Ion-induced doped amorphous material as well as preparation method and application thereof

Abstract

The invention discloses an ion-induced doped amorphous material as well as a preparation method and application thereof, and belongs to the technical field of synthesis of amorphous materials. Wherein the ion-induced doped amorphous material is prepared from the following raw materials in parts by weight: 0.1 to 0.2 part of TiO2, 0.35 to 0.5 part of NaBH4, 0.02 to 0.04 part of NH4F, 0.01 to 0.015 part of Ga (NO3) 3.9 H2O, 0.02 part of (NH4) H2PO4, 0.08 part of citric acid, 0.05 part of PVP (Polyvinyl Pyrrolidone) and 30 parts of alcohol liquid; a crystalline material is used as a base, and hydrothermal anion-induced amorphization and low-temperature liquid-phase in-situ reduction are combined: strong coordination anions break crystal lattices to form a high-activity amorphous matrix, Ga is synchronously reduced into a zero-valent cluster, and the CO2 reduction rate is increased by virtue of a Ga-O-Ti bond; the PO4 < 3-> doped amorphous material is hydrophilic, alkali-resistant, adaptive to multiple pH values, and helpful to dissolve alkaline CO2, so that the traditional limitation is broken through.

Description

Technical Field

[0001] This invention belongs to the field of amorphous material synthesis technology, specifically relating to an ion-induced doped amorphous material, its preparation method, and its application. Background Technology

[0002] Under the "dual carbon" goal, CO2 photocatalytic reduction requires the support of efficient catalysts. Amorphous materials have advantages due to their high defects and multiple active sites, but existing technologies have three major bottlenecks: (1) Difficulty in preparing amorphous materials: high energy consumption and uneven particle size during high-temperature quenching, and complex removal steps required by template agent methods. Moreover, it is difficult to achieve "amorphization" and "anion doping" simultaneously, making it impossible to optimize the adsorption of reaction molecules; (2) Poor anchoring of metal clusters: they mostly rely on physical confinement or weak coordination, are prone to aggregation and have low binding stability, resulting in slow electron transfer and long carrier paths, making it difficult to improve the CO2 reduction rate and selectivity; (3) Insufficient pH adaptability: existing catalysts are mostly designed for a single pH. In alkaline conditions, poor hydrophilicity hinders CO2 dissolution, and in acidic conditions, weak corrosion resistance and easy degradation make them unsuitable for CO2 sources with different pH values ​​in industrial scenarios.

[0003] In summary, existing catalysts have bottlenecks in the synergistic optimization of "amorphization-metal anchoring-pH adaptation", and there is an urgent need to develop novel amorphous catalytic materials with simple processes, stable metal bonding, and wide pH adaptation. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention aims to provide an ion-induced doped amorphous material, taking crystalline materials as a starting point and innovatively combining "hydrothermal anion-induced amorphization" and "low-temperature liquid-phase in-situ reduction": a highly active anion-doped amorphous matrix is ​​formed by disrupting the crystal lattice with strongly coordinated anions, while simultaneously reducing metal salts in-situ to zero-valent metal clusters. A unique Ga-O-Ti bridging bond is used to anchor and enhance the CO2 reduction rate. Simultaneously, PO4 is prepared using a hydrothermal method. 3- By doping amorphous materials, which balances hydrophilicity and alkali resistance to adapt to different pH conditions and promotes CO2 dissolution and diffusion under alkaline conditions, this scheme breaks through the limitations of traditional preparation processes, metal anchoring methods and single pH optimization.

[0005] To achieve the above objectives, the present invention employs the following technical solution: An ion-induced doped amorphous material comprises the following raw materials in parts by weight: 0.1-0.2 parts TiO2, 0.35-0.5 parts NaBH4, 0.02-0.04 parts NH4F, 0.01-0.015 parts Ga(NO3)3·9H2O, 0.02 parts (NH4)H2PO4, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0006] The alcohol solution is composed of the following materials in the following mass ratio: water: ethylene glycol = 0.7: 0.3.

[0007] This invention also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid, 0.02-0.04 parts of NH4F and 0.01-0.015 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.1-0.2 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at 20 kHz for 15 min, then stir at 500 r / min for 10 min. Place it in a hydrothermal treatment at 150-180℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Weigh 0.35 to 0.5 parts of NaBH4 and add it to the suspension. Continue stirring at the above speed for 10 min and treat in an ice bath at -5℃ for 2 h. Then let it stand at room temperature for 4-6 h, filter it using a 0.45 μm filter membrane, and dry it at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: Weigh 0.05 parts of PVP and add it to 30 parts of alcohol solution, wherein the alcohol solution is composed of the following mass ratio of materials: water: ethylene glycol = 0.7: 0.3. Stir for 15 minutes at a speed of 500 r / min. Weigh 0.02 parts of (NH4)H2PO4 and add it to the solution. Continue stirring at the above speed for 15 minutes to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 obtained in Step 3 to the phosphate mixture obtained in Step 4, stir at 500 r / min for 15 min, then place it in a hydrothermal treatment at 120-150℃ for 12 h, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it at 65℃ for 24 h to obtain ion-induced doped amorphous material.

[0008] The ion-induced doped amorphous materials prepared by the above methods were applied to the photocatalytic reduction of CO2.

[0009] Compared with the prior art, the present invention has the following beneficial effects: The ion-induced doped amorphous material prepared in this invention takes crystalline TiO2 material as the starting point and is based on the methods of "hydrothermal anion-induced amorphization" and "low-temperature liquid-phase in-situ reduction". By introducing strongly coordinating anions in the hydrothermal reaction, the ordered crystal structure is destroyed, and the crystal form is induced to transform into a highly defective and highly active anion-doped amorphous TiO2 matrix. At the same time, the metal salt cation is reduced in-situ to zero-valent Ga metal clusters by a low-temperature liquid-phase reducing agent, which are then anchored on the surface of the amorphous matrix through Ga-O-Ti bonds. The formation of these bonds can greatly promote the adsorption of reactant molecules, accelerate the electron transfer efficiency, and significantly shorten the carrier transport path, thereby improving the adsorption of reaction intermediates, increasing the overall CO2 reduction rate, and accelerating the formation of products.

[0010] In order to ensure the compatibility of the catalyst under different pH conditions, the ion-induced doped amorphous material prepared in this invention is obtained by hydrothermal treatment to produce PO4. 3- Materials doped with amorphous TiO2 can improve the hydrophilicity and alkali resistance of the matrix, while promoting the dissolution and diffusion of CO2 under alkaline conditions, thereby improving the overall catalytic reaction efficiency. Attached Figure Description

[0011] Figure 1 The figure shows the preparation method of ion-induced doped amorphous materials proposed in this invention; Figure 2 XRD pattern of ion-induced doped amorphous material prepared for the example; Figure 3 The graph shows the CO yield data of ion-induced doped amorphous materials prepared in the examples and comparative examples; Figure 4 The graph shows the CO yield data of the ion-induced doped amorphous material prepared in Example 2 under different pH conditions. Figure 5 The photocurrent test pattern is shown for the ion-induced doped amorphous material prepared in Example 2. Detailed Implementation

[0012] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0014] The preparation method and characterization in the following examples are based on... Figures 1-5 Unless otherwise specified, all methods are conventional. Unless otherwise specified, the materials used in the following examples are all new materials purchased from the market. The alcohol solution is composed of materials in the following mass ratio: water: ethylene glycol = 0.7: 0.3. All materials involving water are deionized water.

[0015] Example 1: This embodiment provides an ion-induced doped amorphous material, comprising the following raw materials in parts by weight: 0.1 parts TiO2, 0.35 parts NaBH4, 0.02 parts NH4F, 0.01 parts Ga(NO3)3·9H2O, 0.02 parts (NH4)H2PO4, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0016] This embodiment also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid, 0.02 parts of NH4F and 0.01 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.1 part of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at a frequency of 20 kHz for 15 min, then stir at a speed of 500 r / min for 10 min. Place it in a hydrothermal treatment at a temperature of 150℃ for 24 h, cool it naturally to room temperature, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it in a forced-air drying oven at a temperature of 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Weigh 0.35 parts of NaBH4 and add it to the suspension. Continue stirring at the above speed for 10 min. Treat in an ice bath at -5℃ for 2 h, then let stand at room temperature for 4 h. Filter using a 0.45 μm filter membrane and dry at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: Weigh 0.05 parts of PVP and add it to 30 parts of alcohol solution. Stir for 15 minutes at a speed of 500 r / min. Weigh 0.02 parts of (NH4)H2PO4 and add it to the solution. Continue stirring at the speed mentioned above for 15 minutes to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 obtained in Step 3 to the phosphate mixture obtained in Step 4, stir at 500 r / min for 15 min, then place it in a hydrothermal treatment at 120℃ for 12 h, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it at 65℃ for 24 h to obtain ion-induced doped amorphous material.

[0017] The ion-induced doped amorphous materials prepared by the above methods were applied to the photocatalytic reduction of CO2.

[0018] Example 2: This embodiment provides an ion-induced doped amorphous material, comprising the following raw materials in parts by weight: 0.15 parts TiO2, 0.43 parts NaBH4, 0.03 parts NH4F, 0.013 parts Ga(NO3)3·9H2O, 0.02 parts (NH4)H2PO4, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0019] This embodiment also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid, 0.03 parts of NH4F and 0.013 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.15 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at a frequency of 20 kHz for 15 min, then stir at a speed of 500 r / min for 10 min. Place it in a hydrothermal treatment at a temperature of 165℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at a temperature of 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Weigh 0.43 parts of NaBH4 and add it to the suspension. Continue stirring at the above speed for 10 min. Treat under ice bath conditions at -5℃ for 2 h, then let stand at room temperature for 5 h. Filter using a 0.45 μm filter membrane and dry at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: Weigh 0.05 parts of PVP and add it to 30 parts of alcohol solution. Stir for 15 minutes at a speed of 500 r / min. Weigh 0.02 parts of (NH4)H2PO4 and add it to the solution. Continue stirring at the speed mentioned above for 15 minutes to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 obtained in Step 3 to the phosphate mixture obtained in Step 4, stir at 500 r / min for 15 min, then place it in a hydrothermal treatment at 135℃ for 12 h, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it at 65℃ for 24 h to obtain ion-induced doped amorphous material.

[0020] Example 3: This embodiment provides an ion-induced doped amorphous material, comprising the following raw materials in parts by weight: 0.2 parts TiO2, 0.5 parts NaBH4, 0.04 parts NH4F, 0.015 parts Ga(NO3)3·9H2O, 0.02 parts (NH4)H2PO4, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0021] This embodiment also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid, 0.04 parts of NH4F and 0.015 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.2 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at a frequency of 20 kHz for 15 min, then stir at a speed of 500 r / min for 10 min. Place it in a hydrothermal treatment at a temperature of 180℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at a temperature of 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Weigh 0.5 parts of NaBH4 and add it to the suspension. Continue stirring at the above speed for 10 min. Treat in an ice bath at -5℃ for 2 h, then let stand at room temperature for 6 h. Filter using a 0.45 μm filter membrane and dry at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: Weigh 0.05 parts of PVP and add it to 30 parts of alcohol solution. Stir for 15 minutes at a speed of 500 r / min. Weigh 0.02 parts of (NH4)H2PO4 and add it to the solution. Continue stirring at the speed mentioned above for 15 minutes to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 obtained in Step 3 to the phosphate mixture obtained in Step 4, stir at 500 r / min for 15 min, then place it in a hydrothermal treatment at 150℃ for 12 h, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it at 65℃ for 24 h to obtain ion-induced doped amorphous material.

[0022] Comparative Example 1: This comparative example provides an ion-induced doped amorphous material comprising the following raw materials in parts by weight: 0.15 parts TiO2, 0.03 parts NH4F, 0.02 parts (NH4)H2PO4, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0023] This comparative example also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid and 0.03 parts of NH4F and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.15 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at a frequency of 20 kHz for 15 min, then stir at a speed of 500 r / min for 10 min. Place it in a hydrothermal treatment at a temperature of 165℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at a temperature of 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol, stir at 500 r / min for 20 min to obtain a suspension, filter it using a 0.45 μm filter membrane, and dry it at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: Weigh 0.05 parts of PVP and add it to 30 parts of alcohol solution. Stir for 15 minutes at a speed of 500 r / min. Weigh 0.02 parts of (NH4)H2PO4 and add it to the solution. Continue stirring at the speed mentioned above for 15 minutes to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 obtained in Step 3 to the phosphate mixture obtained in Step 4, stir at 500 r / min for 15 min, then place it in a hydrothermal treatment at 135℃ for 12 h, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it at 65℃ for 24 h to obtain ion-induced doped amorphous material.

[0024] Comparative Example 2: This comparative example provides an ion-induced doped amorphous material comprising the following raw materials in parts by weight: 0.15 parts TiO2, 0.43 parts NaBH4, 0.013 parts Ga(NO3)3·9H2O, 0.02 parts (NH4)H2PO4, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0025] This comparative example also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid and 0.013 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.15 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at a frequency of 20 kHz for 15 min, then stir at a speed of 500 r / min for 10 min. Place it in a hydrothermal treatment at a temperature of 165℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at a temperature of 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Weigh 0.43 parts of NaBH4 and add it to the suspension. Continue stirring at the above speed for 10 min. Treat under ice bath conditions at -5℃ for 2 h, then let stand at room temperature for 5 h. Filter using a 0.45 μm filter membrane and dry at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: Weigh 0.05 parts of PVP and add it to 30 parts of alcohol solution. Stir for 15 minutes at a speed of 500 r / min. Weigh 0.02 parts of (NH4)H2PO4 and add it to the solution. Continue stirring at the speed mentioned above for 15 minutes to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 obtained in Step 3 to the phosphate mixture obtained in Step 4, stir at 500 r / min for 15 min, then place it in a hydrothermal treatment at 135℃ for 12 h, wash it alternately with deionized water and anhydrous ethanol 3 times each, and dry it at 65℃ for 24 h to obtain ion-induced doped amorphous material.

[0026] Comparative Example 3: This comparative example provides an ion-induced doped amorphous material comprising the following raw materials in parts by weight: 0.15 parts TiO2, 0.43 parts NaBH4, 0.03 parts NH4F, 0.013 parts Ga(NO3)3·9H2O, 0.08 parts citric acid, 0.05 parts PVP, and 30 parts alcohol solution.

[0027] This comparative example also provides a method for preparing ion-induced doped amorphous materials, the steps of which are as follows: Step 1: Weigh 0.08 parts of citric acid, 0.03 parts of NH4F and 0.013 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.15 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at a frequency of 20 kHz for 15 min, then stir at a speed of 500 r / min for 10 min. Place it in a hydrothermal treatment at a temperature of 165℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at a temperature of 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor. Step 3: Add the composite reduction precursor obtained in Step 2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Weigh 0.43 parts of NaBH4 and add it to the suspension. Continue stirring at the above speed for 10 min. Treat under ice bath conditions at -5℃ for 2 h, then let stand at room temperature for 5 h. Filter using a 0.45 μm filter membrane and dry at 65℃ for 24 h to obtain modified amorphous TiO2. Step 4: The modified amorphous TiO2 obtained in Step 3 is placed in a hydrothermal treatment at a temperature of 135℃ for 12 hours, washed alternately with deionized water and anhydrous ethanol 3 times each, and dried at a temperature of 65℃ for 24 hours to obtain ion-induced doped amorphous material.

[0028] Comparative Example 4: This comparative example uses untreated TiO2, and the remaining steps are the same as in Example 2.

[0029] Comparative Example 5: A method for preparing ion-induced doped amorphous materials, comprising the following steps: Step 1: Add 0.15 parts of TiO2 to 20 parts of anhydrous ethanol and stir at 500 r / min for 20 min to obtain a suspension. Filter the suspension using a 0.45 μm filter membrane and dry it at 65℃ for 24 h to obtain modified amorphous TiO2. Step 2: The modified amorphous TiO2 obtained in Step 1 is subjected to hydrothermal treatment at 135℃ for 12 hours, washed alternately with deionized water and anhydrous ethanol 3 times each, and dried at 65℃ for 24 hours to obtain ion-induced doped amorphous material.

[0030] Comparative Example 6: A method for preparing ion-induced doped amorphous materials, comprising the following steps: Step 1: Weigh 0.08 parts of citric acid, 0.03 parts of NH4F and 0.013 parts of Ga(NO3)3·9H2O and add them to 30 parts of deionized water. Stir at 500 r / min for 20 min to obtain an anionized aqueous solution. Step 2: Weigh 0.15 parts of TiO2 and add it to the anionic aqueous solution obtained in Step 1. Sonicate at 20 kHz for 15 min, then stir at 500 r / min for 10 min. Place it in a hydrothermal treatment at 165℃ for 24 h, cool it naturally to room temperature, wash it three times each with deionized water and anhydrous ethanol, and dry it in a forced-air drying oven at 65℃ for 24 h. Collect the powder to obtain the composite reduction precursor.

[0031] The composite reduction precursor prepared by the above method was applied to the photocatalytic reduction of CO2.

[0032] Obviously, the above comparative examples and embodiments are only a part of the comparative examples and embodiments of the present invention, and they, along with the comparative examples and embodiments referenced based on such examples, are all within the scope of protection of this invention.

[0033] Further on such Figure 1 The ion-induced doped amorphous materials prepared by the method shown were subjected to the following tests. Figure 2 The XRD patterns of the amorphous material and TiO2 prepared in Example 2 show that the characteristic peaks corresponding to the 101 crystal plane are clearly present in the original TiO2 spectrum, while the characteristic diffraction peaks of TiO2 in the amorphous material obtained after amorphous treatment disappear significantly, indicating that the amorphous material was successfully prepared. Figure 3 The figures show the CO yield test data of the ion-induced doped amorphous materials prepared in the examples and comparative examples. The catalyst dosage was 30 mg and the deionized water dosage was 100 ml. The tests revealed that the crystallized material exhibited a significantly higher CO yield compared to the amorphized material from the original TiO2. Furthermore, the CO yield of the ion-induced doped amorphous material prepared in Example 2 was tested under different pH conditions, and the results are shown below. Figure 4As shown in the figure, the CO yield is highest at pH 7 (neutral). The CO yield decreases slightly under alkaline and acidic conditions, indicating that the prepared ion-induced doped amorphous material has strong pH adaptability. Furthermore, the photocurrent of the ion-induced doped amorphous material prepared in Example 2 was tested, and the results are as follows... Figure 5 As shown, amorphous materials exhibit higher current intensity, indicating higher electron-hole separation efficiency.

[0034] As can be seen from the above, the ion-induced doped amorphous material prepared in Example 2 has higher photocatalytic activity, pH suitability, and strong charge separation efficiency.

[0035] In summary, this invention provides an ion-induced doped amorphous material, its preparation method, and its applications. Based on crystalline materials, it combines hydrothermal anion-induced amorphization with low-temperature liquid-phase in-situ reduction: strongly coordinated anions break the crystal lattice to form a highly active amorphous matrix, simultaneously reducing Ga to zero-valent clusters, and improving CO2 reduction rate through Ga-O-Ti bonds; hydrothermal production of PO4... 3- By doping with amorphous materials, it is hydrophilic, alkali-resistant, adaptable to multiple pH levels, and helps dissolve alkaline CO2, breaking through traditional limitations.

[0036] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0037] The present invention and its embodiments have been described above. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention. The actual application is not limited to this. In conclusion, if those skilled in the art are inspired by this description and design similar methods and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. An ion-induced doped amorphous material, characterized in that, The preparation raw materials include the following parts by weight: TiO2 0.1-0.2 parts, NaBH4 0.35-0.5 parts, NH4F 0.02-0.04 parts, Ga(NO3)3·9H2O 0.01-0.015 parts, (NH4)H2PO4 0.02 parts, citric acid 0.08 parts, PVP 0.05 parts, and alcohol solution 30 parts; the alcohol solution is composed of materials in the following mass ratio: water: ethylene glycol = 0.7: 0.

3.

2. A method for preparing an ion-induced doped amorphous material as described in claim 1, characterized in that, The steps are as follows: Step 1: Add citric acid, NH4F and Ga(NO3)3·9H2O to water and stir to obtain an anionic aqueous solution; Step 2: Add TiO2 to an anionic aqueous solution, sonicate, stir, hydrothermally heat, wash, and dry to obtain the composite reduction precursor; Step 3: Add the composite reduction precursor to ethanol, stir to obtain a suspension, add NaBH4, stir, place in an ice bath, let stand, filter, and dry to obtain modified amorphous TiO2. Step 4: Add PVP to the alcohol solution and stir. Then add (NH4)H2PO4 and stir to obtain a phosphate mixture. Step 5: Add the modified amorphous TiO2 to the phosphate mixture, stir, hydrothermally heat, wash, and dry to obtain ion-induced doped amorphous material.

3. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step one, the weight ratio of citric acid, NH4F, Ga(NO3)3·9H2O and water is 0.08:0.02~0.04:0.01~0.015:

30.

4. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step one, the stirring speed is 500 r / min and the stirring time is 20 min.

5. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step two, the frequency of the ultrasound is 20 kHz and the duration is 15 minutes.

6. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step two, the hydrothermal temperature is 150-180℃ and the time is 24 hours.

7. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step three, the temperature of the ice bath is -5℃ and the time is 2 hours.

8. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step three, the settling time is 4-6 hours; the filtration uses a 0.45μm filter membrane.

9. The method for preparing ion-induced doped amorphous materials according to claim 2, characterized in that, In step five, the hydrothermal temperature is 120-150℃, and the time is 12 hours.

10. An ion-induced doped amorphous material as described in claim 1, applied to the photocatalytic reduction of CO2.

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