Method for rapidly and macroscopically preparing iron-loaded porous molecular organic framework catalyst and application of iron-loaded porous molecular organic framework catalyst
By using ultrafast solvothermal and impregnation methods to load iron active components, the problems of long preparation cycle and low yield of MOF materials have been solved, and rapid, large-scale preparation and high-efficiency photocatalytic performance of iron-supported porous molecular organic framework catalysts have been achieved.
Patent Information
- Application Number
- CN202511396974.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-28
- Publication Date
- 2025-12-30
AI Technical Summary
Existing methods for preparing MOF materials suffer from problems such as long reaction cycles, low yields, high costs, and difficulty in scaling up. In particular, iron-supported MOF catalysts have low preparation efficiency and insufficient performance stability, which cannot meet the needs of industrial applications.
MOF support was prepared by an ultrafast solvothermal method, and iron active components were loaded by impregnation. Fe-N4 active sites were formed by mechanical stirring, and finally iron-supported porous molecular organic framework catalyst was obtained by vacuum drying.
Rapid preparation of MOF materials with high yield and easy scalability was achieved. The catalyst active sites were stable, exhibiting highly efficient photocatalytic carbon dioxide reduction performance.
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Figure CN121222490A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalyst preparation technology, and relates to a method for the large-scale preparation of metal-organic framework (MOF) materials, and particularly to a method for the rapid large-scale preparation of iron-supported porous molecular organic framework catalysts. Background Technology
[0002] MOF (Metal-Organic Framework) materials are crystalline porous materials with a periodic network structure formed by the self-assembly of metal ions or metal clusters (inorganic nodes) and organic ligands (organic linkers) through coordination bonds. MOF materials, with their highly designable, porous crystalline structure formed by the self-assembly of metal nodes and organic ligands, possess core advantages such as ultra-high specific surface area and uniformly tunable active sites, demonstrating enormous application potential in constructing efficient and highly selective "nanoreactors" in heterogeneous catalysis, photocatalysis, and electrocatalysis. For example, in heterogeneous catalysis, the porous structure of MOFs can confine reactant molecules, improving reaction selectivity; in photocatalysis, it can optimize the separation and transport efficiency of photogenerated carriers through the synergistic effect of metal nodes and ligands.
[0003] However, traditional MOF methods (such as hydrothermal / solvothermal methods) generally suffer from problems such as long reaction cycles (tens of days to several days), low yields (milligram level), high costs, and difficulty in scaling up, which cannot meet the needs of industrial applications.
[0004] Iron, as one of the most abundant transition metals in the Earth's crust, is inexpensive, environmentally friendly, and exhibits excellent catalytic activity, making it an ideal active component for supported catalysts. Iron-supported MOF catalysts combine the porous structure advantages of MOF materials with the catalytic performance of iron as an active component, showing broad prospects in photocatalysis, catalytic oxidation, Fischer-Tropsch synthesis, and environmental degradation.
[0005] In conclusion, developing a universal method to overcome the aforementioned bottlenecks and achieve rapid, large-scale preparation of iron-supported MOF catalysts is of great significance for promoting their transition from laboratory to practical industrial applications. Summary of the Invention
[0006] To address the problems of long synthesis cycle, low yield, high cost, and difficulty in scaling up of MOFs in existing technologies, as well as the low preparation efficiency and insufficient performance stability of iron-supported MOF catalysts, the present invention aims to disclose a method for preparing iron-supported porous MOF catalysts that is simple to operate, fast in reaction, high in yield, low in cost, and easy to scale up.
[0007] Technical solution
[0008] A method for rapid, large-scale preparation of iron-supported porous molecular organic framework catalysts includes the following steps:
[0009] S1. Rapid large-scale preparation of MOF support: Using 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc) and 4,4'-stilbene dicarboxylic acid (SBDC) as mixed ligands, Al(NO3)3·9H2O as the metal source, and N,N-dimethylformamide (DMF) as the solvent, the reaction was completed within 1 min using an ultrafast solvothermal method to obtain gram-scale MOF precursors (MOF-1).
[0010] S2. Post-loading of iron active components: The obtained MOF support is dispersed in acetonitrile solution to form MOF dispersion, and then FeCl3·6H2O is added to anchor Fe species in the channels or surface of MOF-1 by impregnation method; preferably, mechanical stirring is performed at room temperature to convert Fe species into highly dispersed Fe single atoms, forming Fe-N4 active sites and maintaining a good framework structure;
[0011] S3. Catalyst activation: The loaded material was vacuum dried for 12 hours to obtain an iron-supported porous molecular organic framework catalyst.
[0012] In a preferred embodiment of the present invention, in step S1, the material ratio of 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc) and 4,4'-stilbene dicarboxylic acid (SBDC) in the mixed ligand to the solvent N,N-dimethylformamide (DMF) is 0.08~0.1mmol:0.015~0.02mmol:1~5mL, preferably 0.1mmol:0.02mmol:3mL.
[0013] In a preferred embodiment of the present invention, in step S1, the material ratio of 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc), 4,4'-stilbene dicarboxylic acid (SBDC), N,N-dimethylformamide (DMF), and aluminum nitrate nonahydrate (Al(NO3)3·9H2O) is 0.08~0.1mmol : 0.015~0.02mmol : 1~5mL : 0.45~0.5mmol, preferably 0.1mmol : 0.02mmol : 3mL : 0.46mmol.
[0014] In a preferred embodiment of the present invention, in step S1, the reaction temperature of the ultra-fast solvothermal method is 120~200℃, preferably 200℃; the sample is slowly cooled to room temperature, and the resulting sample is washed with DMF and methanol to remove impurities, and dried at 60℃ for 12h.
[0015] In a preferred embodiment of the present invention, in step S2, the mass-to-volume ratio of FeCl3·6H2O, MOF-1, and acetonitrile solution is 0.5~1.5 mg : 0.5~1.5 mg : 0.5~10 mL, preferably 1.2 mg : 1 mg : 5 mL; the mechanical stirring speed is 400~1000 rpm, preferably 600 rpm, and the stirring time is 8~12 h, preferably 12 h.
[0016] In a preferred embodiment of the present invention, in step S3, the temperature of the vacuum drying is 60~80℃, preferably 70℃; the vacuum degree of the vacuum drying is ≤10Pa.
[0017] In a preferred embodiment of the present invention, in step S1, the 4,4'-stilbene dicarboxylic acid (SBDC) can be replaced with other organic dicarboxylic acid ligands, such as 4,4'-phenylenediacrylic acid, azobenzene-4,4'-dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-bromoterephthalic acid, 2-fluoroterephthalic acid, 2-aminoterephthalic acid, or 4,4'-oxaloyldibenzoic acid, etc.
[0018] The second objective of this invention is to provide an iron-supported porous molecular organic framework catalyst prepared by the above method, which has a nanoflower-like or disc-like microstructure, with the iron active component uniformly dispersed in H-MOF-1, stable active sites, and good visible light absorption performance.
[0019] The third objective of this invention is to apply the prepared iron-supported porous molecular organic framework catalyst to the photocatalysis of carbon dioxide (CO2).
[0020] Beneficial effects
[0021] This invention overcomes the time limitations of traditional solvothermal methods, reducing MOF synthesis time from days to minutes, achieving rapid and efficient preparation. The method disclosed in this invention requires no complex high-pressure equipment, is simple, easy to scale up, and can prepare gram-scale high-quality MOF supports in a single process, achieving large-scale production with outstanding mass production capabilities. Through a post-loading process, the iron active component is highly dispersed within the MOF channels, forming stable active sites. The resulting catalyst exhibits high activity and high stability in the photocatalytic carbon dioxide reduction reaction, demonstrating excellent performance. Attached Figure Description
[0022] Figure 1 A flowchart of the preparation process disclosed in this invention;
[0023] Figure 2Scanning electron microscope (SEM) images of the MOF-1 (a) and Fe / MOF-1 composite material (b) prepared in Example 1;
[0024] Figure 3 High-resolution transmission electron microscopy (HRTEM) image of the Fe / MOF-1 composite material prepared in Example 1;
[0025] Figure 4 X-ray absorption fine structure (XAFS) spectrum of the Fe / H-MOF-1 composite material prepared in Example 1;
[0026] Figure 5 Scanning electron microscope image of the MOF-X prepared in Example 2;
[0027] Figure 6 . Schematic diagram of the apparatus used to prepare the large-scale MOF in Example 3;
[0028] Figure 7 Scanning electron microscope (SEM) image of the large-scale MOF prepared in Example 3;
[0029] Figure 8 Powder X-ray diffraction pattern of the large-scale MOF prepared in Example 3;
[0030] Figure 9 Nitrogen adsorption diagram of the catalyst prepared in Example 1;
[0031] Figure 10 Pore size distribution of the catalyst prepared in Example 1;
[0032] Figure 11 Carbon dioxide adsorption chromatogram of the catalyst prepared in Example 1;
[0033] Figure 12 Photocatalytic carbon dioxide reduction performance of the catalyst prepared in Example 1;
[0034] Figure 13 Photocatalytic carbon dioxide reduction stability test diagram of the catalyst prepared in Example 1;
[0035] Figure 14 Photocatalytic carbon dioxide reduction performance of the catalyst prepared in Example 2;
[0036] Figure 15 Photocatalytic carbon dioxide reduction performance of the catalyst prepared in Example 3. Detailed Implementation
[0037] The present invention will be described in detail below with reference to embodiments, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following embodiments.
[0038] Example 1
[0039] A method for preparing MOF-1 and Fe / MOF-1 catalysts includes: using 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc) and 4,4'-stilbene dicarboxylic acid (SBDC) as mixed ligands, and Al(NO3)3·9H2O as the metal source, MOF-1 is prepared within 1 min via a solvothermal method. Subsequently, Fe single atoms are anchored by impregnation, and Fe / MOF-1 is obtained after vacuum drying. The ratio of 2,2'-bipyridine-5,5'-dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, N,N-dimethylformamide, Al(NO3)3·9H2O, and acetonitrile participating in the MOF-1 reaction is 0.1 mmol: 0.02 mmol: 3 mL: 0.46 mmol: 5 mL, the reaction temperature is 120 °C, and the mass percentage of FeCl3·6H2O participating in the reaction is 20 wt%.
[0040] The prepared catalyst was applied to photocatalytic CO2 reduction. The experimental steps included: conducting a photocatalytic CO2 reduction reaction in a 250 mL sealed Pyrex reactor under a CO2 atmosphere. The reaction system contained 1 mg of the catalyst prepared in this example and 0.05 mmol of [Ru(bpy)3]Cl2, dissolved in a mixed solvent composed of CH3CN (40 mL), H2O (0.5 mL), and TEOA (1 mL), and was continuously magnetically stirred at a mechanical stirring speed of 500 rpm. Dissolved air was removed by three CO2 replacement cycles before irradiation. A 300 W xenon lamp (Beijing Perfect Optoelectronics Microsolar 300) was used as the light source, equipped with a λ≥420 nm cutoff filter, and the temperature was maintained at 298 K through a cooling water circulation system.
[0041] The yield of CO2 reduced to ethylene was measured to be 681 μmol·g. -1 ·h -1 .
[0042] Example 2
[0043] A rapid method for preparing MOF catalysts includes: using 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc) and a second ligand (any one of azobenzene 4,4-dicarboxylic acid (ADC), 4,4'-biphenyl dicarboxylic acid (BP), 1,4-naphthalenedicarboxylic acid (1.4-NDC), 2,6-naphthalenedicarboxylic acid (2.6-NDC), 2,5-dihydroxyterephthalic acid (DHTA), 2-bromoterephthalic acid (Br-TPA), 2-fluoroterephthalic acid (F-TPA), 2-aminoterephthalic acid (ATA), 4,4'-oxaloylterephthalic acid (ODB) as a mixed ligand, and Al(NO3)3·9H2O as a metal source to prepare MOFs in 1 min using a rapid solvothermal method. The reactants in the MOF reaction, including 2,2'-bipyridine-5,5'-dicarboxylic acid, the second ligand, N,N-dimethylformamide, and Al(NO3)3·9H2O, were in the following ratios: acetonitrile: 0.1 mmol: 0.02 mmol: 3 mL: 0.15 mmol: 5 mL. The reaction temperature was 200℃, and the mass percentage of FeCl3·6H2O involved in the reaction was 20 wt%.
[0044] Under the same photocatalytic CO2 reduction test conditions as described in Example 1, the yields of CO2 reduced to ethylene by FeCl3·6H2O-supported ADC-MOF, BP-MOF, 1,4-NDC-MOF, 2,6-NDC-MOF, DHTA-MOF, Br-TPA-MOF, F-TPA-MOF, ATA-MOF, and ODB-MOF were measured to be 481, 357, 246, 491, 223, 424, 458, 290, and 234 μmol·g, respectively. -1 ·h -1 .
[0045] Example 3
[0046] A method for preparing a large-scale MOF catalyst includes: using 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc) and 4,4'-stilbene dicarboxylic acid (SBDC) as mixed ligands, and Al(NO3)3·9H2O as the metal source, MOF-1 is prepared by a simple solvothermal method. The material ratio of 2,2'-bipyridine-5,5'-dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, N,N-dimethylformamide, and Al(NO3)3·9H2O participating in the MOF-1 reaction is 6.4 mmol: 1.3 mmol: 200 mL: 11.1 mmol:. The reaction time is 1 min, and the reaction temperature is 200 °C.
[0047] Under the same photocatalytic CO2 reduction test conditions as described in Example 1, the yield of CO2 reduced to ethylene was measured to be 663 μmol·g. -1 ·h -1 .
[0048] Figure 1 The process flow diagram for the rapid large-scale preparation of iron-supported porous molecular organic framework catalysts and their application in photocatalytic carbon dioxide reduction, as described in this invention.
[0049] Figure 2 The catalyst (MOF-1 and Fe) prepared in Example 1 of this invention 0.2 Scanning electron microscope images of / MOF-1, where (a) and (b) show its different nanodisk morphologies.
[0050] Figure 3 The iron single atom (Fe) in Example 1 of this invention SAs The schematic diagram of the dispersion of iron atoms in the MOF-1 framework visually demonstrates that iron atoms are anchored on the MOF support in an atomically dispersed state.
[0051] Figure 4 This is a comparison of X-ray absorption spectra of different iron species in Example 1 of the present invention, including Fe foil, Fe2O3, FeCl3, iron phthalocyanine, and Fe prepared in this invention. 0.2 By analyzing the bond lengths of Fe-N and Fe-O, the coordination environment of iron in the MOF framework was verified to be Fe-N4Cl2.
[0052] Figure 5 The present invention provides scanning electron microscope images of a series of MOF materials constructed from different organic ligands, which show the morphology of nanodisks.
[0053] Figure 6 The diagram shows the optimized device in Embodiment 3 of the present invention, where the device is increased from 25 mL to 500 mL.
[0054] Figure 7 The scanning electron microscope image of MOF-1-2g prepared in Example 3 of this invention shows the morphology of nanodiscs.
[0055] Figure 8 The X-ray diffraction pattern of MOF-1-2g prepared in Example 3 of this invention is shown. Comparison with the theoretical simulation pattern confirms that the synthesized material has a crystal structure consistent with the design.
[0056] Figure 9 Different samples (including MOF-1 and Fe) in Example 1 of this invention 0.2 The nitrogen adsorption-desorption isotherm of / MOF-1 was used to characterize the specific surface area of the material.
[0057] Figure 10 The diagram shows the pore size distribution of different samples in Example 1 of the present invention, further illustrating the influence of different processing techniques on the pore structure of the material.
[0058] Figure 11 The images show the adsorption performance curves of different catalyst samples for carbon dioxide gas in Example 1 of this invention, demonstrating their CO2 adsorption capacity at room temperature.
[0059] Figure 12 This is a comparison of the performance of different catalysts in the catalytic reaction in Example 1 of the present invention. (a) Comparison of ethylene yield; (b) Comparison of carbon monoxide yield. The results show that Fe... 0.2 The MOF-1 catalyst exhibited the best formation rate in both products.
[0060] Figure 13 Fe in Embodiment 1 of the present invention 0.2 The cycling stability test results of the / MOF-1 catalyst are shown, where (a) represents the change in ethylene yield with the number of cycles; and (b) represents the change in carbon monoxide yield with the number of cycles. The results indicate that Fe... 0.2 / MOF-1 exhibits good stability.
[0061] Figure 14 This is a comparison of the catalytic performance of MOF materials constructed with different ligands after loading iron in Example 2 of the present invention, where (a) represents the carbon monoxide yield and (b) represents the ethylene yield. The ligand structure with the best performance was selected through comparison.
[0062] Figure 15 The graph shows a comparison of the catalytic performance of MOF-1-2g and its iron-loaded form (Fe / MOF-1-2g). (a) represents the carbon monoxide yield; (b) represents the ethylene yield. This further verifies the crucial role of iron loading in improving the catalytic performance of MOF materials.
[0063] Example 4
[0064] Azobenzene-4,4'-dicarboxylic acid was used as the second ligand.
[0065] The reason for choosing the second ligand is that the azophenyl group has unique photoresponsive properties, and its cis-trans isomerization may optimize the separation efficiency of photogenerated electron-hole pairs in the material, thereby improving the photocatalytic performance.
[0066] Objective: To rapidly prepare MOF supports with azobenzene-4,4'-dicarboxylic acid as the second ligand and load iron single atoms in large quantities.
[0067] Preparation steps:
[0068] 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc, 0.1 mmol), azobenzene-4,4'-dicarboxylic acid (ADC, 0.02 mmol), aluminum nitrate nonahydrate (Al(NO3)3·9H2O, 0.15 mmol), and N,N-dimethylformamide (DMF, 3 mL) were mixed in a 25 mL stainless steel reactor lined with polytetrafluoroethylene. The reactor was sealed and placed in an oven and heated to 200 °C for 1 minute. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The resulting solid product was washed three times each with DMF and methanol, and dried at 60 °C for 12 h to obtain the MOF-ADC support.
[0069] Disperse the above MOF-ADC carrier (1 mg) in acetonitrile (5 mL), add ferric chloride hexahydrate (FeCl3·6H2O, 1.2 mg), and mechanically stir at 600 rpm for 12 hours;
[0070] The loaded material was dried under vacuum at 70°C for 1 hour at a vacuum level of ≤10 Pa to obtain the final catalyst Fe / ADC-MOF.
[0071] Under the same photocatalytic CO2 reduction test conditions as described in Example 1, the yield of CO2 reduced to ethylene was measured to be 481 μmol·g. -1 ·h -1 .
[0072] This catalyst exhibits above-average catalytic performance, demonstrating the effectiveness of ADC ligands in constructing highly efficient photocatalysts. Its unique light absorption properties help improve visible light utilization efficiency.
[0073] Example 5
[0074] 2,5-Dihydroxyterephthalic acid was used as the second ligand.
[0075] The rationale for choosing the second ligand is that the hydroxyl functional group can modulate the electronic structure of the MOF, provide additional coordination sites, help stabilize iron-active species, and may enhance the adsorption and activation of CO2 molecules.
[0076] Objective: To rapidly prepare MOF supports with 2,5-dihydroxyterephthalic acid as the second ligand and load iron single atoms in large quantities.
[0077] Preparation steps:
[0078] 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc, 0. mmol), 2,5-dihydroxyterephthalic acid (DHTA, 0.02 mmol), aluminum nitrate nonahydrate (Al(NO3)3·9H2O, 0.15 mmol), and N,N-dimethylformamide (DMF, 3 mL) were mixed in a 25 mL stainless steel reactor lined with polytetrafluoroethylene. The reactor was sealed and placed in an oven and heated to 200°C for 1 minute. Subsequent cooling, washing, and drying steps were the same as in Example 5 to obtain the MOF-DHTA support.
[0079] The iron loading procedure was the same as in Example 5 (FeCl3·6H2O: MOF-DHTA = 1.2 mg : 1 mg, acetonitrile 5 mL, stirring at 600 rpm for 12 h), and the activation conditions were also the same, resulting in the catalyst Fe / DHTA-MOF.
[0080] Under the same photocatalytic CO2 reduction test conditions as described in Example 1, the yield of CO2 reduced to ethylene was measured to be 423 μmol·g. -1 ·h -1 .
[0081] The catalyst exhibited above-average catalytic performance, indicating that the hydroxyl-containing ligand DHTA can also successfully construct a high-performance catalyst framework.
[0082] Example 6
[0083] 4,4'-oxaloyldibenzoic acid was used as the second ligand.
[0084] The rationale for choosing the second ligand is that the oxalyl group has a long, flexible chain and a specific bond angle, which may guide the MOF to form a unique pore structure, which is beneficial for the mass transfer of reactants and products. At the same time, its flexibility may enhance the stability of the skeleton.
[0085] Objective: To rapidly prepare MOF supports with 4,4'-oxaloyldibenzoic acid as the second ligand and load iron single atoms in large quantities.
[0086] Preparation steps:
[0087] 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpydc, 0.1 mmol), 4,4'-oxaloyldibenzoic acid (ODB, 0.02 mmol), aluminum nitrate nonahydrate (Al(NO3)3·9H2O, 0.15 mmol), and N,N-dimethylformamide (DMF, 3 mL) were mixed in a 25 mL stainless steel reactor lined with polytetrafluoroethylene. The reactor was sealed and placed in an oven and heated to 200°C for 1 minute. Subsequent cooling, washing, and drying steps were the same as in Example 5 to obtain the MOF-ODB support. The iron loading steps were the same as in Example 5, and after activation, the catalyst Fe / ODB-MOF was obtained.
[0088] Under the same photocatalytic CO2 reduction test conditions as described in Example 1, the yield of CO2 reduced to ethylene was measured to be 434 μmol·g. -1 ·h -1 .
[0089] The catalyst prepared using ODB ligands exhibited above-average catalytic performance, demonstrating that the technical solution of this invention is also well-suited for dicarboxylic acid ligands with special conformations and flexible chains. Their potentially larger pore size provides a favorable microenvironment for the catalytic reaction.
[0090] The embodiments described above are merely specific implementations of the present invention and do not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made using the present invention specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.
Claims
1. A method for rapid macro-scale preparation of iron-loaded porous molecular organic framework catalysts, characterized in that, Comprising the following steps: S1. Rapid macro-preparation of MOF carrier: using 2,2'-bipyridine-5,5'-dicarboxylic acid Bpydc and 4,4'-stilbene dicarboxylic acid SBDC as mixed ligands, Al(NO3)3·9H2O as metal source, and N,N-dimethylformamide DMF as solvent, the reaction is completed within 1 min by ultrafast solvothermal method to obtain kilogram MOF precursor MOF-1; S2. Post-loading of iron active component: the obtained MOF carrier is dispersed in acetonitrile solution to form a MOF dispersion, and then FeCl3·6H2O is added to anchor Fe species in the pores or surface of MOF-1 by impregnation method; S3. Activation of the catalyst: after vacuum drying treatment of the loaded material for 12 h, an iron-loaded porous molecular organic framework catalyst is obtained.
2. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S1, the material ratio of Bpydc and SBDC in the mixed ligand to solvent DMF is 0.08-0.1 mmol:0.015-0.02 mmol:1-5 mL, preferably 0.1 mmol:0.02 mmol:3 mL.
3. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S1, the material ratio of Bpydc, SBDC, DMF, and Al(NO3)3·9H2O is 0.08-0.1 mmol:0.015-0.02 mmol:1-5 mL:0.45-0.5 mmol, preferably 0.1 mmol:0.02 mmol:3 mL:0.46 mmol.
4. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S1, the reaction temperature of the ultrafast solvothermal method is 120-200°C, preferably 200°C; the obtained sample is washed with DMF and methanol respectively to remove impurities, and then dried at 60°C for 12 h.
5. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S2, the mass-volume ratio of FeCl3·6H2O, MOF-1, and acetonitrile solution is 0.5-1.5 mg:0.5-1.5 mg:0.5-10 mL, preferably 1.2 mg:1 mg:5 mL; the stirring speed of mechanical stirring is 400-1000 rpm, preferably 600 rpm, and the stirring time is 8-12 h, preferably 12 h.
6. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S2, the anchoring of Fe species in the pores or surface of MOF-1 by impregnation method is carried out at room temperature by mechanical stirring treatment to convert Fe species into highly dispersed Fe monatomic atoms, form Fe-N4 active sites, and maintain good framework structure.
7. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S3, the temperature of vacuum drying is 60-80°C, preferably 70°C; the vacuum degree of vacuum drying is ≤10 Pa.
8. The method for rapid macro-preparation of iron-loaded porous molecular organic framework catalyst according to claim 1, characterized in that: In step S1, the 4,4'-stilbene dicarboxylic acid can also be replaced by any one of 4,4'-dipropenylbenzene dicarboxylic acid, azobenzene-4,4'-dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-bromoterephthalic acid, 2-fluoroterephthalic acid, 2-aminoterephthalic acid or 4,4'-oxalylbenzene dicarboxylic acid.
9. The iron-loaded porous molecular organic framework catalyst prepared according to the method of any one of claims 1-8, characterized in that: The catalyst has a nanoflower or disc-like micro-morphology.
10. Use of the iron-loaded porous molecular organic framework catalyst according to claim 9, characterized in that: It is applied to photocatalytic carbon dioxide CO2.