A one-dimensional CuAlO2 material, its preparation method and application
One-dimensional CuAlO2 materials were prepared by combining calcium alginate fiber ion exchange with high-temperature calcination, which solved the problems of complex preparation process and high cost of CuAlO2 materials. This method achieves low-cost, easy-to-control material preparation and high reactivity, and is suitable for transparent electronic devices, heterojunction solar cells and gas sensors.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHAANXI UNIV OF SCI & TECH
- Filing Date
- 2026-04-02
- Publication Date
- 2026-06-26
Smart Images
Figure CN122276809A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of CuAlO2 material preparation technology, specifically to a one-dimensional CuAlO2 material, its preparation method, and its application. Background Technology
[0002] CuAlO2 is a p-type transparent conductive oxide with a copper-iron oxide structure. Since its p-type conductivity was first reported by Hosono et al. in 1997, it has attracted widespread attention in the field of materials science. As a wide-bandgap semiconductor (Eg approximately 3.5 eV), CuAlO2 has high transmittance in the visible light region, and its p-type conductivity is relatively rare among oxide semiconductors. Therefore, it shows broad application prospects in transparent electronic devices, heterojunction solar cells, gas sensors, and other fields.
[0003] Currently, the main methods for preparing CuAlO2 materials include solid-state reaction, sol-gel, hydrothermal / solvothermal, pulsed laser deposition, and magnetron sputtering. In recent years, with the development of nanotechnology, researchers have begun to explore new approaches to prepare fibrous CuAlO2 using biomass materials as templates or electrospinning. Although electrospinning has become one of the main processes for preparing nanofibers, its core equipment is expensive. The high cost of equipment presents a significant economic barrier to the widespread application of electrospinning technology. Secondly, while electrospinning can achieve the desired fiber morphology for CuAlO2 nanofiber membranes, the process is complex and influenced by numerous factors, including solution properties (viscosity, conductivity, surface tension), process conditions, and environmental parameters (temperature, humidity). The combined effect of these factors directly impacts fiber morphology and quality. Furthermore, there is no standardized range for process parameters across different systems, requiring repeated adjustments based on specific conditions, increasing the difficulty of process reproducibility. In addition, research has shown that the surface morphology of the fiber membrane undergoes significant changes during high-temperature heat treatment, with increased fiber diameter, roughened surface, and even particle aggregation. This indicates that simplifying the preparation process while maintaining the integrity of the fiber structure remains a key technical challenge in achieving the desired one-dimensional CuAlO2 material morphology.
[0004] In summary, although CuAlO2 materials possess unique structural characteristics and broad application prospects, their preparation still faces technical challenges such as high-temperature energy consumption, impurity phase control, doping uniformity, morphology regulation, and doping mechanisms. Therefore, developing new methods for preparing CuAlO2 with low energy consumption, high phase purity, and controllable morphology, and exploring the influence of elemental doping on the material's structure and properties, is of great significance for promoting the practical application of this type of material. Summary of the Invention
[0005] To address the problems of complex preparation process and difficulty in morphology control of one-dimensional CuAlO2 materials in existing technologies, this invention provides a one-dimensional CuAlO2 material, preparation method, and application.
[0006] To achieve the above objectives, the present invention employs the following technical solution: This invention provides a method for preparing a one-dimensional CuAlO2 material, comprising: Pretreatment of calcium alginate fiber removes calcium ions from the calcium alginate fiber to obtain alginate fiber. Formulating a product containing Al 3+ and Cu 2+ Ion exchange solution; Alginate fibers were placed in an ion exchange solution for ion exchange to obtain a one-dimensional CuAlO2 material precursor. One-dimensional CuAlO2 material precursors are calcined to obtain one-dimensional CuAlO2 material.
[0007] Optionally, the method for pretreating calcium alginate fiber to remove calcium ions from the calcium alginate fiber to obtain calcium alginate fiber is as follows: After ultrasonic cleaning, the calcium alginate fiber is acid-washed with hydrochloric acid solution, and the hydrogen ions in the hydrochloric acid replace the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0008] Optionally, the concentration of the hydrochloric acid solution is 0.5-1.5 mol / L.
[0009] Optionally, the ion exchange liquid further includes Fe. 3+ Fe 3+ The molar amount of Al 3+ 5%-15%.
[0010] Optionally, the ion exchange solution contains Al 3+ The concentration is 0.01-1 mol / L.
[0011] Optionally, Cu in the ion exchange solution 2+ The concentration is 0.01-1 mol / L.
[0012] Optionally, the method of calcining the one-dimensional CuAlO2 material precursor to obtain the one-dimensional CuAlO2 material is as follows: One-dimensional CuAlO2 material precursors are calcined at 1100-1300℃ for 1.5-3 hours to obtain one-dimensional CuAlO2 material.
[0013] Optionally, the heating rate during the calcination process is 8-12℃ / min.
[0014] The present invention also provides a one-dimensional CuAlO2 material, which is prepared using the above-described method for preparing one-dimensional CuAlO2 material.
[0015] The above-mentioned one-dimensional CuAlO2 material is used in transparent electronic devices, heterojunction solar cells, or gas sensors.
[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a method for preparing one-dimensional CuAlO2 materials. The method uses calcium alginate fiber as a template and prepares the one-dimensional CuAlO2 material through ion exchange combined with high-temperature calcination. Calcium alginate fiber, as a natural polymer fiber, is widely available and can be extracted from marine organisms such as seaweed. Compared to some artificially synthesized polymer template materials, it is lower in cost and renewable, which helps reduce the raw material cost of the entire preparation process. After removing calcium ions, the alginate fiber retains its natural one-dimensional structure, providing a good template basis for the subsequent ion exchange process. Furthermore, the abundant carboxyl groups on the molecular chain provide uniform anchoring sites for metal ions, enabling them to bind with Al. 3+ and Cu 2+ When metal ions undergo an effective ion exchange reaction, the alginate fibers gradually decompose during ion exchange and high-temperature calcination. Simultaneously, the metal ions are transformed in situ into CuAlO2 crystals, perfectly inheriting the fiber morphology of the template. This chemical coordination-based ion exchange method allows metal ions to be rapidly and uniformly adsorbed on the surface and interior of the alginate fibers, forming a CuAlO2 material precursor, thus successfully preparing one-dimensional CuAlO2 materials. Compared to traditional CuAlO2 material preparation methods, this method is simple and easy to implement. It not only yields CuAlO2 materials with a regular one-dimensional structure but also does not involve the use of expensive equipment, significantly reducing production barriers and costs. It has good economic viability and industrialization prospects. The entire process is simple to operate, with clear steps, and the process parameters at each stage are easy to control. It does not require complex equipment debugging or professional operating skills, greatly reducing the technical threshold and laying a solid foundation for large-scale production.
[0017] By using hydrochloric acid solution to treat calcium alginate fibers, calcium ions can be removed more easily, providing a good template basis for subsequent ion exchange processes. Furthermore, the pretreatment process does not introduce complex impurities, which helps to ensure the purity of the final product.
[0018] Fe 3+ Doping with CuAlO2 can improve the dielectric properties of one-dimensional CuAlO2 materials, making them more promising for applications in transparent electronic devices, solar cells and other fields.
[0019] The present invention also provides a one-dimensional CuAlO2 material prepared by the above method. The one-dimensional CuAlO2 material retains a complete one-dimensional structure, has a larger specific surface area, and can provide more surface active sites, so that the one-dimensional CuAlO2 material has higher reactivity and adsorption capacity when interacting with gas molecules, liquid molecules or other substances.
[0020] The aforementioned applications of one-dimensional CuAlO2 materials in transparent electronic devices, heterojunction solar cells, and gas sensors demonstrate several advantages. In transparent electronic devices, one-dimensional CuAlO2, as an intrinsic p-type transparent conductive oxide, allows for linear bonding between Cu and O due to its layered structure, promoting hole migration. This enables high transmittance in the visible light region while maintaining high conductivity, making it an ideal material for fully transparent integrated circuits, display backplanes, and smart windows. In heterojunction solar cells, the band gap of one-dimensional CuAlO2 allows it to absorb high-energy, short-wavelength light, forming complementary absorption with narrow bandgap materials. In heterojunctions, the one-dimensional CuAlO2 structure guides the vertical transport of photogenerated carriers, reducing series resistance, increasing the device fill factor, and improving battery efficiency and lifespan. In gas sensors, the high specific surface area of one-dimensional CuAlO2 provides more active sites, enhancing the adsorption capacity for target gases and thus improving the sensor's response speed. Attached Figure Description
[0021] Figure 1 This is a schematic diagram of the preparation method of a one-dimensional CuAlO2 material according to the present invention.
[0022] Figure 2 The images shown are SEM images of the one-dimensional CuAlO2 materials prepared in Examples 1-3 of the present invention; wherein, Figures a, b and c are SEM images of the one-dimensional CuAlO2 materials prepared in Example 1 at different magnifications, Figures d, e and f are SEM images of the one-dimensional CuAlO2 materials prepared in Example 2 at different magnifications, and Figures g, h and i are SEM images of the one-dimensional CuAlO2 materials prepared in Example 3 at different magnifications.
[0023] Figure 3 The images are XRD patterns of one-dimensional CuAlO2 materials prepared in Examples 1-3 of the present invention; wherein a is the XRD pattern of one-dimensional CuAlO2 material prepared in Example 1, b is the XRD pattern of one-dimensional CuAlO2 material prepared in Example 2, and c is the XRD pattern of one-dimensional CuAlO2 material prepared in Example 3. Detailed Implementation
[0024] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.
[0025] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.
[0026] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values (including integers and fractions) within those ranges.
[0027] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”
[0028] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.
[0029] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0030] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.
[0031] The present invention will be further described in detail below with reference to specific embodiments. These descriptions are for explanation purposes only and are not intended to limit the scope of the invention.
[0032] See Figure 1 This invention discloses a method for preparing a one-dimensional CuAlO2 material, comprising: S1: Pretreatment of calcium alginate fiber to remove calcium ions from the calcium alginate fiber, specifically: After ultrasonic cleaning, the calcium alginate fiber is acid-washed three times or more with a hydrochloric acid solution of 0.5-1.5 mol / L, each time for 30-50 minutes, so that the hydrogen ions in the hydrochloric acid can replace the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0033] S2: Formula containing Al 3+ and Cu 2+ The ion exchange solution is specifically: Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.01-1 mol / L, Cu 2+ The concentration is 0.01-1 mol / L; preferably, the ion exchange solution is also doped with Fe. 3+ Fe 3+ The molar amount of Al 3+ 5%-15%; S3: Alginate fibers were placed in an ion exchange solution for ion exchange to obtain a one-dimensional CuAlO2 material precursor, specifically: After stirring the alginate fiber in the ion exchange solution and then sonicating it, the metal ions in the ion exchange solution are fully exchanged to obtain a one-dimensional CuAlO2 material precursor.
[0034] S4: The one-dimensional CuAlO2 material precursor is calcined to obtain the one-dimensional CuAlO2 material, specifically: The one-dimensional CuAlO2 material precursor was heated to 1100-1300℃ at a heating rate of 8-12℃ / min and held for 1.5-3h to obtain the one-dimensional CuAlO2 material.
[0035] This method uses calcium alginate fibers as a template to prepare one-dimensional CuAlO2 materials via ion exchange combined with high-temperature calcination. The prepared one-dimensional CuAlO2 materials perfectly inherit the fiber morphology of the template. Compared with traditional CuAlO2 material preparation methods, this method is simple, low-cost, and easy to control in terms of morphology, showing good economic viability and prospects for industrialization.
[0036] The present invention also provides a one-dimensional CuAlO2 material prepared by the above method. The one-dimensional CuAlO2 material retains a complete one-dimensional structure, has a larger specific surface area, and can provide more surface active sites, so that the one-dimensional CuAlO2 material has higher reactivity and adsorption capacity when interacting with gas molecules, liquid molecules or other substances.
[0037] The aforementioned applications of one-dimensional CuAlO2 materials in transparent electronic devices, heterojunction solar cells, and gas sensors demonstrate several advantages. In transparent electronic devices, one-dimensional CuAlO2, as an intrinsic p-type transparent conductive oxide, allows for linear bonding between Cu and O due to its layered structure, promoting hole migration. This enables high transmittance in the visible light region while maintaining high conductivity, making it an ideal material for fully transparent integrated circuits, display backplanes, and smart windows. In heterojunction solar cells, the band gap of one-dimensional CuAlO2 allows it to absorb high-energy, short-wavelength light, forming complementary absorption with narrow bandgap materials. In heterojunctions, the one-dimensional CuAlO2 structure guides the vertical transport of photogenerated carriers, reducing series resistance, increasing the device fill factor, and improving battery efficiency and lifespan. In gas sensors, the high specific surface area of one-dimensional CuAlO2 provides more active sites, enhancing the adsorption capacity for target gases and thus improving the sensor's response speed.
[0038] Example 1 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0039] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.1 mol / L, Cu 2+ The concentration was 0.05 mol / L; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0040] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0041] Example 2 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0042] Cu(NO3)2·3H2O, Al(NO3)3·9H2O, and Fe(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.1 mol / L, Cu 2+ The concentration was 0.05 mol / L, Fe 3+ The molar amount of Al 3+ 10%; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0043] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0044] Example 3 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0045] Cu(NO3)2·3H2O, Al(NO3)3·9H2O, and Fe(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.1 mol / L, Cu 2+ The concentration was 0.05 mol / L, Fe 3+ The molar amount of Al 3+ 15%; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0046] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0047] See Figure 2SEM analysis was performed on the one-dimensional CuAlO2 materials prepared in Examples 1-3. The results showed that the one-dimensional CuAlO2 materials prepared in Examples 1-3 basically retained the one-dimensional morphology of alginate fibers, achieving effective control of the one-dimensional morphology. Fe doping was also performed. 3+ Afterwards, the fibrous structure became more obvious and clear. However, Fe... 3+ The molar amount of Al 3+ At 15%, most fibers broke, corresponding to XRD analysis (see...). Figure 3 As the doping concentration increases, a large amount of FeAl2O4 phase is generated in the sample, which destroys the fibrous structure.
[0048] See Figure 3 XRD analysis was performed on the one-dimensional CuAlO2 materials prepared in Examples 1-3. The XRD pattern of the one-dimensional CuAlO2 material prepared in Example 1 showed only the CuAlO2 phase, with no other phases detected, indicating that a pure-phase one-dimensional CuAlO2 material was successfully prepared. When Fe was doped... 3+ The molar amount of doping is Al 3+ At 10%, the XRD pattern showed a large amount of CuO impurities and a small amount of Al2O3 impurities, indicating the introduction of Fe into the CuAlO2 crystal. 3+ Ions can inhibit the formation of the original phase; when Fe is doped... 3+ The molar amount of doping is Al 3+ At 15% doping concentration, the FeAl2O4 phase begins to appear in the XRD pattern, while the CuO diffraction peak weakens, with the CuAlO2 phase still dominating. In general, with increasing trivalent iron ion doping concentration, a large amount of CuO and Al2O3 phases initially appear in the diffraction pattern. As the doping concentration further increases, the CuO phase peak gradually weakens, and correspondingly, the FeAl2O4 phase begins to appear, gradually increasing in quantity with increasing doping concentration.
[0049] Example 4 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0050] Cu(NO3)2·3H2O, Al(NO3)3·9H2O, and Fe(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.1 mol / L, Cu 2+ The concentration was 0.05 mol / L, Fe 3+ The molar amount of Al 3+ 5%; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0051] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0052] Example 5 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1.5 mol / L hydrochloric acid solution for 30 minutes each time, so that the hydrogen ions in the hydrochloric acid could replace the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0053] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.05 mol / L, Cu 2+ The concentration was 0.04 mol / L; 3g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0054] The one-dimensional CuAlO2 material precursor was heated to 1100℃ at a heating rate of 8℃ / min and held for 3h to obtain the one-dimensional CuAlO2 material.
[0055] Example 6 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 0.5 mol / L hydrochloric acid solution for 50 minutes each time, so that the hydrogen ions in the hydrochloric acid could replace the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0056] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.15 mol / L, Cu 2+ The concentration was 0.06 mol / L; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0057] The one-dimensional CuAlO2 material precursor was heated to 1300℃ at a heating rate of 12℃ / min and held for 1.5h to obtain the one-dimensional CuAlO2 material.
[0058] Example 7 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0059] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.5 mol / L, Cu 2+ The concentration is 0.3 mol / L; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0060] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0061] Example 8 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0062] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.01 mol / L, Cu 2+ The concentration was 0.01 mol / L; 5g of alginate fiber was placed in 300mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0063] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0064] Example 9 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0065] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 1 mol / L, Cu 2+ The concentration is 1 mol / L; 5g of alginate fiber was placed in 100mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0066] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0067] Example 10 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0068] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.8 mol / L, Cu 2+ The concentration was 0.6 mol / L; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0069] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0070] Example 11 After ultrasonic cleaning, the calcium alginate fiber was acid-washed 5 times with a 1 mol / L hydrochloric acid solution for 40 minutes each time, so that the hydrogen ions in the hydrochloric acid replaced the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
[0071] Cu(NO3)2·3H2O and Al(NO3)3·9H2O were dissolved in water to obtain an ion exchange solution; wherein, Al in the ion exchange solution... 3+ The concentration is 0.2 mol / L, Cu 2+ The concentration is 0.1 mol / L; 5g of alginate fiber was placed in 150mL of ion exchange solution, stirred evenly, and then sonicated to allow the metal ions in the ion exchange solution to be fully exchanged, thus obtaining a one-dimensional CuAlO2 material precursor.
[0072] The one-dimensional CuAlO2 material precursor was heated to 1200℃ at a heating rate of 10℃ / min and held for 2h to obtain the one-dimensional CuAlO2 material.
[0073] The above description is merely a preferred embodiment of the present invention and is not intended to limit the technical solution of the present invention in any way. Those skilled in the art should understand that, without departing from the spirit and principles of the present invention, the technical solution can be modified and replaced in several simple ways, and these modifications and replacements are all within the scope of protection covered by the claims.
Claims
1. A method for preparing a one-dimensional CuAlO2 material, characterized in that, include: Pretreatment of calcium alginate fiber removes calcium ions from the calcium alginate fiber to obtain alginate fiber. Formulating a product containing Al 3+ and Cu 2+ Ion exchange solution; Alginate fibers were placed in an ion exchange solution for ion exchange to obtain a one-dimensional CuAlO2 material precursor. One-dimensional CuAlO2 material precursors are calcined to obtain one-dimensional CuAlO2 material.
2. The method for preparing one-dimensional CuAlO2 material according to claim 1, characterized in that, The method for pretreating calcium alginate fiber to remove calcium ions from the calcium alginate fiber to obtain alginate fiber is as follows: After ultrasonic cleaning, the calcium alginate fiber is acid-washed with hydrochloric acid solution, and the hydrogen ions in the hydrochloric acid replace the calcium ions in the calcium alginate fiber. The displaced calcium ions are washed away with water to obtain alginate fiber.
3. The method for preparing one-dimensional CuAlO2 material according to claim 2, characterized in that, The concentration of the hydrochloric acid solution is 0.5-1.5 mol / L.
4. The method for preparing one-dimensional CuAlO2 material according to claim 1, characterized in that, The ion exchange solution also includes Fe. 3+ Fe 3+ The molar amount of Al 3+ 5%-15%.
5. The method for preparing one-dimensional CuAlO2 material according to claim 1, characterized in that, Al in ion exchange solution 3+ The concentration is 0.01-1 mol / L.
6. The method for preparing one-dimensional CuAlO2 material according to claim 1, characterized in that, Cu in ion exchange solution 2+ The concentration is 0.01-1 mol / L.
7. The method for preparing one-dimensional CuAlO2 material according to claim 1, characterized in that, The method for obtaining one-dimensional CuAlO2 material by calcining the one-dimensional CuAlO2 material precursor is as follows: One-dimensional CuAlO2 material precursors are calcined at 1100-1300℃ for 1.5-3 hours to obtain one-dimensional CuAlO2 material.
8. The method for preparing one-dimensional CuAlO2 material according to claim 7, characterized in that, The heating rate during the calcination process is 8-12℃ / min.
9. A one-dimensional CuAlO2 material, characterized in that, Prepared using the one-dimensional CuAlO2 material preparation method according to any one of claims 1-8.
10. The application of the one-dimensional CuAlO2 material according to claim 9 in transparent electronic devices, heterojunction solar cells or gas sensors.