Pt and MnO x Nanoparticle in-situ loaded NH2-MIL-101 (Fe) photocatalyst and its preparation method and application

Abstract

The application discloses a kind of Pt and MnO x Nanoparticle in situ loading NH2-MIL-101 (Fe) photocatalyst and its preparation method and application belong to the technical field of photocatalyst preparation.The preparation method disclosed in the application first uses a simple solvothermal method to carry out coordination reaction with 2-amino terephthalic acid as organic ligand and FeCl3·6H2O as metal salt to synthesize NH2-MIL-101 (Fe), then, MnO x NPs and Pt NPs are loaded in sequence by using photodeposition and chemical reduction process, finally, NH2-MIL-101 (Fe) (Pt@NM-101 / MnO x ) composite catalyst loaded with MnO x NPs and Pt NPs is synthesized, which significantly solves the problems of high energy consumption and environmental pollution of traditional industrial nitrogen fixation Haber-Bosch method.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photocatalyst preparation, and particularly relates to a Pt and MnO x Nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, a preparation method thereof and application thereof. BACKGROUND

[0002] Ammonia (NH3) as an important industrial raw material, plays an important role in the processes of chemical fertilizer, medicine, explosive and textile industry, in addition, as its high energy density (4.3 kW h kg -1 ) and clean emission, it is also an ideal zero-carbon energy carrier. At present, the global ammonia is mainly obtained from the industrial synthesis Haber-Bosch method. However, the Haber-Bosch process needs to be carried out under severe reaction conditions, that is, high temperature (450-550 ℃) and high pressure (15-25 Mpa) with the help of iron-based catalyst to synthesize NH3 by using high-purity N2 and H2. This traditional process consumes 1% of the global energy and produces about 2% of the chemical industry CO2 emission. The energy required for the photocatalytic synthesis of ammonia (PNRR) is solar energy, which is inexhaustible and has become a research hotspot in recent years, and is also considered as an effective solution to replace the Haber-Bosch process. However, in the PNRR, the efficient electron-hole separation efficiency is the key to improve the solar energy utilization efficiency. Therefore, how to improve the electron-hole separation efficiency to construct a high-activity catalyst is an urgent problem to be solved by researchers at present.

[0003] The coupling of photocatalyst and cocatalyst is an efficient electron-hole separation method, and the introduction of different cocatalysts can respectively achieve the purpose of promoting the oxidation and reduction half-reaction. Oxidation cocatalysts, including CuO x , CoO x and MnO x , tend to capture holes for oxidation reaction, while reduction cocatalysts including Ru, Pd and Pt tend to capture electrons for reduction reaction. In addition, metal organic framework materials (MOF) with high photosensitivity, regular pore, super high specific surface area and adjustable structure function are considered as ideal catalysts for photocatalytic synthesis of ammonia. However, compared with single oxidation or reduction active site, it is still a difficult problem to design nanoparticle active sites for N2 reduction and H2O oxidation on the photocatalyst at the same time, and to combine the corresponding half-reaction in the photocatalytic system to provide more hydrogen source and more electrons for the multi-electron process of N2 hydrogenation. SUMMARY

[0004] The purpose of the present application is to provide a Pt and MnO xThe application discloses a nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, a preparation method and application thereof, and aims to solve the technical problems of high energy consumption and environmental pollution of a traditional industrial nitrogen fixation Haber-Bosch method.

[0005] In order to achieve the above-mentioned purpose, the application adopts the following technical solutions to achieve the above-mentioned purpose:

[0006] The application discloses a kind of Pt and MnO x The preparation method of the nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst includes the following steps:

[0007] After 2-amino terephthalic acid, FeCl3·6H2O and solvent are stirred and mixed, hydrothermal reaction is carried out, and NH2-MIL-101(Fe) catalyst is obtained;

[0008] After NH2-MIL-101(Fe) catalyst, MnSO4 and water are mixed, reaction is carried out under light condition and constant temperature condition, and NM-101 / MnO x is obtained after reaction is finished.

[0009] NM-101 / MnO x and water are mixed, then H2PtCl6·6H2O aqueous solution is added, and then reducing agent and stabilizer are added drop by drop, to obtain Pt and MnO x nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst.

[0010] Further, in the step of obtaining NH2-MIL-101(Fe), the mass ratio of 2-amino terephthalic acid, FeCl3·6H2O and solvent (DMF) is (0.206 g~0.210 g):(0.675 g~0.680 g):(25 mL~26 mL); and the solvent is DMF.

[0011] Further, in the step of obtaining NH2-MIL-101(Fe), the temperature of the hydrothermal reaction is 110 DEG C, and the time is 24 h.

[0012] Further, in the step of obtaining NM-101 / MnO x , the mass ratio of NH2-MIL-101(Fe) catalyst, MnSO4 and water is (0.1 g~0.105 g):(0.3 g~0.31 g):(50 mL~52 mL).

[0013] Further, the light condition is that 300W xenon lamp is irradiated for 1 h with a 420 nm filter; and the temperature of the constant temperature condition is 25 DEG C.

[0014] Furthermore, NH2-MIL-101(Fe) catalyst, MnSO4 and water were mixed and reacted under light conditions and constant temperature conditions. After the reaction, the obtained reaction product was dried in a freeze dryer for 6 to 6.2 h to obtain NM-101 / MnO x .

[0015] Furthermore, the NM-101 / MnO x The dosage ratio of water, reducing agent and stabilizer is (0.1 g~0.105 g): (20 mL~22 mL): (700 uL ~705 uL): (5 mg~ 7 mg).

[0016] Furthermore, the reducing agent is 1 mol ml -1 The stabilizer is citric acid.

[0017] The present invention also discloses Pt and MnO prepared by the above preparation method. x Nanoparticles were in situ loaded with NH2-MIL-101(Fe) photocatalyst.

[0018] The present invention also discloses the above-mentioned Pt and MnO x Application of nanoparticle in situ loaded NH2-MIL-101(Fe) photocatalyst in photocatalytic conversion of nitrogen to ammonia.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention discloses a Pt and MnO x The preparation method of nanoparticles in situ loaded NH2-MIL-101(Fe) photocatalyst is firstly prepared by a simple solvothermal method with 2-aminoterephthalic acid as an organic ligand and FeCl3·6H2O as a metal salt for coordination reaction to synthesize NH2-MIL-101(Fe). Subsequently, MnO is loaded in sequence by photodeposition and chemical reduction processes respectively. x NPs and Pt NPs, and finally synthesized loaded MnO x NH2-MIL-101(Fe) (Pt@NM-101 / MnO x ) composite catalyst, in which amino-functionalized NH2-MIL-101(Fe) is used as a carrier. The introduction of amino groups in this material can enhance the absorption ability of the photocatalyst to light in a specific band, so that more light energy is converted into chemical energy, thereby improving the photocatalytic nitrogen fixation performance; in addition, MnO xThe in-situ dispersed nanoparticle loaded amino-functionalized NH2-MIL-101(Fe) promotes the oxidation of H2O, and provides more available proton hydrogen for N2 reduction. x The synergistic effect of the nanoparticle loaded NH2-MIL-101(Fe) composite photocatalyst can improve the photocatalytic conversion of nitrogen to ammonia, and significantly solve the problems of high energy consumption and environmental pollution in the traditional industrial Haber-Bosch process.

[0021] The application further discloses a Pt and MnO x The in-situ dispersed nanoparticle loaded NH2-MIL-101(Fe) photocatalyst is a Pt and MnO x The nanoparticle loaded NH2-MIL-101(Fe) is a Pt and MnO x The in-situ dispersed nanoparticle is Pt@NM-101 / MnO x The reduction reaction occurs on the Pt NPs, and the oxidation reaction occurs on the MnOx NPs in the composite photocatalyst. x The composite catalyst not only effectively improves the separation efficiency of photo-generated electrons and holes, but also realizes the synergistic promotion of oxidation and reduction half-reactions, so that the photocatalytic nitrogen fixation activity is improved.

[0022] The application further discloses a Pt and MnO x The application further discloses an application of the in-situ dispersed nanoparticle loaded NH2-MIL-101(Fe) photocatalyst in photocatalytic conversion of nitrogen to ammonia. x The nitrogen fixation activity of the composite photocatalyst is obviously improved, and the ammonia production is increased by about 4.56 times. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The application further discloses a Pt and MnO x , Pt@NM-101 and the Pt and MnO x The XRD pattern of the in-situ dispersed nanoparticle loaded NH2-MIL-101(Fe) photocatalyst.

[0024] Figure 2 The application further discloses a Pt and MnO xSEM image of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles;

[0025] Figure 3 Pt and MnO2 prepared for Example 2 of the present application x TEM image of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles;

[0026] Figure 4 Pt and MnO2 prepared for Example 2 of the present application x HRTEM image of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles;

[0027] Figure 5 NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x UV-Vis absorption spectrum of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles;

[0028] Figure 6 NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x Transient photocurrent response of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles;

[0029] Figure 7 NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x Impedance plot of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles;

[0030] Figure 8 NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x NH2-MIL-101(Fe), NM-101 / MnO2, Pt@NM-101 and Pt and MnO2 prepared for Example 2 of the present application x Photocatalytic conversion of nitrogen to ammonia activity profile of the NH2-MIL-101(Fe) photocatalyst in-situ loaded with nanoparticles. DETAILED DESCRIPTION

[0031] To enable persons skilled in the art to have a better understanding of the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have their usual meanings to those skilled in the art of the present application, and in case of conflict, the definitions contained in the specification shall prevail.

[0032] Theories and mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, which can be practiced without regard to any particular theory or mechanism.

[0033] Herein, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, amounts, contents and concentrations, are for the sake of brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0034] Herein, unless otherwise specified, "comprise", "include", "contain", "have" or similar phrases are intended to encompass the meaning of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meaning of "A comprises a and other" and "A comprises only a".

[0035] Herein, for the sake of brevity, all possible combinations of the various technical features in the various embodiments or examples are not described. Therefore, the various technical features in the various embodiments or examples can be combined in any manner as long as there is no contradiction, and all possible combinations should be considered as falling within the scope of the present specification.

[0036] The present application will be further described with reference to the following specific examples. It is to be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. Furthermore, it is to be understood that various modifications can be made to the present application by those skilled in the art upon reading the teachings of the present application as set forth herein, and such equivalent forms are intended to fall within the scope of the appended claims.

[0037] In the following examples, the instruments and apparatuses of the art are used. In the following examples, the experimental methods not otherwise specified are usually carried out under the conventional conditions or under the conditions recommended by the manufacturers. In the following examples, various raw materials are used, and unless otherwise specified, the conventional commercially available products are used, and the specifications are the conventional specifications in the art. In the specification of the present application and in the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.

[0038] Example 1

[0039] A Pt and MnOx A method for preparing a nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, comprising the following steps:

[0040] 0.206 mg of 2-amino terephthalic acid and 0.675 mg of FeCl3·6H2O were weighed into 25 ml of DMF. The suspension was stirred at room temperature for 30 minutes, and then the mixture was hydrothermally treated at 110°C for 24 hours in a polytetrafluoroethylene liner (100 mL). After the precipitate was cooled to room temperature, it was separated from the reaction mixture by suction filtration and washed thoroughly with DMF, ethanol and water to remove any unreacted raw materials. Finally, the obtained solid was dried in a freeze dryer for 6 hours to obtain NH2-MIL-101(Fe) powder (labeled as NM-101);

[0041] 0.1 g of the prepared NH2-MIL-101(Fe) powder, 0.3 g of MnSO4·H2O and 50 mL of water were respectively placed in a reactor, and a 420 nm filter was irradiated with a 300 W xenon lamp for 1 h, while the reactor was kept at a constant temperature of 25°C by circulating condensed water, and the reaction was carried out. After the reaction was completed, the obtained reaction product was washed with water, and then the obtained solid was dried in a freeze dryer for 6 h to obtain NM-101 / MnO x ;

[0042] 0.1 g of the prepared NM-101 / MnO x was placed in 20 mL of deionized water to form a mixed solution, 500 uL of a 10 mg mL -1 aqueous solution of H2PtCl6·6H2O was added to the prepared mixed solution, and after being stirred uniformly, 1.5 mL of a 0.1 mol L -1 aqueous solution of NaBH4 was added dropwise as a reducing agent and 5 mg of citric acid was added as a stabilizer to obtain Pt and MnO x nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst (Pt@NM-101 / MnO x -1).

[0043] Example 2

[0044] A Pt and MnO x A method for preparing a nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, comprising the following steps:

[0045] A mixture of 0.206 mg of 2-amino terephthalic acid and 0.675 mg of FeCl3-6H2O was added to 25 ml of DMF. The suspension was stirred for 30 minutes at room temperature, then the mixture was hydrothermally treated at 110°C for 24 hours in a polytetrafluoroethylene liner (100 mL). After the precipitate was cooled to room temperature, it was separated from the reaction mixture by suction filtration and washed thoroughly with DMF, ethanol and water to remove any unreacted starting materials. Finally, the obtained solid was dried in a freeze dryer for 6 hours to obtain NH2-MIL-101(Fe) powder.

[0046] The prepared 0.1 g of NH2-MIL-101(Fe) powder, 0.3 g of MnSO4-H2O and 50 mL of water were respectively put into a reactor, and a reaction was carried out by irradiating with a 300 W xenon lamp with a 420 nm filter for 1 h while the reactor was kept constant at 25°C by circulating condensed water. After the reaction was completed, the obtained reaction was washed with water, and then the obtained solid was dried in a freeze dryer for 6 h to obtain NM-101 / MnO x ;

[0047] The prepared 0.1 g of NM-101 / MnO x was put into 20 mL of deionized water to form a mixed solution, 700 uL of 10 mg mL -1 of H2PtCl6-6H2O aqueous solution was added to the prepared mixed solution, and 1.5 mL of 0.1 mol L -1 of NaBH4 aqueous solution was added dropwise as a reducing agent and 5 mg of citric acid was added as a stabilizer, to obtain Pt and MnO x nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst (Pt@NM-101 / MnO x -2).

[0048] Example 3

[0049] A preparation method of a Pt and MnO x nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, comprising the following steps:

[0050] A mixture of 0.206 mg of 2-amino terephthalic acid and 0.675 mg of FeCl3-6H2O was added to 25 ml of DMF. The suspension was stirred for 30 minutes at room temperature, and then the mixture was hydrothermally treated at 110°C for 24 hours in a polytetrafluoroethylene liner (100 mL). After the precipitate was cooled to room temperature, it was separated from the reaction mixture by suction filtration and washed thoroughly with DMF, ethanol and water to remove any unreacted starting materials. Finally, the obtained solid was dried in a freeze dryer for 6 hours to obtain NH2-MIL-101(Fe) powder.

[0051] A prepared 0.1 g of NH2-MIL-101(Fe) powder, 0.3 g of MnSO4-H2O and 50 mL of water were respectively put into a reactor, and a reaction was performed by irradiating with a 300 W xenon lamp with a 420 nm filter for 1 h while the reactor was kept constant at 25°C in temperature by circulating condensed water, and after the reaction was completed, the obtained reaction was washed with water, and then the obtained solid was dried in a freeze dryer for 6 h to obtain NM-101 / MnO x ;

[0052] A prepared 0.1 g of NM-101 / MnO x was put into 20 mL of deionized water to form a mixed solution, 900 uL of 10 mg mL -1 of an aqueous H2PtCl6-6H2O solution was added to the prepared mixed solution, and after being stirred uniformly, 1.5 mL of 0.1 mol L -1 of an aqueous NaBH4 solution was added dropwise as a reducing agent and 5 mg of citric acid was added as a stabilizer to obtain Pt and MnO x nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst (Pt@NM-101 / MnO x -3).

[0053] Figure 1 The XRD pattern of the NH2-MIL-101(Fe), NM-101 / MnO x , Pt@NM-101 and Pt and MnO x nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst prepared in Example 1 to Example 3 of the present application can be seen from the XRD of the sample, which is consistent with the main peak of the NH2-MIL-101(Fe) simulation, which proves the successful synthesis of the composite material.

[0054] Figure 2 The XRD pattern of the NH2-MIL-101(Fe), NM-101 / MnO xSEM image of the nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, which exhibits regular and slightly rough octahedral morphology, with an average diameter of about 500 nm. Figure 3 Pt and MnO x TEM image of the nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, which exhibits regular octahedral morphology, with an average diameter of about 500 nm. Figure 4 Pt and MnO x HRTEM image of the nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, with MnO x and Pt loaded x The presence of MnO x nanoparticles (d = 0.193 nm) and Pt nanoparticles (d = 0.223 nm) with a size of about 5 nm indicates the successful preparation of the Pt@NM-101 / MnO x -2 composite catalyst.

[0055] Figure 5 NH2-MIL-101(Fe), NM-101 / MnO x , Pt@NM-101 and Pt and MnO x UV-Vis absorption spectrum of the nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, with Pt and MnO x nanoparticles in-situ loaded, the light absorption range of the composite photocatalyst Pt@NM-101 / MnO x -3 is further improved.

[0056] Figure 6 NH2-MIL-101(Fe), NM-101 / MnO x , Pt@NM-101 and Pt and MnO x Transient photocurrent response diagram of the nanoparticle in-situ loaded NH2-MIL-101(Fe) photocatalyst, which indicates that Pt@NM-101 / MnO x -3 has a stronger photocurrent density, indicating that Pt@NM-101 / MnO x -3 has a stronger charge transfer rate.

[0057] Figure 7 NH2-MIL-101(Fe), NM-101 / MnO xPt@NM-101 and Pt and MnO prepared in Example 2 x Impedance plots of NH2-MIL-101(Fe) photocatalyst in situ loaded with nanoparticles show that Pt@NM-101 / MnO x -3 has a lower interfacial charge transfer resistance, indicating that Pt@NM-101 / MnO x -3 has a stronger charge transfer rate.

[0058] NH2-MIL-101(Fe), NM-101 / MnO x , Pt@NM-101 and Pt and MnO prepared in Example 2 x NH2-MIL-101(Fe) photocatalyst 30 mg in situ loaded with nanoparticles, six experiments were set up, and six samples were respectively dispersed in a quartz photocatalytic reactor containing 100 mL of deionized water and connected with a circulating water cooling system to maintain a controlled temperature of 25 ℃. The light source was a 300 W xenon lamp (282 mW·cm -2 ). First, the dispersion was bubbled with high-purity N2(80 mL·min -1 ) in the dark and magnetically stirred for 30 min, so that N2 in the solution was saturated and reached the purpose of driving out oxygen in the reactor. Subsequently, the xenon lamp light source was turned on, and 1 mL of dispersion was taken out every 60 min, and the photocatalyst was separated by centrifugation at 5000 rpm to obtain the supernatant. The concentration of NH3 in the supernatant was determined by the Nash reagent spectrophotometry, and the curve shown in Figure 8 was obtained; from Figure 8 it can be seen that the samples of Examples 1-5 have significantly improved efficiency for photocatalytic conversion of nitrogen to ammonia compared with unmodified NH2-MIL-101(Fe), and the production of NH4 + is significantly improved, and Example 5 is the best, with an activity increase of 4.2 times.

[0059] Using NH2-MIL-101(Fe) as a carrier, this material has excellent light absorption and photosensitive properties, can effectively absorb solar energy, and convert it into photo-generated carriers. In addition, Pt and MnO x nanoparticles are in situ loaded on the NH2-MIL-101(Fe) matrix, which not only effectively improves the separation efficiency of photo-generated electrons and holes but also realizes the synergistic promotion of oxidation and reduction half-reactions, thereby improving the photocatalytic nitrogen fixation activity. The synergistic effect of NH2-MIL-101(Fe) composite photocatalyst containing Pt and MnO x nanoparticles is used to improve the production of photocatalytic conversion of nitrogen to ammonia, which significantly solves the problems of high energy consumption and environmental pollution in traditional industrial nitrogen fixation. The preparation process of this method is simple, low in cost, and raw materials are easy to obtain.

[0060] The above merely illustrates the technical idea of the present application, and cannot limit the protection scope of the present application. Any modification made according to the technical idea of the present application, on the basis of the technical scheme, falls within the protection scope of the present application.

Claims

1. A Pt and MnO x The application of nanoparticle in-situ loaded NH2-MIL-101 (Fe) photocatalyst in photocatalytic conversion of nitrogen to synthesize ammonia is characterized by: The preparation method of the photocatalyst comprises the following steps: 2-aminoterephthalic acid, FeCl3·6H2O and a solvent were stirred and mixed, and then subjected to a hydrothermal reaction to obtain NH2-MIL-101(Fe) catalyst; After mixing NH2-MIL-101(Fe) catalyst, MnSO4 and water, the reaction was carried out under light conditions and constant temperature conditions. After the reaction, NM-101 / MnO x ; NM-101 / MnO x and water, followed by adding H2PtCl6·6H2O aqueous solution, and then adding reducing agent and stabilizer dropwise to obtain Pt and MnO x Nanoparticles were in situ loaded with NH2-MIL-101(Fe) photocatalyst.

2. The use according to claim 1, characterized in that In the step of obtaining NH2-MIL-101(Fe), the usage ratio of the 2-aminoterephthalic acid, FeCl3·6H2O, and solvent is (0.206 g to 0.210 g): (0.675 g to 0.680 g): (25 mL to 26 mL); the solvent is DMF.

3. The use according to claim 1, characterized in that In the step of obtaining NH2-MIL-101(Fe), the hydrothermal reaction temperature is 110°C and the time is 24 hours.

4. The use according to claim 1, characterized in that Obtain NM-101 / MnO x In the step, the usage ratio of the NH2-MIL-101(Fe) catalyst, MnSO4 and water is (0.1 g ~ 0.105 g): (0.3 g ~ 0.31 g): (50 mL ~ 52 mL).

5. The use according to claim 1, characterized in that The illumination condition is to use a 300W xenon lamp with a 420 nm filter for 1 hour; the constant temperature condition is 25°C.

6. The use according to claim 1, wherein After mixing NH2-MIL-101(Fe) catalyst, MnSO4 and water, the reaction was carried out under light conditions and constant temperature conditions. After the reaction, the reaction product was dried in a freeze dryer for 6 to 6.2 h to obtain NM-101 / MnO x .

7. The use according to claim 1, characterized in that Obtain Pt and MnO x In the step of in-situ loading of NH2-MIL-101(Fe) photocatalyst on nanoparticles, the NM-101 / MnO x The dosage ratio of water, reducing agent and stabilizer is (0.1 g~0.105 g): (20 mL~22 mL): (700 uL ~705 uL): (5 mg~ 7 mg).

8. The use according to claim 1, characterized in that The reducing agent is 0.1 mol L -1 The stabilizer is citric acid.

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