High-efficiency nickel-containing nanocatalyst, preparation method and application thereof

Abstract

The application relates to the technical field of rare earth catalysts, in particular to a high-efficiency nickel-containing nanometer catalyst and a preparation method and application thereof. The preparation method of the high-efficiency nickel-containing nanometer catalyst comprises the following steps: a pre-prepared carrier is obtained by coordination of tetraethyl orthosilicate and carboxyl-terminated polyamide amine; nickel nitrate and yttrium nitrate are added into anhydrous ethanol and stirred uniformly, the pre-prepared carrier is added into the mixture and ultrasonically treated, the pH value of the system is adjusted and stirred, centrifugation, washing, vacuum drying and crushing are carried out to obtain pre-prepared materials; the pre-prepared materials are calcined at 450-500 DEG C, naturally reduced to room temperature, and reduced by introducing a reducing gas in a tube furnace and reduced to room temperature. The application has high-dispersed nickel active sites and a carrier microenvironment, the stable carrier structure endows the catalyst with outstanding anti-sintering and anti-carbon deposition capacity, guarantees the durability of long-term operation, has an excellent application prospect, and is suitable for large-scale popularization and application.

Description

Technical Field

[0001] This invention relates to the field of rare earth catalyst technology, and in particular to a highly efficient nickel-containing nanocatalyst, its preparation method, and its application. Background Technology

[0002] As a major greenhouse gas, carbon dioxide's excessive emissions have led to global warming, a serious environmental challenge. Achieving efficient catalytic conversion of carbon dioxide can not only alleviate environmental pressures but also generate economically valuable chemicals such as carbon monoxide, making it of significant strategic importance.

[0003] Currently, copper-zinc-aluminum catalysts prepared by traditional co-precipitation methods generally suffer from poor dispersion of active components and large particle size, resulting in low carbon dioxide conversion rates. While nickel-based catalysts are widely used due to their abundant reserves, low cost, and good catalytic performance, their practical applications still face bottlenecks such as easy aggregation of active sites and weak synergistic effects between the support and active components. Silica, as a commonly used support, possesses a high specific surface area and well-developed pore structure, which facilitates the dispersion of active components. However, its chemical inertness limits its synergistic catalytic effect with metal active components, making it difficult for the catalyst to maintain stable function during the reaction. Furthermore, existing catalysts lack selectivity for the target product carbon monoxide and exhibit poor stability during continuous operation, making it difficult to meet the requirements of long-term industrial applications.

[0004] Currently, the development of a nickel-based catalyst that combines high dispersibility, high selectivity, and high stability holds great promise for research. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by proposing a highly efficient nickel-containing nanocatalyst, its preparation method, and its application.

[0006] A method for preparing a highly efficient nickel-containing nanocatalyst includes the following steps: S1. Add tetraethyl orthosilicate to hydrochloric acid and stir at 50-60℃ for 1-2 hours. Add carboxyl-terminated polyamide amine and continue stirring for 2-4 hours. Use a cold source at the bottom to directionally cool down to -30 to -50℃. Let stand for 5-10 hours, wash, freeze dry, vacuum dry, and pulverize to obtain the pre-made carrier. S2. Add nickel nitrate and yttrium nitrate to anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 10-30 min. Adjust the pH of the system to 7.5-8.5. Stir at 70-90℃ for 1-2 h. Centrifuge, wash, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 450-500℃ for 1-2 hours, then naturally cooled to room temperature. A reducing gas is introduced into a tube furnace, and the preform is reduced at 520-580℃ for 1-3 hours, then cooled to room temperature.

[0007] Preferably, the weight ratio of tetraethyl orthosilicate, carboxyl-terminated polyamide amine, nickel nitrate, and yttrium nitrate is 5-10:1-2:5-15:1-3.

[0008] More preferably, the generation of the carboxyl-terminated polyamide amine is 2.0-4.0 generations.

[0009] Preferably, in S1, the concentration of hydrochloric acid is 0.1-0.2 mol / L.

[0010] Preferably, in S1, the cooling rate of directional cooling is 1-5℃ / min.

[0011] Preferably, in S2, the ultrasonic frequency is 60-85kHz.

[0012] Preferably, in S2, the pH value of the system is adjusted to 7.5-8.5 using ammonia water with a mass fraction of 10-12%.

[0013] Preferably, in S3, the reducing gas includes hydrogen and argon, and the volume ratio of hydrogen to argon is 10-20:100.

[0014] Preferably, in S3, the heating rate during the process of raising the temperature to 520-580℃ is 1-5℃ / min.

[0015] The application of the above-mentioned highly efficient nickel-containing nanocatalyst in the catalytic hydrogenation of carbon dioxide to produce carbon monoxide.

[0016] Preferably, the carbon dioxide conversion rate is 15-16.93%.

[0017] Preferably, the carbon monoxide selectivity is 95-97.89%.

[0018] Compared with existing technologies, the present invention has the following advantages: This invention uses tetraethyl orthosilicate and carboxyl-terminated polyamide amine to form a sol structure, which effectively inhibits particle aggregation. Furthermore, by combining it with a directional cooling crystallization method, it effectively induces the formation of a highly oriented porous channel structure, which significantly improves the mechanical strength and pore order of the carrier.

[0019] This invention uses a pre-fabricated carrier as a template to load and fix nickel and yttrium. Combined with a mild deposition process controlled by ultrasonic dispersion and ammonia, it can effectively achieve high dispersion and strong adhesion of nickel nanoparticles. During the calcination process, the pyrolytic carbon of dendritic polyamide amine is doped into the silica framework. Combined with the highly oriented porous structure, it can not only improve the diffusion path of reactants, but also activate the active center of nickel with the synergistic effect of rare earth yttrium, thus greatly improving the catalytic effect.

[0020] This invention combines highly dispersed nickel active sites with a support microenvironment, exhibiting excellent intrinsic activity and selectivity in the catalytic conversion of carbon dioxide to carbon monoxide. Its stable support structure endows the catalyst with outstanding anti-sintering and anti-carbon deposition capabilities, ensuring long-term operational durability. Combined with a simple and controllable preparation process and a low-cost raw material system, it has excellent application prospects and is suitable for large-scale promotion and application. Attached Figure Description

[0021] Figure 1 The graph shows a comparison of the carbon dioxide conversion rates of the nanocatalysts obtained in Example 5 and Comparative Examples 1-3 after 6 hours of operation.

[0022] Figure 2 The graph shows a comparison of the carbon monoxide selectivity and carbon monoxide generation rate of the nanocatalysts obtained in Example 5 and Comparative Examples 1-3 after running for 6 hours.

[0023] Figure 3 The graph shows a comparison of the retention rates of carbon dioxide conversion and carbon monoxide generation after 200 hours of operation of the nanocatalysts obtained in Example 5 and Comparative Examples 1-3. Detailed Implementation

[0024] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0025] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0026] The carboxyl-terminated polyamide amine (PAMAM-COOH, G3.0) used below was purchased from Weihai Chenyuan Molecular New Materials Co., Ltd.

[0027] Example 1 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 5g of tetraethyl orthosilicate, 1g of carboxyl-terminated polyamide amine, 5g of nickel nitrate, and 1g of yttrium nitrate.

[0028] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 50g of 0.1mol / L hydrochloric acid and stirred at 50℃ for 1h. Carboxyl-terminated polyamide amine was added and stirring was continued for 2h. The bottom was used as a cold source, and the temperature was directionally reduced from room temperature to -30℃ at a rate of 1℃ / min. The mixture was allowed to stand for 5h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate and yttrium nitrate to 50g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 10min at a frequency of 60kHz. Adjust the pH of the system to 7.5-8.5 with 10% ammonia water. Stir at 70℃ for 1h at a stirring speed of 400r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 450℃ for 1 hour and then allowed to cool naturally to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 10:100 (50 mL / min) is introduced into a tube furnace and the temperature is increased from room temperature to 520℃ at a rate of 1℃ / min for 1 hour, and then cooled to room temperature.

[0029] Example 2 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 10g of tetraethyl orthosilicate, 2g of carboxyl-terminated polyamide amine, 15g of nickel nitrate, and 3g of yttrium nitrate.

[0030] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 100g of 0.2mol / L hydrochloric acid and stirred at 60℃ for 2h. Carboxyl-terminated polyamide amine was added and stirring was continued for 4h. The bottom was used as a cold source, and the temperature was directionally reduced from room temperature to -50℃ at a rate of 5℃ / min. The mixture was allowed to stand for 10h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate and yttrium nitrate to 150g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 30min at a frequency of 85kHz. Adjust the pH of the system to 7.5-8.5 with 12% ammonia water. Stir at 90℃ for 2h at a stirring speed of 500r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 500℃ for 2 hours and then allowed to cool naturally to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 20:100 (150 mL / min) is introduced into a tube furnace and the temperature is increased from room temperature to 580℃ at a rate of 5℃ / min for 3 hours. The temperature is then allowed to cool to room temperature.

[0031] Example 3 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 7g of tetraethyl orthosilicate, 1.8g of carboxyl-terminated polyamide amine, 8g of nickel nitrate, and 2.5g of yttrium nitrate.

[0032] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 70g of 0.18mol / L hydrochloric acid and stirred at 52℃ for 100min. Carboxyl-terminated polyamide amine was added and stirring was continued for 2.5h. The bottom was used as a cold source, and the temperature was directionally reduced from room temperature to -35℃ at a rate of 4℃ / min. The mixture was allowed to stand for 9h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate and yttrium nitrate to 80g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 25min at a frequency of 65kHz. Adjust the pH of the system to 7.5-8.5 with 11% ammonia water. Stir at 85℃ for 80min at a stirring speed of 480r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 470℃ for 100 min, then naturally cooled to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 12:100 (120 mL / min) is introduced into a tube furnace, and the temperature is increased from room temperature to 560℃ at a rate of 2℃ / min for 1.5 h, then cooled to room temperature.

[0033] Example 4 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 9g of tetraethyl orthosilicate, 1.2g of carboxyl-terminated polyamide amine, 12g of nickel nitrate, and 1.5g of yttrium nitrate.

[0034] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 90g of 0.12mol / L hydrochloric acid and stirred at 58℃ for 80min. Carboxyl-terminated polyamide amine was added and stirring was continued for 3.5h. The bottom was used as a cold source, and the temperature was directionally reduced from room temperature to -45℃ at a rate of 2℃ / min. The mixture was allowed to stand for 7h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate and yttrium nitrate to 120g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 15min at a frequency of 80kHz. Adjust the pH of the system to 7.5-8.5 with 11% ammonia water. Stir at 75℃ for 100min at a stirring speed of 420r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 490℃ for 80 minutes, then naturally cooled to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 18:100 (80 mL / min) is introduced into a tube furnace, and the temperature is increased from room temperature to 540℃ at a rate of 4℃ / min for 2.5 hours to reduce the temperature, and then cooled to room temperature.

[0035] Example 5 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 8g of tetraethyl orthosilicate, 1.5g of carboxyl-terminated polyamide amine, 10g of nickel nitrate, and 2g of yttrium nitrate.

[0036] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 80g of 0.15mol / L hydrochloric acid and stirred at 55℃ for 90min. Carboxyl-terminated polyamide amine was added and stirring was continued for 3h. The bottom was used as a cold source, and the temperature was directionally reduced from room temperature to -40℃ at a rate of 3℃ / min. The mixture was allowed to stand for 8h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate and yttrium nitrate to 100g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 20min at a frequency of 75kHz. Adjust the pH of the system to 7.5-8.5 with 11% ammonia water. Stir at 80℃ for 90min at a stirring speed of 450r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 480℃ for 90 minutes and then allowed to cool naturally to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 15:100 (100 mL / min) is introduced into a tube furnace and the temperature is increased from room temperature to 550℃ at a rate of 3℃ / min for 2 hours to reduce the temperature. The temperature is then allowed to cool to room temperature.

[0037] Comparative Example 1 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 8g of tetraethyl orthosilicate, 1.5g of carboxyl-terminated polyamide amine, and 12g of nickel nitrate.

[0038] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 80g of 0.15mol / L hydrochloric acid and stirred at 55℃ for 90min. Carboxyl-terminated polyamide amine was added and stirring was continued for 3h. The bottom was used as a cold source, and the temperature was directionally reduced from room temperature to -40℃ at a rate of 3℃ / min. The mixture was allowed to stand for 8h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate to 100g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 20min at a frequency of 75kHz. Adjust the pH of the system to 7.5-8.5 with 11% ammonia water. Stir at 80℃ for 90min at a stirring speed of 450r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 480℃ for 90 minutes and then allowed to cool naturally to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 15:100 (100 mL / min) is introduced into a tube furnace and the temperature is increased from room temperature to 550℃ at a rate of 3℃ / min for 2 hours to reduce the temperature. The temperature is then allowed to cool to room temperature.

[0039] Comparative Example 2 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 9.5g of tetraethyl orthosilicate, 10g of nickel nitrate, and 2g of yttrium nitrate.

[0040] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Tetraethyl orthosilicate was added to 80g of 0.15mol / L hydrochloric acid and stirred at 55℃ for 90min. The bottom was used as a cold source, and the temperature was directionally cooled from room temperature to -40℃ at a rate of 3℃ / min. The mixture was allowed to stand for 8h, washed with deionized water, freeze-dried, vacuum-dried, and pulverized to obtain the pre-prepared carrier. S2. Add nickel nitrate and yttrium nitrate to 100g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 20min at a frequency of 75kHz. Adjust the pH of the system to 7.5-8.5 with 11% ammonia water. Stir at 80℃ for 90min at a stirring speed of 450r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 480℃ for 90 minutes and then allowed to cool naturally to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 15:100 (100 mL / min) is introduced into a tube furnace and the temperature is increased from room temperature to 550℃ at a rate of 3℃ / min for 2 hours to reduce the temperature. The temperature is then allowed to cool to room temperature.

[0041] Comparative Example 3 A highly efficient nickel-containing nanocatalyst, the raw materials of which include: 8g of tetraethyl orthosilicate, 1.5g of carboxyl-terminated polyamide amine, 10g of nickel nitrate, and 2g of yttrium nitrate.

[0042] The preparation method of the above-mentioned highly efficient nickel-containing nanocatalyst includes the following steps: S1. Add tetraethyl orthosilicate to 80g of 0.15mol / L hydrochloric acid, stir at 55℃ for 90min, add carboxyl-terminated polyamide amine and continue stirring for 3h, set up a cold source around the perimeter, cool from room temperature to -40℃ at a rate of 3℃ / min, let stand for 8h, wash with deionized water, freeze dry, vacuum dry, and pulverize to obtain the pre-prepared carrier; S2. Add nickel nitrate and yttrium nitrate to 100g of anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 20min at a frequency of 75kHz. Adjust the pH of the system to 7.5-8.5 with 11% ammonia water. Stir at 80℃ for 90min at a stirring speed of 450r / min. Centrifuge, wash with deionized water and ethanol, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 480℃ for 90 minutes and then allowed to cool naturally to room temperature. A reducing gas composed of hydrogen and argon in a volume ratio of 15:100 (100 mL / min) is introduced into a tube furnace and the temperature is increased from room temperature to 550℃ at a rate of 3℃ / min for 2 hours to reduce the temperature. The temperature is then allowed to cool to room temperature.

[0043] 100 mg of the nanocatalysts described in Example 5 and Comparative Examples 1-3 were packed into a fixed-bed reactor. First, a 5 vol% H₂ / Ar gas was introduced at a flow rate of 150 mL / min, and the reactor was pre-run at 350 °C for 100 min. Then, a mixed gas of CO₂ at a flow rate of 45 mL / min and a 5 vol% H₂ / Ar gas at a flow rate of 215 mL / min was introduced, and the reactor was run at 300 °C for 6 h. The products were analyzed online using gas chromatography, and the content of each component in the exhaust gas was quantitatively analyzed using the internal standard method.

[0044] like Figure 1 and Figure 2 As shown, Example 5 exhibits the highest carbon dioxide conversion rate, carbon monoxide selectivity, and carbon monoxide generation rate, significantly outperforming the comparative example.

[0045] The fixed-bed reactor was continued to operate for another 194 hours (total operating time was 200 hours). The carbon dioxide conversion rate and carbon monoxide generation rate were calculated again, and the carbon dioxide conversion rate retention rate and carbon monoxide generation rate retention rate were further calculated.

[0046] Carbon dioxide conversion retention rate = Carbon dioxide conversion rate after 200 hours of operation ÷ Carbon dioxide conversion rate after 6 hours of operation × 100%.

[0047] Carbon monoxide formation rate retention rate = carbon monoxide formation rate after 200 hours of operation ÷ carbon monoxide formation rate after 6 hours of operation × 100%.

[0048] like Figure 3 As shown, Example 5 exhibits the highest retention rates for both carbon dioxide conversion and carbon monoxide generation, significantly outperforming the comparative example.

[0049] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. A method for preparing a highly efficient nickel-containing nanocatalyst, characterized in that, Includes the following steps: S1. Add tetraethyl orthosilicate to hydrochloric acid and stir at 50-60℃ for 1-2 hours. Add carboxyl-terminated polyamide amine and continue stirring for 2-4 hours. Use a cold source at the bottom to directionally cool down to -30 to -50℃. Let stand for 5-10 hours, wash, freeze dry, vacuum dry, and pulverize to obtain the pre-made carrier. S2. Add nickel nitrate and yttrium nitrate to anhydrous ethanol and stir evenly. Add the pre-made carrier and sonicate for 10-30 min. Adjust the pH of the system to 7.5-8.

5. Stir at 70-90℃ for 1-2 h. Centrifuge, wash, vacuum dry, and pulverize to obtain the pre-made material. S3. Under nitrogen protection, the preform is calcined at 450-500℃ for 1-2 hours, then naturally cooled to room temperature. A reducing gas is introduced into a tube furnace, and the preform is reduced at 520-580℃ for 1-3 hours, then cooled to room temperature.

2. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, The weight ratio of tetraethyl orthosilicate, carboxyl-terminated polyamide amine, nickel nitrate, and yttrium nitrate is 5-10:1-2:5-15:1-3.

3. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, The generation of carboxyl-terminated polyamide amines is 2.0-4.

0.

4. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, In S1, the concentration of hydrochloric acid is 0.1-0.2 mol / L.

5. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, In S1, the cooling rate of directional cooling is 1-5℃ / min.

6. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, In S2, the ultrasonic frequency is 60-85kHz.

7. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, In S2, the pH of the system is adjusted to 7.5-8.5 using ammonia water with a mass fraction of 10-12%.

8. The method for preparing the high-efficiency nickel-containing nanocatalyst according to claim 1, characterized in that, In S3, the reducing gases include hydrogen and argon, with a volume ratio of 10-20:

100.

9. A highly efficient nickel-containing nanocatalyst, characterized in that, It is prepared using the method described in any one of claims 1-8 for the preparation of highly efficient nickel-containing nanocatalysts.

10. The application of the highly efficient nickel-containing nanocatalyst as described in claim 9 in the catalytic hydrogenation of carbon dioxide to produce carbon monoxide.

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