MOF-derived ZrO2 surface-loaded nickel composite material and preparation method and application thereof
In the preparation method of the MOF-derived ZrO2 surface-supported composite material, the hydrothermal method and high-temperature calcination step are used to solve the problem of insufficient activity and selectivity of catalytic materials in the prior art, and the efficient thermal catalytic hydrogenation of carbon dioxide is achieved, thereby improving the purity and catalytic stability of the product.
Patent Information
- Application Number
- CN202411478687.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-22
- Publication Date
- 2025-05-02
AI Technical Summary
In the prior art, in the thermally catalytic carbon dioxide hydrogenation to formate reaction, the activity and selectivity of the catalytic material are insufficient, resulting in low product purity and high by-product generation.
By using MOF-derived ZrO2 surface-loaded nickel composite material, Zr-MOF-loaded nickel nanomaterial was prepared by hydrothermal method and calcined at high temperature under an inert gas atmosphere to obtain a MOF-derived ZrO2 surface-loaded nickel composite material with high active surface area and good thermal stability.
The performance of thermally catalyzed carbon dioxide hydrogenation to make formate is significantly improved, including improving catalytic activity and product selectivity, greatly enhancing the purity and catalytic stability of the product.
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Figure CN119909682A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of nanocomposite materials, and in particular to a MOF-derived ZrO2 surface-loaded nickel composite material and a preparation method and application thereof. Background Art
[0002] Energy is an important guarantee for promoting social development and scientific and technological progress. With the development of economy and rapid industrialization, people are facing increasingly serious energy shortage problems. Thermal catalytic carbon dioxide hydrogenation to produce high value-added liquid fuel has great potential in solving the problem of sustainable energy development. At present, the thermal catalytic CO2 hydrogenation to formate reaction is still mainly focused on the development of catalytic materials and the exploration of reaction mechanism. Therefore, the design of highly active catalytic materials has become the focus of people's attention.
[0003] Metal organic frameworks (MOFs) stand out for their unique semiconductor properties, porous structure, high specific surface area and extremely high carbon dioxide storage capacity. When MOFs are derived into oxides, these properties are usually retained, giving the carrier a larger active surface area, which can effectively disperse the active components of the catalyst, prevent their agglomeration and deactivation, and thus improve the catalytic activity. Therefore, in recent years, they have been widely used in the development of carbon dioxide adsorption and conversion. In addition, since MOF-derived oxides support metals with good thermal stability, catalytic performance and gas adsorption properties, their application in carbon dioxide hydrogenation catalytic reactions has also been widely studied.
[0004] Among the loaded metal nanoparticles, transition metal Ni is selected as the active metal. On the one hand, the raw materials of nickel-based catalysts are widely available and the cost is relatively low. Compared with precious metal catalysts (such as palladium, rhodium, etc.), nickel-based catalysts have obvious advantages in price, which makes them more competitive in large-scale industrial applications. In addition, nickel-based catalysts show excellent catalytic activity in CO2 hydrogenation reactions. This is mainly due to the effective adsorption and activation of reactants by nickel metal, which promotes the catalytic reaction. And the target product can be selectively generated. This selectivity is of great significance for improving the purity of the product and reducing the generation of by-products. Summary of the invention
[0005] In order to solve the above technical problems, the present invention provides a MOF-derived ZrO2 surface-loaded nickel composite material and its preparation method and application. The present invention uses zirconium chloride and 2-aminoterephthalic acid as precursors, N,N-dimethylformamide, formic acid and acetic acid as solvents, and obtains Zr-MOF-loaded nickel nanomaterials through a simple hydrothermal method, wherein nickel nitrate is used as a nickel source, and acetic acid is used to adjust the solution pH to make it weakly acidic. Finally, a MOF-derived ZrO2 surface-loaded nickel composite material is prepared by high-temperature calcination under the protection of an inert gas atmosphere. After modification, the adsorption of CO2 and the high selectivity of the product are promoted, and the performance of thermal catalytic CO2 hydrogenation to produce formate is greatly improved.
[0006] The first object of the present invention is to provide a MOF-derived ZrO2 surface-loaded nickel composite material, wherein the composite material is ZrO2 with an octahedral structure, and the surface of the composite material is in situ modified with nickel, and is used for efficient CO2 hydrogenation to produce formate.
[0007] In some embodiments of the present invention, the nickel loading is 0.1 wt% to 0.4 wt%, specifically, 0.1 wt% to 0.2 wt%, 0.2 wt% to 0.4 wt%, 0.2 wt% to 0.3 wt%, 0.1 wt% to 0.3 wt%, etc., or illustratively, an interval value between any two values of 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%.
[0008] The second object of the present invention is to provide a method for preparing the MOF-derived ZrO2 surface-loaded nickel composite material, comprising the following steps:
[0009] S1: adding a zirconium source, 2-aminoterephthalic acid and a nickel source into an acidic organic mixed solvent, mixing them evenly and then heating them to obtain a Zr-MOF loaded nickel nanomaterial;
[0010] S2: calcining the Zr-MOF loaded nickel nanomaterial obtained in step S1 at a high temperature under an inert gas atmosphere to obtain the MOF-derived ZrO2 surface loaded nickel composite material.
[0011] In some embodiments of the present invention, in step S1, the zirconium source is selected from zirconium chloride and / or zirconium nitrate.
[0012] In some embodiments of the present invention, in step S1, the nickel source is selected from nickel nitrate and / or nickel chloride.
[0013] In some embodiments of the present invention, in step S1, the acidic organic mixed solvent includes N,N-dimethylformamide, formic acid and acetic acid; the volume ratio of N,N-dimethylformamide, formic acid and acetic acid is: 10-50:1-10:1-10.
[0014] In some embodiments of the present invention, in step S1, the molar mass ratio of the zirconium source, 2-aminoterephthalic acid and the nickel source is 2-3:3-4:2-4.
[0015] In some embodiments of the present invention, in step S1, the heating temperature is 100-150° C., and the heating time is 15-48 hours.
[0016] In some embodiments of the present invention, in step S2, the inert gas in the inert gas atmosphere is selected from nitrogen and / or argon;
[0017] The high temperature calcination temperature is 500-550°C and the time is 3-5h;
[0018] The heating rate of high temperature calcination is 2 to 10°C / min.
[0019] In some embodiments of the present invention, the method further comprises cleaning the MOF-derived ZrO2 surface-loaded nickel composite material, and the cleaning agent is selected from water and ethanol.
[0020] The third object of the present invention is to provide the use of the MOF-derived ZrO2 surface-loaded nickel composite material in thermal catalytic carbon dioxide reduction.
[0021] The above technical solution of the present invention has the following advantages compared with the prior art:
[0022] 1. The raw materials used in the preparation method of the composite material loaded with nickel on the surface of MOF-derived ZrO2 disclosed in the present invention are low in cost and easy to obtain, and the experimental operation is simple. No expensive equipment is used in the whole process, which is conducive to industrial production.
[0023] 2. The composite material of nickel loaded on the surface of MOF-derived ZrO2 disclosed in the present invention is a new composite material with controllable structure, excellent performance and good thermal stability. It has excellent performance in thermal catalytic carbon dioxide hydrogenation reduction and is conducive to industrial application. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:
[0025] Figure 1 This is a transmission electron microscopy (TEM) image of the MOF-derived ZrO2 surface-loaded nickel composite material obtained in Example 1;
[0026] Figure 2 This is a scanning electron microscope image (SEM) of the MOF-derived ZrO2 surface-loaded nickel composite material obtained in Example 1;
[0027] Figure 3 This is a diagram showing the effect of the MOF-derived ZrO2 surface-loaded nickel composite material obtained in Example 1 and the MOF-derived pure ZrO2 obtained in Comparative Example 1 under thermal catalytic carbon dioxide hydrogenation reduction to produce formate. DETAILED DESCRIPTION
[0028] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.
[0029] Embodiment 1
[0030] This embodiment provides a preparation of a MOF-derived ZrO2 surface-loaded nickel (Ni / ZrO2) composite material, and the specific steps are as follows:
[0031] (1) 93.2 mg of zirconium chloride, 108.7 mg of 2-aminoterephthalic acid, and 0.1, 0.2, 0.3, and 0.4 mmol of nickel nitrate hexahydrate were added to a mixed solution of 50 mL of N,N-dimethylformamide, 5 mL of formic acid and acetic acid (1 / 1 v / v), and the mixture was vigorously stirred at room temperature. After stirring evenly, the mixture was transferred to a high-pressure reactor and heated at 130° C. for 24 hours. The obtained product was washed with ethanol and distilled water, and then dried in a drying oven to obtain Zr-MOF-supported nickel nanomaterials;
[0032] (2) The Zr-MOF-loaded nickel nanomaterial obtained in step (1) was heated to 500°C at 2°C / min in an inert gas atmosphere for high temperature calcination for 3 hours, and finally a MOF-derived ZrO2 surface-loaded nickel composite material with nickel loadings of 0.1wt%, 0.2wt%, 0.3wt%, and 0.4wt% was obtained. The optimal ratio of the MOF-derived ZrO2 surface-loaded nickel composite material was 0.2wt%. The specific morphology was measured by TEM ( Figure 1 ) and SEM( Figure 2 ), from which we can see that the octahedral structure was successfully prepared and has uniform size.
[0033] Comparative Example 1
[0034] This comparative example provides a preparation of pure ZrO2 derived from MOF, and the specific steps are as follows:
[0035] (1) 33.4 mg of zirconium chloride and 27.3 mg of 2-aminoterephthalic acid were added to 40 mL of N,N-dimethylformamide and a mixed solution of 4 mL of formic acid and acetic acid, and the mixture was vigorously stirred at room temperature. After stirring evenly, the mixture was transferred to a high-pressure reactor and heated at 130° C. for 24 hours. The obtained product was washed with ethanol and distilled water, and then dried in a drying oven to obtain a Zr-MOF nanomaterial;
[0036] (2) The Zr-MOF nanomaterial is calcined at 500°C for 3 h in a nitrogen atmosphere to obtain MOF-derived pure ZrO2.
[0037] Performance Testing
[0038] The performance of the MOF-derived ZrO2 surface-loaded nickel composite material for thermal catalytic carbon dioxide reduction obtained in Example 1 and Comparative Example 1 was tested under heating conditions, and the specific steps were as follows:
[0039] 5 mg of the MOF-derived ZrO2 surface-loaded nickel (Ni / ZrO2) composite catalyst obtained in Example 1 was dispersed in 5 ml of ultrapure water saturated with sodium bicarbonate, and then transferred to a magnetic heating stirrer and sealed by ultrasonic dispersion. The air in the system was then removed by nitrogen. After completion, a carbon dioxide / hydrogen (1 / 1 v / v) mixed gas of 1 MPa, 2 MPa, and 3 MPa was injected into the reactor, heated to 50°C, 100°C, and 150°C for one hour, and the yield of formate was obtained by ion chromatography and analysis based on standard samples. The results are shown in FIG. Figure 3 . Figure 3 The performance diagram of the MOF-derived ZrO2 surface-loaded nickel (Ni / ZrO2) composite material for thermal catalytic carbon dioxide reduction is shown in Example 1. Figure 3 It can be seen that the MOF-derived ZrO2 surface-loaded nickel (Ni / ZrO2) composite material has excellent thermal catalytic carbon dioxide reduction performance, among which the optimal catalyst can produce formate efficiency of 388.41mmol formate mol Ni -1 h -1 The composite material not only has excellent performance and good stability, but also has a simple preparation process, low raw material price, and is easy to industrialize.
[0040] Embodiment 2
[0041] This embodiment provides a preparation of a MOF-derived ZrO2 surface-loaded nickel composite material, and the specific steps are as follows:
[0042] (1) 33.4 mg of zirconium chloride, 27.3 mg of 2-aminoterephthalic acid, and 0.1-0.8 mmol of nickel nitrate hexahydrate were added to a mixed solution of 10 mL of N,N-dimethylformamide and 2 mL of formic acid and acetic acid, and stirred vigorously at room temperature. After stirring evenly, the mixture was transferred to a high-pressure reactor and heated at 130° C. for 24 hours. The obtained product was washed with ethanol and distilled water, and then dried in a drying oven to obtain Zr-MOF-supported nickel nanomaterials;
[0043] (2) The Zr-MOF loaded nickel nanomaterial is calcined at 500° C. for 3 h in an inert gas atmosphere to obtain a MOF-derived ZrO2 surface loaded nickel composite material.
[0044] Embodiment 3
[0045] This embodiment provides a preparation of a MOF-derived ZrO2 surface-loaded nickel composite material, and the specific steps are as follows:
[0046] (1) 300 mg of zirconium chloride, 235 mg of 2-aminoterephthalic acid, and 0.1, 0.2, 0.3, and 0.4 mmol of nickel nitrate hexahydrate were added to 30 mL of N,N-dimethylformamide and 2 mL of a mixed solution of formic acid and acetic acid (1 / 1 v / v), and the mixture was vigorously stirred at room temperature. After stirring evenly, the mixture was transferred to a high-pressure reactor and heated at 130° C. for 24 hours. The obtained product was washed with ethanol and distilled water, and then dried in a drying oven to obtain Zr-MOF-supported nickel nanomaterials;
[0047] (2) The Zr-MOF loaded nickel nanomaterial obtained in step (1) is calcined at 500° C. for 3 h in a nitrogen atmosphere to obtain a MOF-derived ZrO2 surface loaded nickel composite material.
[0048] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.
Claims
1. A MOF-derived ZrO2 surface-loaded nickel composite material, characterized in that: The composite material uses MOF material as a template, the composite material is ZrO2 with an octahedral structure, and nickel element is in-situ modified on the surface of the composite material.
2. The MOF-derived ZrO2 surface-loaded nickel composite material according to claim 1, characterized in that: The nickel loading is 0.1 wt% to 0.4 wt%.
3. The method for preparing a composite material of MOF-derived ZrO2 surface loaded with nickel according to claim 1 or 2, characterized in that: The following steps are involved: S1: adding a zirconium source, 2-aminoterephthalic acid and a nickel source into an acidic organic mixed solvent, mixing them evenly and then heating them to obtain a Zr-MOF loaded nickel nanomaterial; S2: calcining the Zr-MOF loaded nickel nanomaterial obtained in step S1 at a high temperature under an inert gas atmosphere to obtain the MOF-derived ZrO2 surface loaded nickel composite material.
4. The preparation method according to claim 1, characterized in that: In step S1, the zirconium source is selected from zirconium chloride and / or zirconium nitrate.
5. The preparation method according to claim 1, characterized in that: In step S1, the nickel source is selected from nickel nitrate and / or nickel chloride.
6. The preparation method according to claim 1, characterized in that: In step S1, the acidic organic mixed solvent includes N,N-dimethylformamide, formic acid and acetic acid; the volume ratio of the N,N-dimethylformamide, formic acid and acetic acid is: 10-50: 1-10: 1-10.
7. The preparation method according to claim 1, characterized in that: In step S1, the molar mass ratio of the zirconium source, 2-aminoterephthalic acid and the nickel source is 2-3:3-4:2-4.
8. The preparation method according to claim 1, characterized in that: In step S1, the heating temperature is 100-150° C., and the heating time is 15-48 hours.
9. The preparation method according to claim 1, characterized in that: In step S2, the inert gas in the inert gas atmosphere is selected from nitrogen and / or argon; The high temperature calcination temperature is 500-550°C and the time is 3-5h; The heating rate of high temperature calcination is 2-10°C / min.
10. Use of the MOF-derived ZrO2 surface-loaded nickel composite material according to claim 1 or 2 in thermal catalytic carbon dioxide reduction.