Preparation and application of a MOF derived catalyst for hydrogenation of carbon dioxide to methanol

Abstract

The present disclosure relates to a preparation and application of a MOF derived carbon dioxide hydrogenation methanol catalyst, the preparation method comprising the following steps: mixing a ZnZr-MOF material, an organic solvent and a copper source to react, and then drying and calcining; the ZnZr-MOF material comprises metal ions and organic ligands, the metal ions comprise Zn 2+ and Zr 4+ ; the content of Zn in the ZnZr-MOF material is 20-30 wt%, based on the total weight of the ZnZr-MOF material; the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:(0.85-15). The MOF derived carbon dioxide hydrogenation methanol catalyst has stable performance, good gas affinity and hydrophobicity, and high CO2 conversion rate and methanol selectivity.

Description

Technical Field

[0001] This disclosure relates to the field of catalytic carbon dioxide hydrogenation to methanol technology, specifically to the preparation and application of a MOF-derived carbon dioxide hydrogenation catalyst for methanol production. Background Technology

[0002] Carbon dioxide hydrogenation to methanol, as a carbon dioxide utilization technology with industrial application potential, not only enables the on-site utilization of carbon dioxide captured from coal-fired power plants / coal chemical plants, but also allows for the high-value-added conversion of carbon dioxide into chemical feedstocks or fuels, attracting widespread attention both domestically and internationally. Catalysts, as the core of carbon dioxide hydrogenation to methanol technology, have been the subject of extensive research both domestically and internationally, focusing on additives, supports, and preparation methods.

[0003] Regarding additives, the presence of Ga2O3 and CeO2 enhances the reducibility of Cu and increases its specific surface area; the addition of MnO and SiO2 promotes the formation of smaller, more reactive copper crystallites and improves the catalyst's adsorption capacity for H2, resulting in strong hydrogenation intensity. Metal oxides, such as ZnO, Al2O3, ZrO2, CeO2, and SiO2, are widely used as support materials. In terms of preparation methods, co-precipitation is the primary method, but impregnation, sol-gel synthesis, combustion synthesis, solid-state synthesis, ammonia evaporation, and atomic layer deposition have also been reported.

[0004] However, the catalysts currently used for the hydrogenation of carbon dioxide to methanol have the following problems: low single-pass conversion rate, poor selectivity of methanol products, and irreversible degradation of reaction performance caused by the aggregation of active sites of the catalyst due to the water generated in the reaction. These problems seriously limit the further large-scale industrial application of the carbon dioxide hydrogenation to methanol technology. Summary of the Invention

[0005] The purpose of this disclosure is to provide a MOF-derived catalyst for the hydrogenation of carbon dioxide to methanol and its application. This MOF-derived catalyst exhibits good gas- and hydrophobic properties and catalytic performance, and is stable, with high CO2 conversion and methanol selectivity, making it suitable for application in the hydrogenation of CO2 to methanol.

[0006] To achieve the above objectives, the first aspect of this disclosure provides a method for preparing a MOF-derived carbon dioxide hydrogenation catalyst for methanol production. The method includes the following steps: mixing a ZnZr-MOF material, an organic solvent, and a copper source for reaction, followed by drying and calcination; the ZnZr-MOF material comprises metal ions and organic ligands, wherein the metal ions include Zn... 2+ and Zr 4+ ;

[0007] Based on the total weight of the ZnZr-MOF material, the Zn content in the ZnZr-MOF material is 20-30% by weight; the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:(0.85-15).

[0008] Optionally, based on the total weight of the ZnZr-MOF material, the Zn content in the ZnZr-MOF material is 23-28% by weight; and the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:(0.85-10).

[0009] Optionally, the organic ligand includes one or more of formic acid ligands, pyromellitic acid ligands, and oxalic acid ligands.

[0010] Optionally, the amount of the organic solvent used is 80-120 mL relative to 1 g of ZnZr-MOF material; the organic solvent includes one or more of ethanol, glycerol and methanol.

[0011] Optionally, the mass ratio of the ZnZr-MOF material to the copper source is 1:(0.01~0.1); the copper source includes one or more of copper nitrate, copper sulfate and copper chloride.

[0012] Optionally, the reaction is carried out under stirring conditions, the temperature of the reaction is 20-30°C, and the time is 8-15 hours.

[0013] Optionally, the drying is oven drying, the drying temperature is 40-70℃, and the drying time is 8-15h; the method further includes centrifuging and washing the reaction product sequentially before drying; the washing uses an ethanol solution.

[0014] Optionally, the calcination temperature is 500–800°C, and the time is 3–8 hours; the calcination is carried out under a nitrogen atmosphere.

[0015] The second aspect of this disclosure provides a MOF-derived carbon dioxide hydrogenation catalyst for methanol production prepared using the preparation method described in the first aspect of this disclosure.

[0016] The third aspect of this disclosure provides the use of the MOF-derived carbon dioxide hydrogenation catalyst described in the second aspect of this disclosure in the production of methanol via CO2 hydrogenation.

[0017] Through the above technical solution, this disclosure relates to the preparation and application of a MOF-derived carbon dioxide hydrogenation to methanol catalyst. A copper source is introduced into a ZnZr-MOF material, and the material is carbonized by calcination to prepare the MOF-derived carbon dioxide hydrogenation to methanol catalyst. Cu exhibits good selectivity and catalytic activity. The presence of Zr in the ZnZr-MOF material maintains the catalyst's gas- and hydrophobic properties, while Zn is hydrophilic. By jointly adjusting the Zn and Zr contents, the catalytic performance is improved while maintaining a high overall gas- and hydrophobic profile. This catalyst exhibits stable performance, high CO2 conversion rate, and high methanol selectivity, and can be applied to CO2 hydrogenation to methanol.

[0018] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Detailed Implementation

[0019] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of this disclosure.

[0020] The first aspect of this disclosure provides a method for preparing a MOF-derived catalyst for the hydrogenation of carbon dioxide to methanol. The method includes the following steps: mixing a ZnZr-MOF material, an organic solvent, and a copper source for reaction, followed by drying and calcination; the ZnZr-MOF material comprises metal ions and organic ligands, wherein the metal ions include Zn... 2+ and Zr 4+ The Zn content in the ZnZr-MOF material is 20-30% by weight, based on the total weight of the ZnZr-MOF material; the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:(0.85-15).

[0021] This disclosure discloses a MOF-derived carbon dioxide hydrogenation to methanol catalyst prepared by introducing a copper source into a ZnZr-MOF material and carbonizing the material through calcination. Cu exhibits good selectivity and catalytic activity. The presence of Zr in the ZnZr-MOF material maintains the catalyst's gas- and hydrophobic properties, while Zn is hydrophilic. By jointly adjusting the contents of Zn and Zr, the catalytic performance of the catalyst is improved while maintaining a high overall gas- and hydrophobicity.

[0022] According to one embodiment of this disclosure, the Zn content in the ZnZr-MOF material, based on the total weight of the ZnZr-MOF material, is 23-28% by weight, preferably 24-26% by weight; the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:(0.85-10), preferably 1:(0.85-2.53). In the above embodiment, the preferred Zn content and molar ratio of Zn to Zr in the ZnZr-MOF material help to improve the hydrophobicity, CO2 conversion rate, and methanol selectivity of the MOF-derived carbon dioxide hydrogenation to methanol catalyst.

[0023] According to one embodiment of this disclosure, the organic ligand includes one or more of formic acid ligands, trimesic acid ligands, and oxalic acid ligands. In the above embodiment, selecting the above-mentioned organic ligands helps to improve the catalytic performance of the MOF-derived carbon dioxide hydrogenation to methanol catalyst.

[0024] According to one embodiment of this disclosure, the amount of the organic solvent used relative to 1g of ZnZr-MOF material is 80-120mL, preferably 80-100mL; the organic solvent includes one or more of ethanol, glycerol, and methanol. In the above embodiment, by selecting the above-mentioned organic solvent and the preferred amount of organic solvent, the catalytic performance of the MOF-derived carbon dioxide hydrogenation to methanol catalyst can be improved.

[0025] According to one embodiment of this disclosure, the mass ratio of the ZnZr-MOF material to the copper source is 1:(0.01-0.1), preferably 1:(0.03-0.07); the copper source includes one or more of copper nitrate, copper sulfate, and copper chloride. In the above embodiment, by selecting the above-mentioned copper source and the preferred mass ratio of ZnZr-MOF material to copper source, it is helpful to form a stable MOF-derived carbon dioxide hydrogenation catalyst for methanol production.

[0026] According to one embodiment of this disclosure, the reaction is carried out under stirring conditions, the reaction temperature is 20–30°C, preferably 25–28°C, and the reaction time is 8–15 h, preferably 10–12 h. In the above embodiment, the preferred reaction temperature and time help to improve the catalytic performance of the MOF-derived carbon dioxide hydrogenation catalyst for methanol production.

[0027] According to one embodiment of this disclosure, the drying is oven drying, the drying temperature is 40–70°C, preferably 50–60°C, and the drying time is 8–15 hours, preferably 10–12 hours. In the above embodiment, the preferred drying temperature and time can maintain the pore structure of the material.

[0028] According to one embodiment of this disclosure, the calcination temperature is 500–800°C, preferably 600–700°C, and the time is 3–8 hours, preferably 5–6 hours; the calcination is carried out under a nitrogen atmosphere. In the above embodiment, the preferred calcination temperature and time facilitate material carbonization and improve the catalytic performance of the MOF-derived carbon dioxide hydrogenation to methanol catalyst.

[0029] According to one embodiment of this disclosure, the method further includes, prior to drying, sequentially centrifuging and washing the reaction product; the washing is performed using an ethanol solution. In this disclosure, the "centrifugation" employs conventional apparatus and methods in the art.

[0030] According to one embodiment of this disclosure, ZnZr-MOF materials can be prepared by the following method:

[0031] (1) The organic ligand was mixed with ZrOCl2·8H2O in an organic solvent and subjected to a hydrothermal reaction. The resulting product was centrifuged and washed, and then dried to obtain the MOF precursor material.

[0032] The organic ligand is trimesic acid; the organic solvent includes N,N-dimethylformamide and formic acid; the volume ratio of N,N-dimethylformamide to formic acid is 1:(0.5-2), preferably 1:(0.8-1.2); the mass ratio of the organic ligand to ZrOCl2·8H2O is 1:(4-5), preferably 1:(4.2-4.5); the amount of formic acid used relative to 1g ZrOCl2·8H2O is 30-45mL, preferably 35-43mL; the hydrothermal reaction temperature is 80-120℃, preferably 95-120℃, and the time is 20-30h, preferably 22-26h; the washing is performed sequentially with N,N-dimethylformamide and acetone; the drying temperature is 40-70℃, preferably 50-65℃.

[0033] (2) The MOF precursor material was mixed with a cyclohexane solution of diethylzinc in a tetrahydrofuran solution and reacted. The product obtained from the reaction was centrifuged and washed.

[0034] The molar concentration of the diethylzinc cyclohexane solution is 0.5–2 mol / L, preferably 0.8–1.2 mol / L; the amount of the tetrahydrofuran solution used relative to 1 g of MOF precursor material is 250–350 mL, preferably 280–320 mL; the volume ratio of the diethylzinc cyclohexane solution to the tetrahydrofuran solution is 1:(50–65), preferably 1:(55–60); the reaction time is 2–5 h, preferably 3–4 h; the washing is performed using tetrahydrofuran solution; the number of washing cycles is 2–6, preferably 4–6 h. In the above embodiments, the ZnZr-MOF material prepared under the preferred conditions helps to improve the hydrophobicity, CO2 conversion rate, and methanol selectivity of the prepared MOF-derived carbon dioxide hydrogenation to methanol catalyst.

[0035] The second aspect of this disclosure provides a MOF-derived carbon dioxide hydrogenation catalyst for methanol production prepared using the preparation method described in the first aspect of this disclosure.

[0036] A third aspect of this disclosure provides the use of the MOF-derived carbon dioxide hydrogenation catalyst described in the second aspect of this disclosure in the hydrogenation of CO2 to methanol. The conditions for CO2 hydrogenation to methanol include: (1) pre-reducing the catalyst, wherein the pre-reduction conditions are: a hydrogen flow rate of 40-100 mL / min relative to 0.2-0.5 g of the MOF-derived carbon dioxide hydrogenation catalyst, preferably relative to 0.3-0.4 g of the catalyst. The MOF-derived carbon dioxide hydrogenation to methanol catalyst has a hydrogen flow rate of 50-80 mL / min and is heated to 200-400℃ at a heating rate of 2-10℃ / min for pre-reduction, preferably to 250-350℃ at a heating rate of 4-8℃ / min, and the pre-reduction time is 2-6 h, preferably 3-5 h; (2) CO2 hydrogenation to methanol reaction is carried out: the reaction temperature is 200-300℃, preferably 220-300℃, the reaction pressure is 2-10 MPa, preferably 3-7 MPa; the reaction gas composition is V(H2) / V(CO2) / V(N2)=(5-15):(1-8):1, preferably V(H2) / V(CO2) / V(N2)=(6-10):(2-4):1; the reaction gas space velocity is 3000-25000 mL·h -1 ·g cat -1 The preferred concentration is 4000–10000 mL·h -1 ·g cat -1 .

[0037] The present disclosure is further illustrated by the following embodiments, but the present disclosure is not limited thereto. In the following embodiments of the present disclosure, all raw materials used are commercially available products;

[0038] The single-point fully automatic contact angle measuring instrument is model KZS-21 (Dongguan Kezhong Precision Instrument Co., Ltd.); the continuous hydrogenation reactor is model GC-2021 (Shanghai Baikal Experimental Instrument Co., Ltd.).

[0039] Example 1

[0040] ZnZr-MOF material was dissolved in 100 ml of ethanol solution, and copper nitrate was added. After dissolution, the mixture was stirred at 25 °C for 12 h, then centrifuged, washed thoroughly with ethanol solution, and dried in an oven at 60 °C for 12 h to obtain catalyst precursor powder. The precursor powder was placed in a tube furnace and calcined at 600 °C under nitrogen protection for 5 h to obtain a MOF-derived carbon dioxide hydrogenation to methanol catalyst. The mass ratio of ZnZr-MOF material to copper nitrate was 1:0.05.

[0041] The preparation method of ZnZr-MOF material is as follows: (1) Tristyric acid and ZrOCl2·8H2O are mixed in N,N-dimethylformamide and hydrothermally reacted at 100℃ for 24h. After centrifugation, the obtained product is washed with N,N-dimethylformamide and acetone in sequence, and dried at 60℃ to obtain MOF precursor material; wherein, the mass ratio of tristyric acid to ZrOCl2·8H2O is 1:4.5;

[0042] (2) The MOF precursor material was mixed with a 1 mol / L diethylzinc cyclohexane solution in a tetrahydrofuran solution and reacted for 3 h. The product obtained from the reaction was centrifuged and washed 5 times with a tetrahydrofuran solution to obtain the ZnZr-MOF material.

[0043] The amount of tetrahydrofuran solution used was 300 mL relative to 1 g of MOF precursor material; the volume ratio of diethylzinc cyclohexane solution to tetrahydrofuran solution was 1:60.

[0044] ZnZr-MOF materials include Zn 2+ Zr 4+ The Zn content in the ZnZr-MOF material is 25.8% by weight, based on the total weight of the ZnZr-MOF material. The molar ratio of Zn to Zr in the ZnZr-MOF material is 1:2.53.

[0045] Example 2

[0046] The preparation method of the MOF-derived carbon dioxide hydrogenation to methanol catalyst in this embodiment is the same as that in Example 1, except that the mass ratio of ZnZr-MOF material to copper nitrate is 1:0.07.

[0047] Example 3

[0048] The preparation method of the MOF-derived carbon dioxide hydrogenation to methanol catalyst in this embodiment is the same as that in Example 1, except that: the volume ratio of diethylzinc cyclohexane solution to tetrahydrofuran solution is 1:51; the Zn content in the ZnZr-MOF material is 22% by weight; and the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:2.5.

[0049] Example 4

[0050] The preparation method of the MOF-derived carbon dioxide hydrogenation to methanol catalyst in this embodiment is the same as that in Example 1, except that the mass ratio of ZnZr-MOF material to copper nitrate is 1:0.15.

[0051] Example 5

[0052] The preparation method of the MOF-derived carbon dioxide hydrogenation to methanol catalyst in this embodiment is the same as that in Example 1, except that the precursor powder is placed in a tube furnace and calcined at 450°C under nitrogen protection for 2.5 h to obtain the MOF-derived carbon dioxide hydrogenation to methanol catalyst.

[0053] Comparative Example 1

[0054] The preparation method of the MOF-derived carbon dioxide hydrogenation catalyst for this comparative example is the same as that in Example 1, except that the volume ratio of diethylzinc cyclohexane solution to tetrahydrofuran solution is 1:300; the Zn content in the ZnZr-MOF material is 5.4% by weight; and the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:15.9. Comparative material 1 was obtained.

[0055] Comparative Example 2

[0056] The preparation method of the MOF-derived carbon dioxide hydrogenation catalyst for this comparative example is the same as that in Example 1, except that the volume ratio of the diethylzinc cyclohexane solution to the tetrahydrofuran solution is 1:120; the Zn content in the ZnZr-MOF material is 9.6% by weight; and the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:8.47. Comparative material 2 was obtained.

[0057] Comparative Example 3

[0058] The preparation method of the MOF-derived carbon dioxide hydrogenation catalyst for this comparative example is the same as that in Example 1, except that the volume ratio of the diethylzinc cyclohexane solution to the tetrahydrofuran solution is 1:20; the Zn content in the ZnZr-MOF material is 49.4% by weight; and the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:0.86. Comparative material 3 was obtained.

[0059] Comparative Example 4

[0060] The preparation method of the MOF-derived carbon dioxide hydrogenation catalyst for this comparative example is the same as that in Example 1, except that copper nitrate and ethanol are not added, and the ZnZr-MOF material is the comparative material 4.

[0061] Comparative Example 5

[0062] The preparation method of the MOF-derived carbon dioxide hydrogenation catalyst for this comparative example is the same as that in Example 1, except that: ZnZr-MOF material is mixed with copper nitrate to obtain comparative material 5; wherein, the mass ratio of ZnZr-MOF material to copper nitrate is 1:0.05.

[0063] Test example:

[0064] (1) CO2 hydrogenation to methanol: This was carried out in a pressurized fixed-bed continuous flow reactor combined system. 0.3 g of MOF-derived CO2 hydrogenation to methanol catalyst was loaded into the reaction tube, and the temperature was increased to 300 °C at a rate of 4 °C / min. The catalyst was then pre-reduced with hydrogen at a flow rate of 60 mL / min for 4 h. The temperature was then lowered to 240 °C, and the hydrogen was switched to the reaction gas, with a reaction gas composition of V(H2) / V(CO2) / V(N2) = 69:23:8. The reaction gas was then flowed at a rate of 5000 mL·h. -1 ·gcat -1 The pressure was maintained at 6 MPa. The products of CO2 hydrogenation were qualitatively and quantitatively analyzed by gas chromatography (GC). CO2 conversion was calculated using the N2-internal standard method, and methanol selectivity was calculated using the C-based internal normalization method. The results are shown in Table 1.

[0065] (2) Performance stability test: The CO2 conversion rate was measured 6 times within 1 hour (measured once every 10 minutes), and the average value of the 6 CO2 conversion rates was taken. The change of CO2 conversion rate was continuously observed every hour to evaluate the duration of stable CO2 conversion rate (the change of CO2 conversion rate within ±3% is considered stable). The results are shown in Table 1.

[0066] Table 1

[0067]

[0068]

[0069] As can be seen from the results in Tables 1 and 2, compared with Comparative Examples 1 to 5, the MOF-derived carbon dioxide hydrogenation catalysts for methanol production obtained in Examples 1 to 5 of this disclosure are hydrophobic, have high CO2 conversion and methanol selectivity, and exhibit stable performance.

[0070] Compared with Example 3, in Example 1, the Zn content and the molar ratio of Zn to Zr in the ZnZr-MOF material are within the preferred range, thus the obtained MOF-derived carbon dioxide hydrogenation to methanol catalyst has better hydrophobicity, higher CO2 conversion rate and methanol selectivity, and more stable performance. Compared with Example 4, in Example 1, the mass ratio of ZnZr-MOF material to copper source is within the preferred range, thus the obtained MOF-derived carbon dioxide hydrogenation to methanol catalyst has better hydrophobicity, higher CO2 conversion rate and methanol selectivity, and more stable performance. Compared with Example 5, in Example 1, the calcination temperature and time are within the preferred range, thus the obtained MOF-derived carbon dioxide hydrogenation to methanol catalyst has better hydrophobicity, higher CO2 conversion rate and methanol selectivity, and more stable performance.

[0071] Compared with Comparative Example 1, the Zn content and the molar ratio of Zn to Zr in the ZnZr-MOF material in Example 1 are within the range defined by this invention. Therefore, the obtained MOF-derived carbon dioxide hydrogenation to methanol catalyst has good hydrophobicity, high CO2 conversion rate and methanol selectivity, and stable performance.

[0072] Compared with Comparative Examples 2 and 3, the Zn content in the ZnZr-MOF material in Example 1 is within the range defined by this invention. Therefore, the obtained MOF-derived carbon dioxide hydrogenation to methanol catalyst has good hydrophobicity, high CO2 conversion rate and methanol selectivity, and stable performance.

[0073] Compared with Comparative Example 4, Example 1 introduced a copper source, which improved the selectivity and catalytic activity of the catalyst. However, Comparative Example 4 did not introduce a copper source or organic solvent into the ZnZr-MOF material, so the performance of the resulting catalyst was poor.

[0074] Compared with Comparative Example 5, Comparative Example 5 directly mixed ZnZr-MOF material with copper nitrate without solvent dissolution, resulting in a catalyst with poor performance.

[0075] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0076] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0077] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A method for preparing a MOF-derived carbon dioxide hydrogenation catalyst for methanol production, characterized in that, The preparation method includes the following steps: mixing ZnZr-MOF material, organic solvent, and copper source for reaction, followed by drying and calcination; the ZnZr-MOF material comprises metal ions and organic ligands, wherein the metal ions include Zn 2+ and Zr 4+ ; Based on the total weight of the ZnZr-MOF material, the Zn content in the ZnZr-MOF material is 23~28% by weight; the molar ratio of Zn to Zr in the ZnZr-MOF material is 1:(0.85~10). The calcination temperature is 500~800℃, and the time is 3~8h; the calcination is carried out under a nitrogen atmosphere.

2. The preparation method according to claim 1, characterized in that, The organic ligands include one or more of formic acid ligands, pyromellitic acid ligands, and oxalic acid ligands.

3. The preparation method according to claim 1, characterized in that, The amount of organic solvent used relative to 1g of ZnZr-MOF material is 80~120mL; the organic solvent includes one or more of ethanol, glycerol and methanol.

4. The preparation method according to claim 1, characterized in that, The mass ratio of the ZnZr-MOF material to the copper source is 1:(0.01~0.1); the copper source includes one or more of copper nitrate, copper sulfate and copper chloride.

5. The preparation method according to claim 1, characterized in that, The reaction is carried out under stirring conditions at a temperature of 20-30°C for 8-15 hours.

6. The preparation method according to claim 1, characterized in that, The drying process is a baking process, and the drying temperature is 40~70℃ for 8~15 hours. The method also includes centrifuging and washing the reaction product sequentially before drying; The washing process uses an ethanol solution.

7. The MOF-derived carbon dioxide hydrogenation catalyst for methanol prepared by any one of claims 1 to 6.

8. Use of the MOF-derived carbon dioxide hydrogenation catalyst of claim 7 in the production of methanol via CO2 hydrogenation.

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