Changxin Chemical) was placed in a tube furnace and annealed in air at 600°C for 0.8 hours. Open-ended multi-walled carbon nanotubes were added to deionized water to obtain a 1.5 mg / ml aqueous solution of multi-walled carbon nanotubes. Then, vanadium chloride hydrolysate was added to the multi-walled carbon nanotube aqueous solution, and the mixture was stirred at 300 rpm for 48 hours. The mass ratio of vanadium chloride to multi-walled carbon nanotubes was 20:1.
[0076] The sample was filtered by vacuum filtration, washed three times with deionized water, and then placed in a fume hood to dry for 24 hours to prepare vanadium chloride-embedded carbon nanotube material.
[0077] A vanadium chloride-embedded carbon nanotube nanomaterial was prepared by annealing the material at 400℃ and 80 sccm of argon for 6 hours.
[0078] Example 5
[0079] The preparation method of the metal oxide embedded carbon nanotube flexible nanomaterial in this embodiment is as follows:
[0080] Few-walled carbon nanotube powder (purchased from Jiangsu Tiannai Technology Co., Ltd.) was placed in a tube furnace and annealed in air at 600℃ for 3 hours. Open-ended few-walled carbon nanotubes were added to deionized water to obtain a few-walled carbon nanotube aqueous solution with a concentration of 2.5 mg / ml. Then, hydrolyzed ferrous chloride was added to the few-walled carbon nanotube aqueous solution, and the mixture was stirred at 350 rpm for 72 hours. The mass ratio of ferrous chloride to few-walled carbon nanotubes was 30:1.
[0081] The sample was filtered by vacuum filtration, washed three times with deionized water, and then placed in a fume hood to dry for 20 hours to prepare ferrous chloride-embedded carbon nanotube material.
[0082] The ferrous chloride-embedded carbon nanotube material was annealed at 450℃ in 100 sccm argon for 8 hours to prepare a strip-shaped iron oxide-embedded carbon nanotube nanoflexible material.
[0083] Example 6
[0084] The preparation method of the metal oxide embedded carbon nanotube flexible nanomaterial in this embodiment is as follows:
[0085] Single-walled carbon nanotube powder (purchased from Ocsial, Russia) was placed in a tube furnace and annealed in air at 500°C for 1.2 hours. Open-ended single-walled carbon nanotubes were added to deionized water to obtain a 1.5 mg / ml aqueous solution of single-walled carbon nanotubes. Then, vanadium chloride hydrolysate was added to the single-walled carbon nanotube aqueous solution, and the mixture was stirred at 250 rpm for 24 hours. The mass ratio of vanadium chloride to single-walled carbon nanotubes was 50:1.
[0086] The sample was filtered by vacuum filtration, washed three times with deionized water, and then freeze-dried at -40°C for 48 hours to prepare vanadium chloride-embedded carbon nanotube material.
[0087] Vanadium chloride embedded carbon nanotube material was annealed at 700℃ and 150 sccm argon for 3 hours to prepare a strip-shaped vanadium oxide embedded carbon nanotube flexural material.
[0088] Comparative Example 1
[0089] The preparation method of the metal oxide embedded carbon nanotube nanoflexible material in this comparative example is basically the same as that in Example 1, except that single-walled carbon nanotubes were not added to the aqueous solution.
[0090] Comparative Example 2
[0091] The preparation method of the metal oxide embedded carbon nanotube nanoflexible material in this comparative example is basically the same as that in Example 1, except that: no hydrolyzed salt zirconium chloride was added to the aqueous solution of single-walled carbon nanotubes.
[0092] Comparative Example 3
[0093] The preparation method of the metal oxide embedded carbon nanotube nanoflexible material in this comparative example is basically the same as that in Example 1, except that the obtained zirconium chloride embedded carbon nanotube material was not annealed at 500°C and 100 sccm in argon for 1 hour.
[0094] Comparative Example 4
[0095] The preparation method of the metal oxide embedded carbon nanotube nanoflexible material in this comparative example is basically the same as that in Example 3, except that the obtained ferrous chloride embedded carbon nanotube material was not annealed at 650°C and 200 sccm argon for 5 hours.
[0096] Comparative Example 5
[0097] The preparation method of the metal oxide embedded carbon nanotube nanoflexible material in this comparative example is basically the same as that in Example 4, except that the obtained vanadium chloride embedded carbon nanotube material was not annealed at 400°C and 80 sccm in argon for 6 hours.
[0098] The metal oxide embedded carbon nanotube nanoflexible material prepared in Example 1 is as follows: Figures 2-4 As shown, from Figures 2-4 As can be seen, the metal oxide is in the form of a band within the carbon nanotube, successfully realizing the preparation of a nano-flexible electrical material with a band of metal oxide embedded in carbon nanotubes.
[0099] Figure 5 The figures show the lattice arrangement, left and right interplanar spacing, and width of the metal oxide nanoribbons within the carbon nanotubes in the product obtained in Example 2. The lattice arrangement shows that the nanoribbons have twin dislocations and distortions. Compared with the standard interplanar spacing of metal oxides, the actual measured interplanar spacing shows a certain degree of contraction and expansion, indicating that the confinement space of the carbon nanotubes brings an internal strain gradient to the nanoribbons.
[0100] Figure 6 and Figure 7 To illustrate the morphology of the metal oxide obtained in Comparative Example 1 without the addition of single-walled carbon nanotubes in aqueous solution, the scanning electron microscope image shows that the product is rod-shaped with sizes ranging from several to tens of micrometers. This is because the absence of single-walled carbon nanotubes in the mechanically stirred aqueous solution prevents the acquisition of nanoscale ribbon-shaped flexible electrical materials without confinement and control by the single-walled carbon nanotubes.
[0101] Figure 8 and Figure 9The graph shows the efficiency and reaction rate constant of the ultrasonic degradation of the organic pollutant Rhodamine B by the carbon nanotubes obtained in Comparative Example 2, the zirconium salt@carbon nanotubes obtained in Comparative Example 3, and the zirconia@carbon nanotubes obtained in Example 1. The specific operation was as follows: The same dosage of catalyst (0.1 g / L of the products from Example 1 and Comparative Examples 2 and 3) was added to a Rhodamine B solution of a certain concentration. The solution was stirred in the dark for 1 hour, then continuously ultrasonicated in a water bath at a constant temperature of 25°C. Every 10 minutes, a certain amount of Rhodamine B solution was extracted, centrifuged, and the absorbance was measured and recorded using a UV spectrometer. The graph shows that the zirconia-embedded carbon nanotube flexoelectric material in Example 1 achieved an 84% degradation efficiency of Rhodamine B in 60 minutes under low loading and low power ultrasonic action (0.1 g / L, 40 kHz - 110 W), which is higher than the 66% of the pure single-walled carbon nanotubes in Comparative Example 2. This indicates that the catalytic efficiency and reaction rate constant of the prepared carbon nanotube-embedded metal oxide nanoribbons far exceed those of pure carbon nanotubes.
[0102] The products obtained in Comparative Example 3 (zirconium salt@carbon nanotube), Comparative Example 4 (iron salt@carbon nanotube), Comparative Example 5 (vanadium salt@carbon nanotube), and Example 1 (zirconia@carbon nanotube) were applied to the field of energy harvesting. Specifically, energy harvesting was performed on 1 mol / L KCl under magnetic stirring. A ribbon-like metal oxide embedded with carbon nanotube flexible nanomaterials was used as an electrode. Using a potentiostatic chronoamperometry method, with the voltage set to zero, the current output was recorded under both the on and off states of magnetic stirring. Figure 10 (For the working principle diagram). From Figure 11 It can be seen that, compared with pure carbon nanotubes, the time-current curve amplitude of the ribbon metal oxide embedded carbon nanotube nanoflexible material is larger. In terms of short-circuit current, the output current of zirconium oxide@carbon nanotube is 8 times that of zirconium salt@carbon nanotube. This indicates that after the nano metal oxide is embedded with carbon nanotubes, it can convert the force generated by magnetic stirring into a larger output current, and the electromechanical conversion efficiency is higher.
[0103] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.
[0104] It will be apparent to those skilled in the art that this disclosure is not limited to the details of the exemplary embodiments described above, and that this disclosure can be implemented in other specific forms without departing from the spirit or essential characteristics of this disclosure. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of this disclosure is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within this disclosure.
[0105] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A method for preparing a metal oxide-embedded carbon nanotube flexible nanomaterial, characterized in that, The preparation method includes the following steps: Open the carbon nanotubes to obtain open carbon nanotubes; Open carbon nanotubes, hydrolyzed salt, and water are mixed to obtain a hydrolyzed salt carbon nanotube solution. The hydrolyzed salt carbon nanotube solution was vacuum filtered and dried to obtain a hydrolyzed salt embedded carbon nanotube material. Annealing of hydrolyzed salt-embedded carbon nanotube materials yields metal oxide-embedded carbon nanotube nanoflexible materials.
2. The method for preparing the metal oxide-embedded carbon nanotube flexible nanomaterial according to claim 1, characterized in that, The hydrolyzed salt is at least one of zirconium chloride, ferrous chloride, and vanadium chloride; and / or, The carbon nanotubes are at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, and few-walled carbon nanotubes.
3. The method for preparing the metal oxide-embedded carbon nanotube flexible nanomaterial according to claim 1, characterized in that, The mass ratio of the hydrolyzed salt to the open carbon nanotubes is 1:1 to 50:
1.
4. The method for preparing the metal oxide-embedded carbon nanotube flexible nanomaterial according to claim 1, characterized in that, The carbon nanotubes are subjected to air oxidation annealing to create openings. The air oxidation annealing temperature is 400℃-700℃ and the time is 0.5h-3h.
5. The method for preparing the metal oxide-embedded carbon nanotube flexible nanomaterial according to claim 1, characterized in that, The open carbon nanotubes were mixed with water to make the concentration of open carbon nanotubes 0.5 mg / ml-3 mg / ml; then hydrolyzed salt was added and stirred at 100 rpm-500 rpm for 5 h-96 h to obtain a hydrolyzed salt carbon nanotube solution.
6. The method for preparing the metal oxide-embedded carbon nanotube flexible nanomaterial according to claim 1, characterized in that, The hydrolyzed salt carbon nanotube solution was vacuum filtered, washed with deionized water, and dried to obtain the hydrolyzed salt embedded carbon nanotube material. The drying operation uses any of the following: Air dry naturally for 24-96 hours; Dry at 50℃-80℃ for 8h-24h; Freeze-dry at -40℃ to -60℃ for 24-72 hours.
7. The method for preparing the metal oxide-embedded carbon nanotube flexible nanomaterial according to claim 1, characterized in that, The hydrolyzed salt embedded carbon nanotube material was annealed in an inert atmosphere at a temperature of 400℃-800℃ for 0.5h-8h and a gas flow rate of 50sccm-200sccm.
8. A metal oxide embedded carbon nanotube flexible nanomaterial, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. The metal oxide-embedded carbon nanotube nanoflexible material according to claim 8, characterized in that, The metal oxide is arranged in nanoribbons within the carbon nanotubes, with a width of 1 nm to 1.8 nm; and / or, The mass percentage of metal oxide in the metal oxide-embedded carbon nanotube nanoflexible material is 3wt.%-6wt.%.
10. The application of the metal oxide embedded carbon nanotube nanoflexible material of claim 8 in the field of organic matter degradation and / or energy harvesting.