A hPW-ceo2 catalyst based on three-dimensional MOFs configuration, and a preparation method and application thereof

Abstract

The application relates to the technical field of atmospheric pollution catalyst preparation, in particular to a HPW-CeO2 catalyst based on a three-dimensional MOFs configuration and a preparation method and application thereof; the microstructure of the HPW-CeO2 catalyst is a nanospindle self-assembly spherical structure, and in the self-assembly process of the single spherical structure, HPW components are uniformly anchored around CeO2 components through electrostatic reaction between the HPW components and CeBDC-NH2 as MOFs anchoring templates; a brand-new synthesis path is designed to prepare the HPW-CeO2 catalyst, electrostatic interaction between the amido MOFs and the HPW is utilized, the HPW is uniformly anchored in the highly-ordered oxidation metal cluster of the MOFs, good dispersion of the HPW is realized at the molecular level, active sites closer to a theoretical value are exposed, and finally, the catalyst for catalytic oxidation of CVOCs with low-temperature activity and chlorine-poisoning resistance is prepared.

Description

Technical Field

[0001] This invention relates to the field of atmospheric pollution catalyst preparation technology, specifically to an HPW-CeO2 catalyst based on a three-dimensional MOF configuration, its preparation method, and its application. Background Technology

[0002] Chlorine-containing volatile organic compounds (CVOCs) are harmful to both the ecological environment and human health. CeO2 itself has excellent oxygen storage / release capacity and exhibits considerable activity in the catalytic oxidation of CVOCs. However, the inorganic chlorine species generated during the reaction are easily adsorbed onto the CeO2 surface, leading to catalyst deactivation. Phosphotungstic acid (HPW) is a stronger acid than traditional inorganic acids, and its acidity is tunable. It also possesses certain redox properties. Phosphotungstic acid can promote the dissociation of CVOCs, and its Brønsted acid sites can also promote the exit of inorganic chlorine species from the reaction system in the form of HCl, thereby improving the catalyst's resistance to chlorine poisoning.

[0003] For the reasons mentioned above, HPW / CeO2 catalysts have become a research hotspot. For example, in "The performance of medium and low temperature SCR denitration of phosphotungstic acid supported cerium oxide catalyst" (Section 1.1) and "Application study of NOx selective catalytic reduction of heteropolyacid supported cerium dioxide" (Section 3.2.1), HPW / CeO2 catalysts were prepared by dry mixing method.

[0004] In Section 1.1, the effects of acid properties on the selective catalytic reduction of NO by NH3 on phosphotungstic acid modified CeO2 were discussed, and in Section 4.1.1, the HPW / CeO2 catalysts were prepared by impregnation.

[0005] While impregnation and dry mixing are currently the mainstream preparation methods, they offer advantages such as ease of operation and large production volumes. However, these methods, which involve physically mixing components, have the following two significant drawbacks:

[0006] 1) The simple physical bonding method cannot guarantee that the HPW component is evenly distributed around the CeO2 component at the micro level, which makes it difficult for the HPW / CeO2 catalyst to maintain macroscopic uniformity and microscopic continuity.

[0007] 2) The strong physical mixing method will cause the exposed surface of CeO2 component to be covered by HPW component, which will greatly reduce the specific surface area and active sites of the former, thus affecting the overall physicochemical performance of the catalyst. Summary of the Invention

[0008] To address the aforementioned issues, this invention provides an HPW-CeO2 catalyst based on a three-dimensional MOF configuration and its preparation method. By utilizing the electrostatic interaction between amination-modified MOFs and HPW, HPW is uniformly anchored within highly ordered oxidizing metal clusters in the MOFs, achieving good dispersion of HPW at the molecular level and exposing active sites closer to theoretical values. Ultimately, a catalyst with low-temperature activity resistant to chlorine poisoning for the catalytic oxidation of CVOCs is prepared. The scheme is described below.

[0009] 1. Composition and structure of HPW-CeO2 catalyst

[0010] The HPW-CeO2 catalyst designed in this invention, based on a three-dimensional MOF configuration, is a spherical structure self-assembled from nanospindles, with a specific surface area of ​​76.74–132.5 g / m² for a single spherical structure. 2 ;

[0011] The HPW-CeO2 catalyst comprises an HPW component as a strong acid component and a CeO2 component as a redox component; during the self-assembly of a single spherical structure, the HPW component is uniformly anchored around the CeO2 component through electrostatic reaction with CeBDC-NH2, which serves as an anchoring template for MOFs.

[0012] In the individual spherical structure of the HPW-CeO2 catalyst, the HPW component and the CeO2 component are connected by Ce-OW bonds.

[0013] 2. Preparation method of HPW-CeO2 catalyst

[0014] S1. Preparation of MOF anchoring templates via hydrothermal method:

[0015] S1-1. Prepare the reaction reagents required for the hydrothermal method: solution A, solution B and solution C;

[0016] Solution A is an organic solution containing Ce transition metal salt, solution B is an organic solution containing amine ligands, and solution C is ultrapure water;

[0017] S1-2. Place solution A under ultrasonic conditions, add solution B and solution C in sequence, sonicate for 10-15 min, and then react at 100-110℃ for 24-30 h to obtain CeBDC-NH2, i.e. MOF anchoring template.

[0018] Note: CeBDC-NH2 is a MOF formed by cerium salt and 2-aminoterephthalic acid. The metal oxide obtained by its pyrolysis has certain activity for the catalytic oxidation of CVOCs. Using MOFs as a precursor of metal oxides can inherit the highly ordered pore structure of MOFs, which is beneficial to the macroscopic mass transfer of reaction substrates.

[0019] S2. Based on the MOFs anchoring template prepared in S1, the HPW component is uniformly anchored around the CeO2 component by electrostatic force, resulting in CeBDC-NH2-HPW:

[0020] S2-1: Dissolve HPW in acetonitrile, then add CeBDC-NH2 from S1-2 and stir thoroughly for 30-40 minutes to obtain mixture 2-4;

[0021] Let n be the multiplier and n∈R + Therefore, the amount of HPW added in mixture 2-4 is n·[0.1,0.12]g, the amount of acetonitrile added is n·[20,22]mL, and the amount of CeBDC-NH2 added is n·1g;

[0022] S2-2, centrifuge the mixture 2-4 in S2-1 to obtain precipitate, wash and dry the precipitate to obtain CeBDC-NH2-HPW;

[0023] Explanation: The amine ligand -NH2 interacts electrostatically with HPW, which makes HPW uniformly anchored on the organic ligand in MOFs, promotes the interaction between CeO2 and HPW and the high dispersion of HPW, which is beneficial to the mass transfer of reaction intermediates between HPW and CeO2, and improves the activity of the catalyst and its resistance to chlorine poisoning.

[0024] S3, pyrolysis of CeBDC-NH2-HPW in S2 to obtain HPW-CeO2 catalyst that inherits the microstructure of MOF anchor template;

[0025] The pyrolysis parameters are as follows: under air atmosphere, the temperature is increased from room temperature to 400-450℃ at a heating rate of 3-5℃ / min, and calcined for 3-4 hours.

[0026] Note: The surface-anchored HPW forms a confinement effect, which is beneficial to prevent the MOF structure from collapsing during the pyrolysis process, so that the HPW-CeO2 catalyst inherits the morphology and pore structure characteristics of MOFs.

[0027] Furthermore, in S1-1, the Ce transition metal salt is Ce(NO3)3·6H2O, the amino ligand is 2-aminoterephthalic acid, and the organic solution is DMF;

[0028] Let n be the multiplier and n∈R + ,but:

[0029] In solution A, the amount of Ce(NO3)3·6H2O added is n·[1.9,2.0]mol, and the amount of DMF added is n·[40,45]L;

[0030] In solution B, the amount of 2-aminoterephthalic acid added is n·[3.1,3.2]mol, and the amount of DMF added is n·[40,45]L;

[0031] In solution C, the amount of ultrapure water added is n·[15,20]L.

[0032] 3. Application of HPW-CeO2 catalyst

[0033] When the HPW-CeO2 catalyst based on the three-dimensional MOF configuration designed in this invention is applied to the degradation of chlorine-containing volatile organic compounds, at the temperature T corresponding to a chlorobenzene conversion rate of 90%, it achieves this result. 90％ As a criterion for evaluating catalyst activity, the T0 of the HPW-CeO2 catalyst was determined under the condition of an initial chlorobenzene concentration of 1000 ppm. 90％ 312℃; with CO x The temperature T corresponding to a formation rate of 90% 90％ As a criterion for evaluating catalyst selectivity, the Ti of the HPW-CeO2 catalyst... 90％ The temperature is 312℃.

[0034] Compared with existing methods for preparing HPW / CeO2 catalysts, the advantages of this invention are:

[0035] (1) This invention utilizes the oxidizing properties and highly ordered pore structure of MOFs, and the electrostatic interaction between the amine ligand -NH2 and HPW, so that HPW is uniformly anchored on the organic ligand in MOFs, which promotes the interaction between CeO2 and HPW and the high dispersion of HPW. This is beneficial to the mass transfer of reaction intermediates between HPW and CeO2, and improves the activity and resistance to chlorine poisoning of HPW-CeO2 catalyst.

[0036] (2) The present invention anchors HPW on the surface of MOFs to form a confinement effect, which is beneficial to prevent the MOFs structure from collapsing during the pyrolysis process. This allows the HPW-CeO2 catalyst to inherit the morphology and pore structure of MOFs, thus solving the problem of easy collapse of MOFs structure during pyrolysis.

[0037] (3) Since the HPW-CeO2 catalyst prepared by this invention does not adopt the preparation method of physical mixing components, the exposed surface of CeO2 component will not be covered by HPW component, thus reducing the specific surface area and active sites of the former. Moreover, this invention establishes a large number of stable pore structures between HPW and CeO2 components by anchoring templates with MOFs—CeBDC-NH2, which increases the specific surface area of ​​HPW-CeO2 catalyst and increases the number of active sites.

[0038] (4) The HPW-CeO2 catalyst prepared in this invention has excellent low-temperature activity and resistance to chlorine poisoning: with the temperature T corresponding to a chlorobenzene conversion rate of 90% as an example. 90％ As a criterion for evaluating catalyst activity, under the condition of an initial chlorobenzene concentration of 1000 ppm, the T0.1 of the 0.1 g HPW-modified MOFs-derived metal oxide catalyst was used. 90％ At a temperature of 312℃, it significantly reduces energy consumption compared to conventional catalysts and exhibits excellent resistance to chlorine poisoning. Attached Figure Description

[0039] Figure 1 These are the XRD patterns of CeO2, HPW-CeO2-2.5%, HPW-CeO2-5%, HPW-CeO2-10%, and HPW-CeO2-15%.

[0040] Figure 2 middle:

[0041] (a) is a SEM image of CeBDC-NH2-HPW-10%;

[0042] (b) is a SEM image of HPW-CeO2-10%;

[0043] (c) is a TEM image of HPW-CeO2-10%;

[0044] (d) is a mapping diagram of Ce, O, W and P in HPW-CeO2-10%. Detailed Implementation

[0045] To further illustrate the methods and effects of this invention, the technical solution of this invention will be clearly and completely described below in conjunction with experiments.

[0046] Example 1

[0047] Example 1 mainly illustrates the composition and structure of the HPW-CeO2 catalyst designed in this invention.

[0048] See Figure 2 The HPW-CeO2 catalyst based on the three-dimensional MOF configuration designed in this invention has a microstructure of a spherical structure self-assembled by nanospindles; the HPW-CeO2 catalyst includes an HPW component as a strong acid component and a CeO2 component as a redox component.

[0049] During the self-assembly of a single spherical structure, the HPW component is uniformly anchored around the CeO2 component through electrostatic reaction with CeBDC-NH2, which serves as an anchoring template for MOFs.

[0050] In the individual spherical structure of the HPW-CeO2 catalyst, the HPW component and the CeO2 component are connected by Ce-

[0051] Connect the OW keys.

[0052] Example 2

[0053] Example 2 mainly illustrates the preparation method of the HPW-CeO2 catalyst designed in this invention under specific parameters.

[0054] S1. Preparation of MOF anchoring templates via hydrothermal method:

[0055] S1-1. Prepare the reaction reagents required for the hydrothermal method: solution A, solution B and solution C;

[0056] Solution A is a DMF solution of Ce(NO3)3·6H2O, solution B is a DMF solution of 2-aminoterephthalic acid, and solution C is ultrapure water;

[0057] In solution A, the amount of Ce(NO3)3·6H2O added is 1.9 mol, and the amount of DMF added is 40 L;

[0058] In solution B, the amount of 2-aminoterephthalic acid added is 3.1 mol, and the amount of DMF added is 40 L;

[0059] In solution C, the amount of ultrapure water added is 15L;

[0060] S1-2. Place solution A under ultrasonic conditions, add solution B and solution C in sequence, sonicate for 10 min, and then react at 100℃ for 24 h to obtain CeBDC-NH2, i.e. MOF anchoring template;

[0061] S2. Based on the MOFs anchoring template prepared in S1, the HPW component is uniformly anchored around the CeO2 component by electrostatic force, resulting in CeBDC-NH2-HPW:

[0062] S2-1: Dissolve HPW in acetonitrile, then add CeBDC-NH2 from S1-2 and stir thoroughly for 30 minutes to obtain mixture 2-4;

[0063] The amount of HPW added in mixture 2-4 is 0.1g, the amount of acetonitrile added is 20mL, and the amount of CeBDC-NH2 added is 1g.

[0064] S2-2, centrifuge the mixture 2-4 in S2-1 to obtain precipitate, wash and dry the precipitate to obtain CeBDC-NH2-HPW;

[0065] S3, pyrolysis of CeBDC-NH2-HPW in S2 to obtain HPW-CeO2 catalyst that inherits the microstructure of MOF anchor template;

[0066] The pyrolysis parameters were as follows: under an air atmosphere, the temperature was increased from room temperature to 400℃ at a heating rate of 3℃ / min, and then calcined for 3 hours.

[0067] Example 3

[0068] Example 3 mainly illustrates the preparation method of the HPW-CeO2 catalyst designed in this invention under another specific parameter.

[0069] S1. Preparation of MOF anchoring templates via hydrothermal method:

[0070] S1-1. Prepare the reaction reagents required for the hydrothermal method: solution A, solution B and solution C;

[0071] Solution A is a DMF solution of Ce(NO3)3·6H2O, solution B is a DMF solution of 2-aminoterephthalic acid, and solution C is ultrapure water;

[0072] In solution A, the amount of Ce(NO3)3·6H2O added is 2.0 mol, and the amount of DMF added is 45 L;

[0073] In solution B, the amount of 2-aminoterephthalic acid added is 3.2 mol, and the amount of DMF added is 45 L;

[0074] In solution C, the amount of ultrapure water added is 20L;

[0075] S1-2. Place solution A under ultrasonic conditions, add solution B and solution C in sequence, sonicate for 15 min, and then react at 110℃ for 30 h to obtain CeBDC-NH2, i.e. MOFs anchoring template.

[0076] S2. Based on the MOFs anchoring template prepared in S1, the HPW component is uniformly anchored around the CeO2 component by electrostatic force, resulting in CeBDC-NH2-HPW:

[0077] S2-1: Dissolve HPW in acetonitrile, then add CeBDC-NH2 from S1-2 and stir thoroughly for 40 min to obtain mixture 2-4;

[0078] The amount of HPW added in mixture 2-4 is 0.12g, the amount of acetonitrile added is 22mL, and the amount of CeBDC-NH2 added is 1g.

[0079] S2-2, centrifuge the mixture 2-4 in S2-1 to obtain precipitate, wash and dry the precipitate to obtain CeBDC-NH2-HPW;

[0080] S3, pyrolysis of CeBDC-NH2-HPW in S2 to obtain HPW-CeO2 catalyst that inherits the microstructure of MOF anchor template;

[0081] The pyrolysis parameters were as follows: under air atmosphere, the temperature was increased from room temperature to 450℃ at a heating rate of 5℃ / min, and calcined for 4 hours.

[0082] Example 4

[0083] The description of Example 4 is based on the preparation method in Example 3. The main objective of this example is to prepare the HPW-CeO2-10% catalyst, which refers to the HPW and CeBDC-NH2 mass ratio of 10%.

[0084] S1. Preparation of MOF anchoring templates via hydrothermal method:

[0085] S1-1. Prepare the reaction reagents required for the hydrothermal method: solution A, solution B and solution C;

[0086] Solution A is a DMF solution of Ce(NO3)3·6H2O, solution B is a DMF solution of 2-aminoterephthalic acid, and solution C is ultrapure water;

[0087] In solution A, the amount of Ce(NO3)3·6H2O added is 0.00199 mol, and the amount of DMF added is 40 mL;

[0088] In solution B, the amount of 2-aminoterephthalic acid added is 0.00314 mol, and the amount of DMF added is 40 mL;

[0089] In solution C, the amount of ultrapure water added is 15 mL;

[0090] S1-2. Place solution A under ultrasonic conditions, add solution B and solution C in sequence, sonicate for 10 min, and then react at 100℃ for 24 h to obtain CeBDC-NH2, i.e. MOF anchoring template;

[0091] S2. Based on the MOFs anchoring template prepared in S1, the HPW component is uniformly anchored around the CeO2 component by electrostatic force, resulting in CeBDC-NH2-HPW:

[0092] S2-1: Dissolve HPW in acetonitrile, then add CeBDC-NH2 from S1-2 and stir thoroughly for 40 min to obtain mixture 2-4;

[0093] The amount of HPW added in mixture 2-4 is 0.08g, the amount of acetonitrile added is 20mL, and the amount of CeBDC-NH2 added is 0.8g.

[0094] S2-2, centrifuge the mixture 2-4 in S2-1 to obtain precipitate, wash and dry the precipitate to obtain CeBDC-NH2-HPW;

[0095] S3, pyrolysis of CeBDC-NH2-HPW in S2 to obtain HPW-CeO2 catalyst that inherits the microstructure of MOF anchor template;

[0096] The pyrolysis parameters were as follows: under air atmosphere, the temperature was increased from room temperature to 400℃ at a heating rate of 3℃ / min and calcined for 4 hours to obtain HPW-CeO2-10% catalyst.

[0097] Example 5

[0098] The preparation method of HPW-CeO2 catalyst in this embodiment is basically the same as in Example 4. The main difference is that the mass ratio of HPW to CeBDC-NH2 is 2.5%, which is denoted as HPW-CeO2-2.5%.

[0099] Example 6

[0100] The preparation method of HPW-CeO2 catalyst in this embodiment is basically the same as in Example 4. The main difference is that the mass ratio of HPW to CeBDC-NH2 is 5%, which is denoted as HPW-CeO2-5%.

[0101] Example 7

[0102] The preparation method of HPW-CeO2 catalyst in this embodiment is basically the same as in Example 4. The main difference is that the mass ratio of HPW to CeBDC-NH2 is 15%, which is denoted as HPW-CeO2-15%.

[0103] Comparative Example

[0104] Comparative synthesis of CeO2 catalyst: The synthesis method is the same as in Example 4, except that HPW was not added during the synthesis process. The specific steps are as follows:

[0105] S1. Preparation of MOF anchoring templates via hydrothermal method:

[0106] S1-1. Prepare the reaction reagents required for the hydrothermal method: solution A, solution B and solution C;

[0107] Solution A is a DMF solution of Ce(NO3)3·6H2O, solution B is a DMF solution of 2-aminoterephthalic acid, and solution C is ultrapure water;

[0108] In solution A, the amount of Ce(NO3)3·6H2O added is 0.00199 mol, and the amount of DMF added is 40 mL;

[0109] In solution B, the amount of 2-aminoterephthalic acid added is 0.00314 mol, and the amount of DMF added is 40 mL;

[0110] In solution C, the amount of ultrapure water added is 15 mL;

[0111] S1-2. Place solution A under ultrasonic conditions, add solution B and solution C in sequence, sonicate for 10 min, and then react at 100℃ for 24 h to obtain CeBDC-NH2, i.e. MOF anchoring template;

[0112] S2, CeBDC-NH2 in pyrolysis of S1;

[0113] The pyrolysis parameters were as follows: under air atmosphere, the temperature was increased from room temperature to 400℃ at a heating rate of 3℃ / min, and calcined for 4 hours to obtain CeO2 catalyst.

[0114] Experimental Example

[0115] The description of this experimental example is based on the scheme described in Example 4, and aims to illustrate the catalytic performance of the HPW-CeO2 catalyst designed in this invention.

[0116] The catalysts synthesized in the examples and comparative examples were evaluated using a fixed-bed catalyst evaluation device coupled with online gas chromatography. The specific steps are as follows: 0.1 g of catalyst was accurately weighed and loaded into a 5 mm quartz tube, which was then placed in a reactor. Under the condition that the initial concentration of chlorobenzene (CB) was 1000 ppm, the outlet chlorobenzene concentration was measured at different temperatures. The temperature at which the chlorobenzene conversion rate was 90% was used as the catalyst activity evaluation standard, and the temperature at which the inorganic carbon oxide formation rate was 90% was used as the catalyst selectivity evaluation standard. The results are shown in the table.

[0117] Table 1 Catalytic performance of different catalysts for chlorobenzene

[0118]

[0119] From Table 1, we can obtain the T value for Experiment Example 4. 90％ The Tg of the HPW-CeO2-10% catalyst prepared in Example 4 was significantly lower than that of the comparative example. 90％ The catalyst, capable of reaching 312℃, significantly reduces the energy consumption required for the reaction compared to conventional catalysts. This demonstrates that the novel preparation method designed in this invention can effectively control the heterojunction interface, thereby significantly improving the low-temperature activity of the catalyst in the catalytic oxidation of CVOCs, and thus greatly reducing the required energy consumption. Furthermore, it exhibits high selectivity for carbon oxides (conversion rate To of chlorobenzene). 90％ With CO x Generation rate T 90％ The results were basically the same, both at 312℃, indicating that fewer chlorine byproducts were generated.

[0120] Comparison of specific surface area: CeO2: 78.07 m² 2 / g, HPW-CeO2-2.5%: 82.32m 2 / g, HPW-CeO2-5%: 125.2m 2 / g, HPW-CeO2-10%: 132.5m 2 / g, HPW-CeO2-15%: 76.74m 2 / g, it can be seen that the specific surface area of ​​HPW-CeO2-2.5%, HPW-CeO2-5%, and HPW-CeO2-10% are all greater than that of CeO2 and show an increasing trend. This is because the CeBDC-NH2-HPW structure inherits the microstructure of MOFs, and the porous channels support the gap between HPW and CeO2, so that the exposed surface of CeO2 is not covered by HPW and the active sites are exposed closer to the theoretical value. Moreover, its pore structure itself can also play a role in improving the specific surface area and mass transfer.

[0121] However, it is worth noting that HPW-CeO2-15% has a specific surface area of ​​76.74 m². 2 The specific surface area ( / g) actually decreased, and was lower than that of CeO2 (78.07m²). 2 This is because excessive HPW doping affects the stability of MOFs structure during pyrolysis, causing the three-dimensional porous structure to collapse and form closed pores. Consequently, the specific surface area of ​​the modified catalyst is actually lower than that of CeO2 itself. Therefore, when preparing HPW-CeO2 catalysts, the amount of HPW doping should not be increased excessively, and the doping range should be carefully controlled according to parameter characterization.

Claims

1.A HPW-CeO 2 catalyst based on three-dimensional MOFs configuration, characterized in that: the microstructure of the HPW-CeO 2 catalyst is a nanospindle self-assembled spherical structure, which comprises a HPW component as a strong acid component and a CeO 2 component as a redox component, the HPW component is uniformly anchored around the CeO 2 component through electrostatic reaction with a CeBDC-NH 2 as a MOFs anchoring template; in a single spherical structure of the HPW-CeO 2 catalyst, the HPW component and the CeO 2 component are connected through Ce-O-W bonds; the catalyst is used for degradation of volatile organic compounds containing chlorine. comprising the following steps: S1, preparing a MOFs anchoring template by a hydrothermal method: S1-1, preparing reaction reagents required by the hydrothermal method: solution A, solution B and solution C; 2. The preparation method of the HPW-CeO2 catalyst based on the three-dimensional MOFs configuration according to claim 1, wherein the HPW component is uniformly distributed around the CeO2 component, and the target catalyst is obtained by combining the two components through the force. the solution A is an organic solution containing Ce transition metal salt, the solution B is an organic solution containing amine ligand, and the solution C is ultrapure water; S1-2, placing the solution A under ultrasonic conditions, sequentially adding the solution B and the solution C, ultrasonic treatment for 10-15 min, and then reacting at 100-110℃ for 24-30 h to obtain CeBDC-NH 2, i.e. the MOFs anchoring template; S2, based on the MOFs anchoring template prepared in S1, uniformly anchoring the HPW component around the CeO 2 component through electrostatic force; obtaining CeBDC-NH 2 -HPW: S2-1, dissolving HPW in acetonitrile, then adding CeBDC-NH 2 in S1-2, and fully stirring for 30-40 min; obtaining a mixed solution 2-4; S2-2, centrifuging the mixed solution 2-4 in S2-1 to obtain a precipitate, washing and drying the precipitate to obtain CeBDC-NH 2 -HPW; S3, pyrolyzing CeBDC-NH 2 -HPW in S2 to obtain a HPW-CeO 2 catalyst inheriting the micro-morphology of the MOFs anchoring template; the pyrolysis parameters are: under air atmosphere, the temperature is increased from room temperature to 400-450℃ at a heating rate of 3-5 ℃ / min, and the calcination is continued for 3-4 h. Let n be the magnification factor and n∈R + Therefore, the amount of HPW added in the mixed solution 2-4 is n·[0.1, 0.12] g, the amount of acetonitrile added is n·[20, 22] mL, and the amount of CeBDC-NH2 added is n·1 g. in S1-1, the Ce transition metal salt is Ce(NO 3 ) 3 ·6H 2 O, and the amine ligand is 2-amino terephthalic acid, and the organic solution is DMF; in solution A, the addition amount of Ce(NO 3 ) 3 ·6H 2 O is n·[1.9, 2.0] mol, and the addition amount of DMF is n·[40, 45] L; in solution B, the addition amount of 2-amino terephthalic acid is n·[3.1, 3.2] mol, and the addition amount of DMF is n·[40, 45] L; 3. A method for preparing a HPW-Ce02 catalyst based on a three-dimensional MOFs configuration according to claim 2, characterized in that, in solution C, the addition amount of ultrapure water is n·[15, 20] L. Let n be the scale factor and n e R + Then: 4.The application of a HPW-CeO 2 catalyst based on three-dimensional MOFs configuration in the degradation of volatile organic compounds containing chlorine according to claim 1. ​ ​ ​

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